Tribology Letters

, 66:2 | Cite as

Direct Formation of Lubricious and Wear-Protective Carbon Films from Phosphorus- and Sulfur-Free Oil-Soluble Additives

  • Blake Johnson
  • Hongxing Wu
  • Michael Desanker
  • David Pickens
  • Yip-Wah Chung
  • Q. Jane Wang
Original Paper


Extreme pressure (EP) lubricant additives form protective tribofilms at the site of contact using the heat and pressure of contact and relative motion. Common EP additives contain undesirable elements such as phosphorus and sulfur. A novel EP lubricant additive, which contains no phosphorus and sulfur, is presented for generating lubricious carbon films. The additive consists of a surface-active molecule with a metastable cycloalkane ring, which dissociates readily during tribological contact to form lubricious carbon films. Friction and wear performance of PAO4 with this additive under a range of loads and speeds were shown to be superior to that without the additive. Optical and scanning electron microscopy and Raman spectroscopy were used to analyze the tribofilms formed on post-test contact surfaces, providing direct evidence for the formation of carbon films. Quantitative kinetics for the carbon tribofilm formation was analyzed as a function of temperature and stress, from which the activation energy for carbon tribofilm formation was obtained.


Extreme pressure additives Antiwear additives Additive deposition 



The authors would like to thank the support from the US National Science Foundation (Grant No. CMMI-1662606) and Northwestern University (the McCormick Research Catalyst Awards Fund Grant No. 10038293). This work made use of the Keck-II Facility of Northwestern University’s NUANCE Center, which has received support from the Keck Foundation, the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the Materials Research Center (NSF DMR-1121262), the McCormick Research Catalyst Awards Fund, Grant No. 10038293, and the International Institute for Nanotechnology (IIN) at Northwestern University. Hongxing Wu would also like to acknowledge the scholarship support from China Scholarship Council (CSC, No. 201606280181).


  1. 1.
    Holmberg, K., Erdemir, A.: Influence of tribology on global energy consumption, costs and emissions. Friction 5(3), 263–284 (2017). CrossRefGoogle Scholar
  2. 2.
    Nosonovsky, M., Bhushan, B.: SpringerLink (Online service): Green Tribology: Biomimetics, Energy Conservation and Sustainability. Green Energy and Technology. Springer, Berlin (2012)Google Scholar
  3. 3.
    Holmberg, K., Andersson, P., Nylund, N.-O., Mäkelä, K., Erdemir, A.: Global energy consumption due to friction in trucks and buses. Tribol. Int. 78, 94–114 (2014). CrossRefGoogle Scholar
  4. 4.
    Holmberg, K., Siilasto, R., Laitinen, T., Andersson, P., Jäsberg, A.: Global energy consumption due to friction in paper machines. Tribol. Int. 62, 58–77 (2013). CrossRefGoogle Scholar
  5. 5.
    Russell, L.S.D.J.A.: A review of DOE ECUT tribology. J. Tribol. 108(4), 497–501 (1986)CrossRefGoogle Scholar
  6. 6.
    Holmberg, K., Andersson, P., Erdemir, A.: Global energy consumption due to friction in passenger cars. Tribol. Int. 47, 221–234 (2012). CrossRefGoogle Scholar
  7. 7.
    Marr, L.C., Kirchstetter, T.W., Harley, R.A., Miguel, A.H., Hering, S.V., Hammond, S.K.: Characterization of polycyclic aromatic hydrocarbons in motor vehicle fuels and exhaust emissions. Environ. Sci. Technol. 33(18), 3091–3099 (1999)CrossRefGoogle Scholar
  8. 8.
    Jost, H.P.: Tribology—origin and future. Wear 136(1), 1–17 (1990)CrossRefGoogle Scholar
  9. 9.
    Jost, H.P., Schofield, J.: Energy saving through tribology: a techno-economic study. Proc. Inst. Mech. Eng. 195(1), 151–173 (1981)CrossRefGoogle Scholar
  10. 10.
    Bishop, J., Nedungadi, A., Ostrowski, G., Surampudi, B., Armiroli, P., Taspinar, E.: An engine start/stop system for improved fuel economy. In: SAE Technical Paper, (2007)Google Scholar
  11. 11.
    Tanaka, K., Korematsu, K., Yamazaki, Y.: Study on intelligent idling stop system. In: 2000 FISITA World Automotive Congress: Automotive Innovation for the New Millennium Seoul, pp. 1–4 (2000)Google Scholar
  12. 12.
    Rudnick, L.R.: Lubricant Additives: Chemistry and Applications. CRC Press, Boca Raton (2010)Google Scholar
  13. 13.
    Dake, L., Russel, J., Debrodt, D.: A review of DOE ECUT tribology surveys. J. Tribol. 108(4), 497–501 (1986)CrossRefGoogle Scholar
  14. 14.
    Elo, R., Jacobson, S.: Formation and breakdown of oil residue tribofilms protecting the valves of diesel engines. Wear 330, 193–198 (2015)CrossRefGoogle Scholar
  15. 15.
    Speed, L.: Engine oils. Engine Professional, pp. 46–47 (2009)Google Scholar
  16. 16.
    Guinther, G.H., Danner, M.M.: Development of an engine-based catalytic converter poisoning test to assess the impact of volatile ZDDP decomposition products from passenger car engine oils. In: SAE Technical Paper, (2007)Google Scholar
  17. 17.
    Bardasz, E.A.: 26 Crankcase Lubricants. Synthetics, Mineral Oils, and Bio-Based Lubricants: Chemistry and Technology, p. 433 (2013)Google Scholar
  18. 18.
    Parekh, K., Mourhatch, R., Aswath, P.: ZDDP-additive-catalyst interactions in engine oil. In: World Tribology Congress III 2005, pp. 661–662. American Society of Mechanical EngineersGoogle Scholar
  19. 19.
    Grill, A.: Review of the tribology of diamond-like carbon. Wear 168(1–2), 143–153 (1993)CrossRefGoogle Scholar
  20. 20.
    Grill, A.: Tribology of diamondlike carbon and related materials: an updated review. Surf. Coat. Technol. 94, 507–513 (1997)CrossRefGoogle Scholar
  21. 21.
    Ferrari, A.C., Robertson, J.: Raman spectroscopy of amorphous, nanostructured, diamond–like carbon, and nanodiamond. Philos. Trans. R. Soc. Lond. A Math. Phys. Eng. Sci. 362(1824), 2477–2512 (2004)CrossRefGoogle Scholar
  22. 22.
    Lemoine, P., Quinn, J., Maguire, P., McLaughlin, J.: Mechanical characterisation and properties of DLC films. In: Tribology of Diamond-Like Carbon Films. pp. 83–101. Springer, (2008)Google Scholar
  23. 23.
    Chung, Y.-W., Bhatia, S.: Tribological behavior of amorphous carbon nitride overcoats for magnetic thin-film rigid disks. J. Tribol. 118, 543 (1996)CrossRefGoogle Scholar
  24. 24.
    Kovalchenko, A., Ajayi, O.O., Erdemir, A., Fenske, G.R.: Friction and wear performance of low-friction carbon coatings under oil lubrication. In: SAE Technical Paper, (2002)Google Scholar
  25. 25.
    Singer, I.L., Dvorak, S.D., Wahl, K.J., Scharf, T.W.: Role of third bodies in friction and wear of protective coatings. J. Vac. Sci. Technol., A 21(5), S232 (2003). CrossRefGoogle Scholar
  26. 26.
    Bull, S.: Tribology of carbon coatings: DLC, diamond and beyond. Diam. Relat. Mater. 4(5–6), 827–836 (1995)CrossRefGoogle Scholar
  27. 27.
    Haque, T., Morina, A., Neville, A., Kapadia, R., Arrowsmith, S.: Study of the ZDDP antiwear tribofilm formed on the DLC coating using AFM and XPS techniques. J. ASTM Int. 4(7), 1–11 (2007)CrossRefGoogle Scholar
  28. 28.
    Gupta, P.: Iron-Doped Diamond-Like Carbon Coatings (Fe-DLCs): Synthesis, Characterization, and Tribology. Northwestern University (2016)Google Scholar
  29. 29.
    Vlad, M., Szczerek, M., Michalczewski, R., Kajdas, C., Tomastik, C., Osuch-SŁomka, E.: The influence of antiwear additive concentration on the tribological behaviour of aC: H: W/steel tribosystem. Proc. Inst. Mech. Eng. Part J J. Eng. Tribol. 224(10), 1079–1089 (2010)CrossRefGoogle Scholar
  30. 30.
    Hoffman, E.E., Marks, L.D.: Graphitic carbon films across systems. Tribol. Lett. 63(3), 32 (2016)CrossRefGoogle Scholar
  31. 31.
    Erdemir, A., Ramirez, G., Eryilmaz, O.L., Narayanan, B., Liao, Y., Kamath, G., Sankaranarayanan, S.K.: Carbon-based tribofilms from lubricating oils. Nature 536(7614), 67–71 (2016)CrossRefGoogle Scholar
  32. 32.
    Erdemir, A.A.E.O.,: Tribochemically driven diamond-like carbon boundary films from base lubricating oils. 2013 STLE Annual Meeting (2013)Google Scholar
  33. 33.
    Gao, F., Furlong, O., Kotvis, P., Tysoe, W.: Tribological properties of films formed by the reaction of carbon tetrachloride with iron. Tribol. Lett. 20(2), 171–176 (2005)CrossRefGoogle Scholar
  34. 34.
    Hsu, S., Klaus, E., Cheng, H.: A mechano-chemical descriptive model for wear under mixed lubrication conditions. Wear 128(3), 307–323 (1988)CrossRefGoogle Scholar
  35. 35.
    Hsu, S.M., Gates, R.S.: Effect of materials on tribochemical reactions between hydrocarbons and surfaces. J. Phys. D Appl. Phys. 39(15), 3128 (2006)CrossRefGoogle Scholar
  36. 36.
    Yu, Y., Gu, J., Kang, F., Kong, X., Mo, W.: Surface restoration induced by lubricant additive of natural minerals. Appl. Surf. Sci. 253(18), 7549–7553 (2007)CrossRefGoogle Scholar
  37. 37.
    Yuansheng, J., Shenghua, L.: Superlubricity of in situ generated protective layer on worn metal surfaces in presence of Mg 6 Si 4 O 10 (OH) 8. Superlubricity 447 (2007)Google Scholar
  38. 38.
    Yuansheng, J., Shenghua, L., Zhengye, Z., He, Y., Feng, W.: In situ mechanochemical reconditioning of worn ferrous surfaces. Tribol. Int. 37(7), 561–567 (2004)CrossRefGoogle Scholar
  39. 39.
    Blanchet, T., Lauer, J., Liew, Y.-F., Rhee, S., Sawyer, W.: Solid lubrication by decomposition of carbon monoxide and other gases. Surf. Coat. Technol. 68, 446–452 (1994)CrossRefGoogle Scholar
  40. 40.
    Yeon, J., He, X., Martini, A., Kim, S.H.: Mechanochemistry at solid surfaces: polymerization of adsorbed molecules by mechanical shear at tribological interfaces. ACS Appl. Mater. Interface 9(3), 3142–3148 (2017)CrossRefGoogle Scholar
  41. 41.
    He, X., Barthel, A.J., Kim, S.H.: Tribochemical synthesis of nano-lubricant films from adsorbed molecules at sliding solid interface: tribo-polymers from α-pinene, pinane, and n-decane. Surf. Sci. 648, 352–359 (2016)CrossRefGoogle Scholar
  42. 42.
    Faust, R.: Fascinating natural and artificial cyclopropane architectures. Angew. Chem. Int. Ed. 40(12), 2251–2253 (2001)CrossRefGoogle Scholar
  43. 43.
    de Meijere, A.: Bonding properties of cyclopropane and their chemical consequences. Angew. Chem., Int. Ed. Engl. 18(11), 809–826 (1979)CrossRefGoogle Scholar
  44. 44.
    Liu, S., Wang, Q.: Studying contact stress fields caused by surface tractions with a discrete convolution and fast fourier transform algorithm. J. Tribol. 124(1), 36–45 (2002)CrossRefGoogle Scholar
  45. 45.
    Liu, G., Wang, Q., Liu, S.: A three-dimensional thermal-mechanical asperity contact model for two nominally flat surfaces in contact. J. Tribol. 123(3), 595–602 (2001)CrossRefGoogle Scholar
  46. 46.
    Liu, Y., Wang, Q.J., Zhu, D., Shi, F.: A Generalized thermal EHL model for point contact problems. In: STLE/ASME 2008 International Joint Tribology Conference 2008, pp. 281–282. American Society of Mechanical EngineersGoogle Scholar
  47. 47.
    Chen, W.W., Wang, Q.J., Kim, W.: Transient thermomechanical analysis of sliding electrical contacts of elastoplastic bodies, thermal softening, and melting inception. J. Tribol. 131(2), 021406 (2009)CrossRefGoogle Scholar
  48. 48.
    Chen, W.W., Wang, Q.J.: Thermomechanical analysis of elastoplastic bodies in a sliding spherical contact and the effects of sliding speed, heat partition, and thermal softening. J. Tribol. 130(4), 041402 (2008)CrossRefGoogle Scholar
  49. 49.
    Martini, A., Liu, S., Wang, Q.J.: Transient three-dimensional solution for thermoelastic displacement due to surface heating and convective cooling. J. Tribol. 127(4), 750–755 (2005)CrossRefGoogle Scholar
  50. 50.
    Zhang, C., Cheng, H., Wang, Q.J.: Scuffing behavior of piston-pin/bore bearing in mixed lubrication—part II: scuffing mechanism and failure criterion. Tribol. Trans. 47(1), 149–156 (2004)CrossRefGoogle Scholar
  51. 51.
    Wang, Y., Zhang, C., Wang, Q.J., Lin, C.: A mixed-TEHD analysis and experiment of journal bearings under severe operating conditions. Tribol. Int. 35(6), 395–407 (2002)CrossRefGoogle Scholar
  52. 52.
    Bhushan, B., Fuchs, H., Tomitori, M.: Applied Scanning Probe Methods VIII: Scanning Probe Microscopy Techniques. Nanoscience and Technology. Springer, Berlin (2008)CrossRefGoogle Scholar
  53. 53.
    Erdemir, A., Eryilmaz, O., Kim, S.: Effect of tribochemistry on lubricity of DLC films in hydrogen. Surf. Coat. Technol. 257, 241–246 (2014)CrossRefGoogle Scholar
  54. 54.
    Totolin, V., Ripoll, M.R., Jech, M., Podgornik, B.: Enhanced tribological performance of tungsten carbide functionalized surfaces via in situ formation of low-friction tribofilms. Tribol. Int. 94, 269–278 (2016)CrossRefGoogle Scholar
  55. 55.
    Field, S., Jarratt, M., Teer, D.: Tribological properties of graphite-like and diamond-like carbon coatings. Tribol. Int. 37(11), 949–956 (2004)CrossRefGoogle Scholar
  56. 56.
    Steiner, L., Bouvier, V., May, U., Hegadekatte, V., Huber, N.: Modelling of unlubricated oscillating sliding wear of DLC-coatings considering surface topography, oxidation and graphitisation. Wear 268(9), 1184–1194 (2010)CrossRefGoogle Scholar
  57. 57.
    Morina, A., Neville, A.: Understanding the composition and low friction tribofilm formation/removal in boundary lubrication. Tribol. Int. 40(10), 1696–1704 (2007)CrossRefGoogle Scholar
  58. 58.
    Wang, Y., Wang, Q.J., Lin, C., Shi, F.: Development of a set of Stribeck curves for conformal contacts of rough surfaces. Tribol. Trans. 49(4), 526–535 (2006)CrossRefGoogle Scholar
  59. 59.
    Jung, I., Rhyee, J.-S., Son, J.Y., Ruoff, R.S., Rhee, K.-Y.: Colors of graphene and graphene-oxide multilayers on various substrates. Nanotechnology 23(2), 025708 (2011)CrossRefGoogle Scholar
  60. 60.
    Kim, D.-W., Kim, K.-W.: Effects of sliding velocity and normal load on friction and wear characteristics of multi-layered diamond-like carbon (DLC) coating prepared by reactive sputtering. Wear 297(1), 722–730 (2013)CrossRefGoogle Scholar
  61. 61.
    Farrow, R., Benner, R., Nagelberg, A., Mattern, P.: Characterization of surface oxides by Raman spectroscopy. Thin Solid Films 73(2), 353–358 (1980)CrossRefGoogle Scholar
  62. 62.
    Ferrari, A.C., Robertson, J.: Interpretation of Raman spectra of disordered and amorphous carbon. Phys. Rev. B 61(20), 14095–14107 (2000)CrossRefGoogle Scholar
  63. 63.
    Furlong, O., Gao, F., Kotvis, P., Tysoe, W.: Understanding the tribological chemistry of chlorine-, sulfur-and phosphorus-containing additives. Tribol. Int. 40(5), 699–708 (2007)CrossRefGoogle Scholar
  64. 64.
    Lara, J., Surerus, K., Kotvis, P., Contreras, M., Rico, J., Tysoe, W.: The surface and tribological chemistry of carbon disulfide as an extreme-pressure additive. Wear 239(1), 77–82 (2000)CrossRefGoogle Scholar
  65. 65.
    Spikes, H., Tysoe, W.: On the commonality between theoretical models for fluid and solid friction, wear and tribochemistry. Tribol. Lett. 59(1), 21 (2015)CrossRefGoogle Scholar
  66. 66.
    Tysoe, W.: On stress-induced tribochemical reaction rates. Tribol. Lett. 65(2), 48 (2017)CrossRefGoogle Scholar
  67. 67.
    Gosvami, N., Bares, J., Mangolini, F., Konicek, A., Yablon, D., Carpick, R.: Mechanisms of antiwear tribofilm growth revealed in situ by single-asperity sliding contacts. Science 348(6230), 102–106 (2015)CrossRefGoogle Scholar
  68. 68.
    Hirani, H.: Fundamentals of Engineering Tribology with Applications. Cambridge University Press, Cambridge (2016)CrossRefGoogle Scholar
  69. 69.
    Anslyn, E.V., Dougherty, D.A.: Modern Physical Organic Chemistry. University Science Books, Sausalito, CA (2006)Google Scholar
  70. 70.
    Steele, W., Chirico, R., Knipmeyer, S., Nguyen, A.: Measurements of vapor pressure, heat capacity, and density along the saturation line for ε-caprolactam, pyrazine, 1, 2-propanediol, triethylene glycol, phenyl acetylene, and diphenyl acetylene. J. Chem. Eng. Data 47(4), 689–699 (2002)CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC 2017

Authors and Affiliations

  1. 1.Department of Mechanical EngineeringNorthwestern UniversityEvanstonUSA
  2. 2.Department of ChemistryNorthwestern UniversityEvanstonUSA
  3. 3.Department of Materials Science and EngineeringNorthwestern UniversityEvanstonUSA
  4. 4.Key Laboratory of Education Ministry for Modern Design and Rotor Bearing SystemsXi’an Jiaotong UniversityXi’anPeople’s Republic of China

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