Synthesis, characterization and tribological evaluation of novel 1,4-diazabicyclo[2.2.2]octane based dicationic ionic liquids as efficient antiwear lubricant additives

  • LiNa Zhao
  • Tao CaiEmail author
  • YunXiao Zhang
  • MengTing Ye
  • WangJi Shang
  • Dan Liu
  • DingYi Tong
  • ShengGao LiuEmail author


Ionic liquids have developed and been applied in lubricant field since 2001. Nevertheless, it is little known about novel dicationic ionic liquids for tribology applications in the past several years. In this paper, a sequence of novel dicationic ionic liquids based on 1,4-diazabicyclo[2.2.2]octane cations (DABCO) and different anions have been designed and identified. The structures of ILs were confirmed by Fourier transform infrared (FTIR) spectra, multinuclear (1H, 13C, 11B, 31P and 19F) magnetic resonance and mass spectrometry. The effects of anion type on thermal properties, wettability, kinematic viscosity and tribological properties were studied. It is found that all of these dicationic ionic liquids as additives exhibit excellent anti-wear and friction-reducing properties in PEG synthetic base oil under boundary lubrication conditions for steel-to-steel contact, which offers great potential for the highly efficient lubricant additives. Simultaneously, novel 1,4-diazabicyclo[2.2.2]octane cation offers an exceptional chance for the research and development of dicationic ionic liquids in various applications.


dicationic ionic liquids lubricant additives tribological performance 


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  1. 1.
    Zhou Y, Qu J. Ionic liquids as lubricant additives: A review. ACS Appl Mater Interfaces, 2017, 9: 3209–3222CrossRefGoogle Scholar
  2. 2.
    Amiril S A S, Rahim E A, Syahrullail S. A review on ionic liquids as sustainable lubricants in manufacturing and engineering: Recent research, performance, and applications. J Cleaner Production, 2017, 168: 1571–1589CrossRefGoogle Scholar
  3. 3.
    Oster K, Jacquemin J, Hardacre C, et al. Further development of the predictive models for physical properties of pure ionic liquids: Thermal conductivity and heat capacity. J Chem ThermoDyn, 2018, 118: 1–15CrossRefGoogle Scholar
  4. 4.
    Zhang D, Qu Y, Gong Y Y, et al. Physicochemical properties of [cnmim][thr] (n=3, 5, 6) amino acid ionic liquids. J Chem ThermoDyn, 2017, 115: 47–51CrossRefGoogle Scholar
  5. 5.
    De Leo F, Cardiano P, De Carlo G, et al. Testing the antimicrobial properties of an upcoming “environmental-friendly” family of ionic liquids. J Mol Liquids, 2017, 248: 81–85CrossRefGoogle Scholar
  6. 6.
    Iwasaki K, Yoshii K, Tsuda T, et al. Physicochemical properties of phenyltrifluoroborate-based room temperature ionic liquids. J Mol Liquids, 2017, 246: 236–243CrossRefGoogle Scholar
  7. 7.
    Pillai P, Pal N, Mandal A. Synthesis, characterization, surface properties and micellization behaviour of imidazolium-based ionic liquids. J Surfact Deterg, 2017, 20: 1321–1335CrossRefGoogle Scholar
  8. 8.
    Qiao K, Hagiwara H, Yokoyama C. Acidic ionic liquid modified silica gel as novel solid catalysts for esterification and nitration reactions. J Mol Catal A-Chem, 2006, 246: 65–69CrossRefGoogle Scholar
  9. 9.
    Simonetti E, Carewska M, Di Carli M, et al. Towards improvement of the electrochemical properties of ionic liquid-containing polyethylene oxide-based electrolytes. Electrochim Acta, 2017, 235: 323–331CrossRefGoogle Scholar
  10. 10.
    Drvarič Talian S, Bešter-Rogač M, Dominko R. The physicochemical properties of a [DEME][TFSI] ionic liquid-based electrolyte and their influence on the performance of lithium-sulfur batteries. Electrochim Acta, 2017, 252: 147–153CrossRefGoogle Scholar
  11. 11.
    Tarkhanova I G, Anisimov A V, Buryak A K, et al. Immobilized ionic liquids based on molybdenum- and tungsten-containing heteropoly acids: Structure and catalytic properties in thiophene oxidation. Pet Chem, 2017, 57: 859–867CrossRefGoogle Scholar
  12. 12.
    Al Kaisy G M J, Mutalib M I A, Leveque J M, et al. Novel low viscosity ammonium-based ionic liquids with carboxylate anions: Synthesis, characterization, and thermophysical properties. J Mol Liquids, 2017, 230: 565–573CrossRefGoogle Scholar
  13. 13.
    Pejaković V, Kronberger M, Kalin M. Influence of temperature on tribological behaviour of ionic liquids as lubricants and lubricant additives. Lubr Sci, 2014, 26: 107–115CrossRefGoogle Scholar
  14. 14.
    Minami I. Ionic liquids in tribology. Molecules, 2009, 14: 2286–2305CrossRefGoogle Scholar
  15. 15.
    Zhu L, Zhao Q, Wu X, et al. A novel phosphate ionic liquid plays dual role in synthetic ester oil: From synthetic catalyst to anti-wear additive. Tribol Int, 2016, 97: 192–199CrossRefGoogle Scholar
  16. 16.
    Shah F U, Glavatskih S, MacFarlane D R, et al. Novel halogen-free chelated orthoborate–phosphonium ionic liquids: Synthesis and tribophysical properties. Phys Chem Chem Phys, 2011, 13: 12865–12873CrossRefGoogle Scholar
  17. 17.
    Xiao H, Guo D, Liu S, et al. Film thickness of ionic liquids under high contact pressures as a function of alkyl chain length. Tribol Lett, 2010, 41: 471–477CrossRefGoogle Scholar
  18. 18.
    Kawada S, Sato K, Watanabe S, et al. Lubricating property of cyanobased ionic liquids against hard materials. J Mech Sci Technol, 2017, 31: 5745–5750CrossRefGoogle Scholar
  19. 19.
    Viesca J L, Mallada M T, Blanco D, et al. Lubrication performance of an ammonium cation-based ionic liquid used as an additive in a polar oil. Tribol Int, 2017, 116: 422–430CrossRefGoogle Scholar
  20. 20.
    Dong R, Wen P, Zhang S, et al. The synthesis and tribological properties of dicarboxylic acid ionic liquids. Tribol Int, 2017, 114: 132–140CrossRefGoogle Scholar
  21. 21.
    Blanco D, González R, Viesca J L, et al. Antifriction and antiwear properties of an ionic liquid with fluorine-containing anion used as lubricant additive. Tribol Lett, 2017, 65: 66CrossRefGoogle Scholar
  22. 22.
    Wu J, Lu X, Feng X, et al. Halogen-free ionic liquids as excellent lubricants for PEEK-stainless steel contacts at elevated temperatures. Tribol Int, 2016, 104: 1–9CrossRefGoogle Scholar
  23. 23.
    Hernández Battez A, Blanco D, Fernández-González A, et al. Friction, wear and tribofilm formation with a [NTf 2] anion-based ionic liquid as neat lubricant. Tribol Int, 2016, 103: 73–86CrossRefGoogle Scholar
  24. 24.
    Cooper P K, Li H, Rutland M W, et al. Tribotronic control of friction in oil-based lubricants with ionic liquid additives. Phys Chem Chem Phys, 2016, 18: 23657–23662CrossRefGoogle Scholar
  25. 25.
    Barnhill W C, Luo H, Meyer H M, et al. Tertiary and quaternary ammonium-phosphate ionic liquids as lubricant additives. Tribol Lett, 2016, 63: 22CrossRefGoogle Scholar
  26. 26.
    Ye C, Liu W, Chen Y, et al. Room-temperature ionic liquids: A novel versatile lubricant. Chem Commun, 2001, 21: 2244–2245CrossRefGoogle Scholar
  27. 27.
    Xu W, Wang L M, Nieman R A, et al. Ionic liquids of chelated orthoborates as model ionic glassformers. J Phys Chem B, 2003, 107: 11749–11756CrossRefGoogle Scholar
  28. 28.
    Moosavi M, Khashei F, Sedghamiz E. Molecular dynamics simulation of geminal dicationic ionic liquids [Cn (mim)2 ][NTf2 ]2-structural and dynamical properties. Phys Chem Chem Phys, 2017, 20: 435–448CrossRefGoogle Scholar
  29. 29.
    Anderson J L, Ding R, Ellern A, et al. Structure and properties of high stability geminal dicationic ionic liquids. J Am Chem Soc, 2005, 127: 593–604CrossRefGoogle Scholar
  30. 30.
    Mahrova M, Pagano F, Pejakovic V, et al. Pyridinium based dicationic ionic liquids as base lubricants or lubricant additives. Tribol Int, 2015, 82: 245–254CrossRefGoogle Scholar
  31. 31.
    Gusain R, Gupta P, Saran S, et al. Halogen-free bis(imidazolium)/bis (ammonium)-di[bis(salicylato)borate] ionic liquids as energy-efficient and environmentally friendly lubricant additives. ACS Appl Mater Interfaces, 2014, 6: 15318–15328CrossRefGoogle Scholar
  32. 32.
    Gusain R, Bakshi P S, Panda S, et al. Physicochemical and tribophysical properties of trioctylalkylammonium bis(salicylato)borate (N888n-BScB) ionic liquids: Effect of alkyl chain length. Phys Chem Chem Phys, 2017, 19: 6433–6442CrossRefGoogle Scholar
  33. 33.
    Lohar T, Kumbhar A, Barge M, et al. DABCO functionalized dicationic ionic liquid (DDIL): A novel green benchmark in multicomponent synthesis of heterocyclic scaffolds under sustainable reaction conditions. J Mol Liquids, 2016, 224: 1102–1108CrossRefGoogle Scholar
  34. 34.
    Zhiltsova E P, Lukashenko S S, Pashirova T N, et al. Supramolecular catalytic systems based on 1, 4-diazabicyclo[2.2.2]octane, its alkylated quaternary derivatives, and lanthanum nitrate. Russ Chem Bull, 2015, 64: 2690–2696CrossRefGoogle Scholar
  35. 35.
    Zhan S P, Duan H T, Hua M, et al. Studies of antioxidant performance of amine additives in lubricating oil using 3D-QSAR. Sci China Technol Sci, 2017, 60: 299–305CrossRefGoogle Scholar
  36. 36.
    Li Y, Zhang S, Ding Q, et al. The corrosion and lubrication properties of 2-Mercaptobenzothiazole functionalized ionic liquids for bronze. Tribol Int, 2017, 114: 121–131CrossRefGoogle Scholar
  37. 37.
    Amorim P M, Ferraria A M, Colaço R, et al. Imidazolium-based ionic liquids used as additives in the nanolubrication of silicon surfaces. Beilstein J Nanotechnol, 2017, 8: 1961–1971CrossRefGoogle Scholar
  38. 38.
    Tang X W, Zhang C H, Wang Y, et al. Analysis of surface and subsurface of cold-rolled Al plate lubricated with water- or oil-based lubricants. Sci China Technol Sci, 2017, 60: 1407–1414CrossRefGoogle Scholar
  39. 39.
    Sun Y F, Chai Z M, Lu X C, et al. A direct atomic layer deposition method for growth of ultra-thin lubricant tungsten disulfide films. Sci China Technol Sci, 2017, 60: 51–57CrossRefGoogle Scholar
  40. 40.
    Beattie D A, Harmer-Bassell S L, Ho T T M, et al. Spectroscopic study of ionic liquid adsorption from solution onto gold. Phys Chem Chem Phys, 2015, 17: 4199–4209CrossRefGoogle Scholar
  41. 41.
    Wu X, Liu J, Zhao Q, et al. In situ formed ionic liquids in polyol esters as high performance lubricants for steel/steel contacts at 300°C. ACS Sustain Chem Eng, 2015, 3: 2281–2290CrossRefGoogle Scholar
  42. 42.
    Ali G, Rahman G, Chung K Y. Cobalt-doped pyrochlore-structured iron fluoride as a highly stable cathode material for lithium-ion batteries. Electrochim Acta, 2017, 238: 49–55CrossRefGoogle Scholar
  43. 43.
    Yan J, Zeng X, van der Heide E, et al. The tribological performance and tribochemical analysis of novel borate esters as lubricant additives in rapeseed oil. Tribol Int, 2014, 71: 149–157CrossRefGoogle Scholar
  44. 44.
    Zhang Y, Cai T, Shang W, et al. Environmental friendly polyisobutylene-based ionic liquid containing chelated orthoborate as lubricant additive: Synthesis, tribological properties and synergistic interactions with ZDDP in hydrocarbon oils. Tribol Int, 2017, 115: 297–306CrossRefGoogle Scholar
  45. 45.
    Zhu L, Zhao G, Wang X. Investigation on three oil-miscible ionic liquids as antiwear additives for polyol esters at elevated temperature. Tribol Int, 2017, 109: 336–345CrossRefGoogle Scholar
  46. 46.
    Qian X, Ren M, Zhu Y, et al. Visible light assisted heterogeneous fenton-like degradation of organic pollutant via α-FeOOH/mesoporous carbon composites. Environ Sci Technol, 2017, 51: 3993–4000CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • LiNa Zhao
    • 1
    • 2
  • Tao Cai
    • 1
    Email author
  • YunXiao Zhang
    • 1
    • 3
  • MengTing Ye
    • 1
    • 2
  • WangJi Shang
    • 1
    • 3
  • Dan Liu
    • 1
  • DingYi Tong
    • 1
  • ShengGao Liu
    • 1
    Email author
  1. 1.Ningbo Institute of Materials Technology and EngineeringChinese Academy of SciencesNingboChina
  2. 2.University of Chinese Academy of SciencesBeijingChina
  3. 3.School of Materials Science and EngineeringShanghai UniversityShanghaiChina

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