Tribology Letters

, 67:42 | Cite as

Antiwear Properties of Binary Ashless Blend of Phosphonium Ionic Liquids and Borate Esters in Partially Formulated Oil (No Zn)

  • Vibhu Sharma
  • Nicole Dörr
  • Ali Erdemir
  • Pranesh B. AswathEmail author
Original Paper


In this study, interaction of ionic liquid (IL) and borate esters (SBs) as antiwear (AW) additives with steel surfaces in tribological contacts was examined using blends which contained no prior AW additives but all the other ingredients present in a fully formulated engine oil. In detail, low phosphorus oil blends were prepared by adding trihexyltetradecylphosphonium bis(2-ethylhexyl)phosphate (P_DEHP) at 700 ppm phosphorus and 2-methoxy-4,4,6-trimethyl-1,3,2-dioxaborinane or trimethoxyboroxine at 200 ppm boron treat rate to a partially formulated oil. The tribological properties of these novel ionic liquid (IL) additive and IL + SB additive mixtures were compared with those of zinc dialkyldithiophosphate (ZDDP) at equal phosphorus levels in the oil blends. Tribological experiments with a reciprocating cylinder on flat contact revealed that both P_DEHP and binary mixtures of P_DEHP + SB offer superior wear protection than ZDDP and the partially formulated oil without AW additives, expressed by a wear reduction of minimum 50%. X-ray absorption near edge structure spectroscopy (XANES) analysis revealed that tribologically formed films are primarily composed of calcium phosphate for oils with AW additives. The interaction of P_DEHP with SB results in additional boron oxide/boric acid and to some extent boron phosphate domains incorporated into the tribofilms.


Ionic liquids Wear Borate esters XANES Fully formulated oils 



XANES experiments were conducted at the Canadian Light Source, Saskatoon, Saskatchewan, Canada that is supported by NSERC, NRC, CIHR and the University of Saskatchewan. Tribological tests were performed at Argonne National Laboratory and were supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Office of Vehicle Technology under contract DE-AC02-06CH11357. Scanning probe microscopy experiments were conducted at Center for Characterization for Materials and Biology at The University of Texas at Arlington. This work was also supported by the “Austrian COMET-Program” in the frame of K2 XTribology (Project No. 849109).


  1. 1.
    Sharma, V., Doerr, N., Aswath, P.: Chemical-mechanical properties of tribofilms and its relation to ionic liquid chemistry. RSC Adv. 6, 22341–22356 (2016)CrossRefGoogle Scholar
  2. 2.
    Somers, A.E., Khemchandani, B., Howlett, P.C., Sun, J., MacFarlane, D.R., Forsyth, M.: Ionic liquids as antiwear additives in base oils: influence of structure on miscibility and antiwear performance for steel on aluminum. ACS Appl. Mater. Interfaces 5, 11544–11553 (2013)CrossRefGoogle Scholar
  3. 3.
    Anand, M., Hadfield, M., Viesca, J., Thomas, B., Battez, A.H., Austen, S.: Ionic liquids as tribological performance improving additive for in-service and used fully-formulated diesel engine lubricants. Wear 334, 67–74 (2015)CrossRefGoogle Scholar
  4. 4.
    Barnhill, W.C., Qu, J., Luo, H., Meyer, H.M., Ma, C., Chi, M., et al.: Phosphonium-organophosphate ionic liquids as lubricant additives: effects of cation structure on physicochemical and tribological characteristics. ACS Appl. Mater. Interfaces 6, 22585–22593 (2014)CrossRefGoogle Scholar
  5. 5.
    Pisarova, L., Gabler, C., Dörr, N., Pittenauer, E., Allmaier, G.: Thermo-oxidative stability and corrosion properties of ammonium based ionic liquids. Tribol. Int. 46, 73–83 (2012)CrossRefGoogle Scholar
  6. 6.
    Cai, M., Liang, Y., Yao, M., Xia, Y., Zhou, F., Liu, W.: Imidazolium ionic liquids as antiwear and antioxidant additive in poly (ethylene glycol) for steel/steel contacts. ACS Appl. Mater. Interfaces 2, 870–876 (2010)CrossRefGoogle Scholar
  7. 7.
    Minami, I.: Ionic liquids in tribology. Molecules 14, 2286–2305 (2009)CrossRefGoogle Scholar
  8. 8.
    Yu, B., Bansal, D.G., Qu, J., Sun, X., Luo, H., Dai, S., et al.: Oil-miscible and non-corrosive phosphonium-based ionic liquids as candidate lubricant additives. Wear. 289, 58–64 (2012)CrossRefGoogle Scholar
  9. 9.
    Gusain, R., Gupta, P., Saran, S., Khatri, O.P.: Halogen-free bis (imidazolium)/bis (ammonium)-di [bis (salicylato) borate] ionic liquids as energy efficient and environment-friendly lubricant additives. ACS Appl. Mater. Interfaces 6(17), 15318–15328 (2014)CrossRefGoogle Scholar
  10. 10.
    Qu, J., Luo, H., Chi, M., Ma, C., Blau, P.J., Dai, S., et al.: Comparison of an oil-miscible ionic liquid and ZDDP as a lubricant anti-wear additive. Tribol. Int. 71, 88–97 (2014)CrossRefGoogle Scholar
  11. 11.
    Totolin, V., Minami, I., Gabler, C., Brenner, J., Dörr, N.: Lubrication mechanism of phosphonium phosphate ionic liquid additive in alkylborane–imidazole complexes. Tribol. Lett. 53, 421–432 (2014)CrossRefGoogle Scholar
  12. 12.
    Qu, J., Blau, P.J., Dai, S., Luo, H., Meyer, H.M.: Ionic liquids as novel lubricants and additives for diesel engine applications. Tribol. Lett. 35, 181–189 (2009)CrossRefGoogle Scholar
  13. 13.
    Jiménez, A.E., Bermúdez, M.: Ionic liquids as lubricants of titanium–steel contact. Tribol. Lett. 33, 111–126 (2009)CrossRefGoogle Scholar
  14. 14.
    Jimenez, A., Bermudez, M.: Ionic liquids as lubricants of titanium–steel contact. Part 2: friction, wear and surface interactions at high temperature. Tribol. Lett. 37, 431–443 (2010)CrossRefGoogle Scholar
  15. 15.
    Kronberger, M., Pejaković, V., Gabler, C., Kalin, M.: (2012) How anion and cation species influence the tribology of a green lubricant based on ionic liquids. Proc. Inst. Mech. Eng. Part J. 226, 933–951CrossRefGoogle Scholar
  16. 16.
    Bermúdez, M., Jiménez, A., Sanes, J., Carrión, F.: Ionic liquids as advanced lubricant fluids. Molecules 14, 2888–2908 (2009)CrossRefGoogle Scholar
  17. 17.
    Sharma, V., Gabler, C., Doerr, N., Aswath, P.B.: Mechanism of tribofilm formation with P and S containing ionic liquids. Tribol. Int. 92, 353–364 (2015)CrossRefGoogle Scholar
  18. 18.
    González, R., Bartolomé, M., Blanco, D., Viesca, J., Fernández-González, A., Battez, A.H.: Effectiveness of phosphonium cation-based ionic liquids as lubricant additive. Tribol. Int. 98, 82–93 (2016)CrossRefGoogle Scholar
  19. 19.
    Sharma, V., Doerr, N., Erdemir, A., Aswath, P.: Interaction of phosphonium ionic liquids with borate esters at tribological interfaces. RSC Adv. 6, 53148–53161 (2016)CrossRefGoogle Scholar
  20. 20.
    Qu, J., Bansal, D.G., Yu, B., Howe, J.Y., Luo, H., Dai, S., et al.: Antiwear performance and mechanism of an oil-miscible ionic liquid as a lubricant additive. ACS Appl. Mater. Interfaces 4, 997–1002 (2012)CrossRefGoogle Scholar
  21. 21.
    Grocholski, B.: Additive explanation for anti-wear. Science. 348, 87–88 (2015)Google Scholar
  22. 22.
    Qu, J., Barnhill, W.C., Luo, H., Meyer, H.M., Leonard, D.N., Landauer, A.K., et al.: Synergistic effects between phosphonium-alkylphosphate ionic liquids and zinc dialkyldithiophosphate (ZDDP) as lubricant additives. Adv. Mater. 27, 4767–4774 (2015)CrossRefGoogle Scholar
  23. 23.
    Kasrai, M., Lennard, W.N., Brunner, R.W., Bancroft, G.M., Bardwell, J.A., Tan, K.H.: Sampling depth of total electron and fluorescence measurements in Si L- and K-edge absorption spectroscopy. Appl. Surf. Sci. 99, 303–312 (1996)CrossRefGoogle Scholar
  24. 24.
    Parekh, K., Chen, X., Aswath, P.B.: Synthesis of fluorinated ZDDP compounds. Tribol. Lett. 34, 141–153 (2009)CrossRefGoogle Scholar
  25. 25.
    Sharma, V., Erdemir, A., Aswath, P.B.: An analytical study of tribofilms generated by the interaction of ashless antiwear additives with ZDDP using XANES and nano-indentation. Tribol. Int. 82, 43–57 (2015)CrossRefGoogle Scholar
  26. 26.
    Sharma, V., Uy, D., Gangopadhyay, A., O’Neill, A., Paxton, W.A., Sammut, A., et al.: Structure and chemistry of crankcase and exhaust soot extracted from diesel engines. Carbon. 103, 327–338 (2016)CrossRefGoogle Scholar
  27. 27.
    Chen, X., Elsenbaumer, R.L., Aswath, P.B.: Synthesis and tribological behavior of ashless alkylphosphorofluoridothioates. Tribol. Int. 69, 114–124 (2013)CrossRefGoogle Scholar
  28. 28.
    Chen, X., Kim, B., Elsenbaumer, R., Aswath, P.B.: Synthesis and antiwear behavior of alkylthioperoxydiphosphates. Tribology 6(3), 121–133 (2012)Google Scholar
  29. 29.
    Nicholls, M., Najman, M.N., Zhang, Z., Kasrai, M., Norton, P.R., Gilbert, P.U.P.A.: The contribution of XANES spectroscopy to tribology. Can. J. Chem. 85, 816–830 (2007)CrossRefGoogle Scholar
  30. 30.
    Kim, B., Mourhatch, R., Aswath, P.B.: Properties of tribofilms formed with ashless dithiophosphate and zinc dialkyl dithiophosphate under extreme pressure conditions. Wear. 268, 579–591 (2010)CrossRefGoogle Scholar
  31. 31.
    Li, Y., Pereira, G., Lachenwitzer, A., Kasrai, M., Norton, P.R.: X-ray absorption spectroscopy and morphology study on antiwear films derived from ZDDP under different sliding frequencies. Tribol. Lett. 27, 245–253 (2007)CrossRefGoogle Scholar
  32. 32.
    Li, Y., Pereira, G., Kasrai, M., Norton, P.R.: Studies on ZDDP anti-wear films formed under different conditions by XANES spectroscopy, atomic force microscopy and 31P NMR. Tribol. Lett. 28, 319–328 (2007)CrossRefGoogle Scholar
  33. 33.
    Nicholls, M.A., Do, T., Bancroft, G.M., Norton, P.R., Kasrai, M., Capehart, T.W., et al.: Chemical and mechanical properties of ZDDP antiwear films on steel and thermal spray coatings studied by XANES spectroscopy and nanoindentation techniques. Tribol. Lett. 15(3), 241–248 (2003)CrossRefGoogle Scholar
  34. 34.
    Najman, M.N., Kasrai, M., Bancroft, G.M., Frazer, B.H., DeStatio, G.: The correlation of microchemical properties to antiwear (AW) performance in ashless thiophosphate oil additives. Tribol. Lett. 17(4), 811–822 (2004)CrossRefGoogle Scholar
  35. 35.
    Najman, M.N., Kasrai, M., Bancroft, G.M.: Chemistry of anti-wear films from ashless thiophosphate oil additives. Tribol. Lett. 17(2), 217–229 (2004)CrossRefGoogle Scholar
  36. 36.
    Najman, M., Kasrai, M., Michael Bancroft, G., Davidson, R.: Combination of ashless antiwear additives with metallic detergents: Interactions with neutral and overbased calcium sulfonates. Tribol. Int. 39, 342–355 (2006)CrossRefGoogle Scholar
  37. 37.
    Pereira, G., Munoz-Paniagua, D., Lachenwitzer, A., Kasrai, M., Norton, P.R., Capehart, T.W., et al.: A variable temperature mechanical analysis of ZDDP-derived antiwear films formed on 52100 steel. Wear 262, 461–470 (2007)CrossRefGoogle Scholar
  38. 38.
    Warren, O.L., Graham, J.F., Norton, P.R., Houston, J.E., Michalske, T.A.: Nanomechanical properties of films derived from zinc dialkyldithiophosphate. Tribol. Lett. 4, 189–198 (1998)CrossRefGoogle Scholar
  39. 39.
    Aswath, P., Chen, X., Sharma, V., Igartua, M.A., Pagano, F., Binder, W., et al.: (2013) Synergistic mixtures of ionic liquids with other ionic liquids and/or with ashless thiophosphates for antiwear and/or friction reduction applications. U.S. Patent Application No. 13/889,037Google Scholar
  40. 40.
    Willermet, P.A., Dailey, D.P., Carter, R.O., Schmitz, P.J., Zhu, W., Bell, J.C., et al.: The composition of lubricant-derived surface layers formed in a lubricated cam/tappet contact, II. Effects of adding overbased detergent and dispersant to a simple ZDTP solution. Tribol. Int. 28(3), 163–175 (1995)CrossRefGoogle Scholar
  41. 41.
    Wan, Y., Suominen Fuller, M.L., Kasrai, M., Bancroft, G.M., Fyfe, K., Torkelson, J.R., et al.: Effects of detergent on the chemistry of tribofilms from ZDDP: studied by X-ray absorption spectroscopy and XPS. In: Dowson, D., Priest, M., Dalmaz, G., Lubrecht, A.A. (eds.) Tribology Series, vol. 40, pp. 155–166. Elsevier, Amsterdam (2002)Google Scholar
  42. 42.
    Kasrai, M., Fuller, M.S., Bancroft, G.M., Ryason, P.R.: X-ray absorption study of the effect of calcium sulfonate on antiwear film formation generated from neutral and basic ZDDPs: part 1—phosphorus species. Tribol. Trans. 46, 534–542 (2003)CrossRefGoogle Scholar
  43. 43.
    Yin, Z., Kasrai, M., Bancroft, G.M., Tan, K.H., Feng, X.: X-ray-absorption spectroscopic studies of sodium polyphosphate glasses. Phys. Rev. B 51, 742–750 (1995)CrossRefGoogle Scholar
  44. 44.
    Kasrai, M., Fleet, M.E., Muthupari, S., Li, D., Bancroft, G.: Surface modification study of borate materials from B K-edge X-ray absorption spectroscopy. Phys. Chem. Miner. 25, 268–272 (1998)CrossRefGoogle Scholar
  45. 45.
    Zhang, Z., Yamaguchi, E.S., Kasrai, M., Bancroft, G.M.: Interaction of ZDDP with borated dispersant using XANES and XPS. Tribol. Trans. 47, 527–536 (2004)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Vibhu Sharma
    • 1
  • Nicole Dörr
    • 2
  • Ali Erdemir
    • 3
  • Pranesh B. Aswath
    • 1
    Email author
  1. 1.Materials Science and Engineering DepartmentUniversity of Texas at ArlingtonArlingtonUSA
  2. 2.AC2T research GmbHWiener NeustadtAustria
  3. 3.Argonne National LaboratoryArgonneUSA

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