Abstract
Graphene is considered a wonder material for fundamental research and industrial application, whereas its poor dispersibility and incompatibility in lubricants have impeded the application for solving lubrication problems. Here, in situ fabrication of effectively functionalized graphene sheets was developed through a moderate electrochemical method for exfoliating graphite into graphene sheets in ionic liquids solution. The as-fabricated graphene sheets with the charged groups of ionic liquids (ILs) could be self-assembled together to form the multilayer sandwich structure through the electrostatic interaction. Self-assembly multilayer graphene (MLG) exhibits so high-density coverage of functional groups that some amorphous regions are formed on the graphene basal plane, which significantly improves its dispersibility and stability in ILs lubricant. Moreover, the functionalized MLG as a novel lubricant additive greatly enhances the friction-reducing and antiwear abilities for the contact of steel/steel (friction coefficient and wear volume lubricated by ILs with MLG at applied load of 200 N and 150 °C were reduced by up to 55.9 and 84.2 %, and under high vacuum were reduced by up to 36 and 94.3 % with pure ILs as a comparison, respectively), which is attributed to the synergies of ILs and MLG because ILs with functionalized MLG can form the physical adsorptive film and tribo-chemical reaction film on the rubbing surface during friction process.
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Novoselov, K.S., Geim, A.K., Morozov, S.V., Jiang, D., Katsnelson, M.I., Grigorieva, I.V., Dubonos, S.V., Firsov, A.A.: Two-dimensional gas of massless dirac fermions in graphene. Nature 438, 197–200 (2005)
Geim, A.K., Novoselov, K.S.: The rise of graphene. Nat. Mater. 6, 183–191 (2007)
Geim, A.K.: Graphene: status and prospects. Science 324, 1530–1534 (2009)
Pu, J., Mo, Y., Wan, S., Wang, L.: Fabrication of novel graphene–fullerene hybrid lubricating films based on self-assembly for MEMS applications. Chem. Commun. 50, 469–471 (2014)
Stankovich, S., Dikin, D.A., Dommettm, G.H.B., Kohlhaas, K.M., Zimney, E.J., Stach, E.A., Piner, R.D., Nguyen, S.T., Ruoff, R.S.: Graphene-based composite materials. Nature 442, 282–286 (2006)
Kim, T.Y., Lee, H.W., Stoller, M., Dreyer, D.R., Bielawski, C.W., Ruoff, R.S., Suh, K.S.: High-performance supercapacitors based on poly(ionic liquid)-modified graphene electrodes. ASC Nano 5, 436–442 (2011)
Shan, C., Yang, H., Song, J., Han, D., Ivaska, A., Niu, L.: Direct electrochemistry of glucose oxidase and biosensing for glucose based on graphene. Anal. Chem. 81, 2378–2382 (2009)
Liang, M., Zhi, L.: Graphene-based electrode materials for rechargeable lithium batteries. J. Mater. Chem. 19, 5871–5878 (2009)
Zhang, L., Yu, J., Yang, M., **e, Q., Peng, H., Liu, Z.: Janus graphene from asymmetric two-dimensional chemistry. Nat. Commun. 4, 1443 (2013)
Boukhvalov, D.W., Katsnelson, M.I.: Chemical functionalization of graphene with defects. Nano Lett. 8, 4373–4379 (2008)
Park, J., Yan, M.D.: Covalent functionalization of graphene with reactive intermediates. Acc. Chem. Res. 46, 181–189 (2012)
Chen, Y., Zhang, X., Zhang, D., Yu, P., Ma, Y.: High performance supercapacitors based on reduced graphene oxide in aqueous and ionic liquid electrolytes. Carbon 49, 573–580 (2011)
Park, S., Lee, K.S., Bozoklu, G., Cai, W., Nguyen, S.T., Ruoff, R.S.: Graphene oxide papers modified by divalent ions-enhancing mechanical properties via chemical cross-linking. ACS Nano 2, 572–578 (2008)
Lin, J., Wang, L., Chen, G.: Modification of graphene platelets and their tribological properties as a lubricant additive. Tribol. Lett. 41, 209–215 (2011)
Quintana, M., Vazquez, E., Prato, M.: Organic functionalization of graphene in dispersions. Acc. Chem. Res. 46, 138–148 (2012)
Park, S., An, J., Piner, R.D., Jung, I., Yang, D., Velamakanni, A., Nguyen, S.T., Ruoff, R.S.: Aqueous suspension and characterization of chemically modified graphene sheets. Chem. Mater. 20, 6592–6594 (2008)
Ryu, S., Han, M.Y., Maultzsch, J., Heinz, T.F., Kim, P., Steigerwald, M.L., Brus, L.E.: Reversible basal plane hydrogenation of graphene. Nano Lett. 8, 4597–4602 (2008)
Hernandez, Y., Nicolsi, V., Loyta, M., Blighe, F.M., Sun, Z., De, S., McGovern, I.T., Holland, B., Byrne, M., Gun’Ko, Y.K., Boland, J.J., Niraj, P., Duesberg, G., Krishnamurty, S., Goodhue, R., Hutchinson, J., Scardaci, V., Ferrari, A.C., Coleman, J.N.: High–yield production of graphene by liquid-phase exfoliation of graphite. Nat. Nanotechnol. 3, 563–568 (2008)
Emtsev, K.V., Bostwick, A., Horn, K., Jobst, J., Kellogg, G.L., Ley, L., McChesney, J.L., Ohta, T., Reshanov, S.A., Röhrl, J., Rotenberg, E., Schmid, A.K., Waldmann, D., Weber, H.B., Seyller, T.: Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide. Nat. Mater. 8, 203–207 (2009)
Reina, A., Jia, X., Ho, J., Nezich, D., Son, H., Bulovic, V., Dresselhaus, M.S., Kong, J.: Large area, few-layer graphene films by chemical vapor deposition. Nano Lett. 9, 30–35 (2009)
Hagiwara, R., Ito, Y.: Room temperature ILs of alkylimidazolium cations and fluoroanions. J. Fluor. Chem. 105, 221–227 (2000)
Freire, M.G., Carvalho, P.J., Fernandes, A.M., Marrucho, I.M., Queimada, A.J., Coutinho, J.A.P.: Surface tension of imidazolium based ILs: anion, cation, temperature and water effect. J. Colloid Interface Sci. 314, 621–630 (2007)
Wang, J., Wang, H., Zhang, S., Zhang, H., Zhao, Y.: Conductivities, volumes, fluorescence, and aggregation behavior of ILs [C4mim][BF4] and [Cnmim]Br (n = 4, 6, 8, 10, 12) in aqueous solutions. J. Phys. Chem. B 111, 6181–6188 (2007)
Ye, C., Liu, W., Chen, Y., Yu, L.: Room-temperature ILs: a novel versatile lubricant. Chem. Commun. 21, 2244–2245 (2001)
Lu, W., Fadeev, A.G., Qi, B., Smela, E., Mattes, B.R., Ding, J., Spinks, G.M., Mazurkiewicz, J., Zhou, D., Wallace, G.G., Macfarlane, D.R., Forsyth, S.A., Forsyth, M.: Use of ionic liquids for π-conjugated polymer electrochemical devices. Science 297, 983–987 (2002)
Cai, M., Liang, Y., Yao, M., **a, Y., Zhou, F., Liu, W.: Imidazolium ILs as antiwear and antioxidant additive in poly(ethylene glycol) for steel/steel contacts. ACS Appl. Mater. Interfaces 2, 870–876 (2010)
Liu, N., Luo, F., Wu, H., Liu, Y., Zhang, C., Chen, J.: One-step ionic-liquid-assisted electrochemical synthesis of ionic-liquid-functionalized graphene sheets directly from graphite. Adv. Funct. Mater. 18, 1518–1525 (2008)
Kim, K.S., Shin, B.K., Lee, H., Ziegler, F.: Refractive index and heat capacity of 1-butyl-3-methylimidazolium bromide and 1-butyl-3-methylimidazolium tetrafluoroborate, and vapor pressure of binary systems for 1-butyl-3-methylimidazolium bromide + trifluoroethanol and 1-butyl-3-methylimidazolium tetrafluoroborate + trifluoroethanol. Fluid Phase Equilib. 218, 215–220 (2004)
Yuan, G., Li, X., Dong, Z., Westwood, A., Cui, Z., Cong, Y., Du, H., Kang, F.: Graphite blocks with preferred orientation and high thermal conductivity. Carbon 50, 175–182 (2012)
Park, J.S., Reina, A., Saito, R., Kong, J., Dresselhaus, G., Dresselhaus, M.S.: G’ band Raman spectra of single, double and triple layer graphene. Carbon 47, 1303–1310 (2009)
Ni, Z., Wang, Y., Yu, T., Shen, Z.: Ramam spectroscopy and imaging of graphene. Nano Res. 1, 273–291 (2008)
Fan, X., Wang, L.: Highly conductive ionic liquids towards high-performance space lubricating greases. ACS Appl. Mater. Interface. 6, 14660–14671 (2014)
Heimer, N.E., Del, S.R.E., Meng, Z.Z., Wilkes, J.S., Carper, W.R.: Vibrational spectra of imidazolium tetrafluoroborate ionic liquids. J. Mol. Liq. 124, 84–95 (2006)
Englert, J.M., Dotzer, C., Yang, G., Schmid, M., Papp, C., Gottfried, J.M., Steinrück, H.P., Spiecker, E., Hauke, F., Hirsch, A.: Covalent bulk functionalization of graphene. Nat. Chem. 3, 279–286 (2011)
Liu, X., Pu, J., Wang, L., Xue, Q.: Novel DLC/ionic liquid/graphene nanocomposite coatings towards high-vacuum related space applications. J. Mater. Chem. A 1, 3797–3809 (2013)
NIST X-ray Photoelectron Spectroscopy Database, version 4.1; National Institute of Standards and Technology, Gaithersburg, MD (2012). http://srdata.nist.gov/xps/. Accessed on 26 Mar 2013
**e, H., Saito, T., Hickner, M.A.: Zeta potential of ion-conductive membranes by streaming current measurements. Langmuir 27, 4721–4727 (2011)
Thielbeer, F., Donaldson, K., Bradley, M.: Zeta potential mediated reaction monitoring on nano and microparticles. Bioconj. Chem. 22, 144–150 (2011)
Wu, Y.Y., Tsui, W.C., Liu, T.C.: Experimental analysis of tribological properties of lubricating oils with nanoparticle additives. Wear 262, 819–825 (2007)
Seki, T., Grunwaldt, J.D., Baiker, A.: In situ attenuated total reflection infrared spectroscopy of imidazolium-based room-temperature ionic liquids under “supercritical” CO2. J. Phys. Chem. B 113, 114–122 (2009)
Berman, D., Erdemir, A., Sumant, A.V.: Reduced wear and friction enabled by graphene layers on sliding steel surfaces in dry nitrogen. Carbon 59, 167–175 (2013)
Lin, J., Wang, L., Chen, G.: Modification of graphene platelets and their tribological properties as a lubricant additive. Tribol. Lett. 41, 209–215 (2011)
Fan, X., **a, Y., Wang, L., Li, W.: Multi-layer graphene as a lubricating additive in bentone grease. Tribol. Lett. 55, 455–464 (2014)
Ferrari, A.C., Meyer, J.C., Scardaci, V., Casiraghi, C., Lazzeri, M., Mauri, F., Piscanec, S., Jiang, D., Novoselov, K.S., Roth, S., Geim, A.K.: Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. 97, 187401 (2006)
Phillips, B.S., John, G., Zabinski, J.S.: Surface chemistry of fluorine containing ionic liquids on steel substrates at elevated temperature using mössbauer spectroscopy. Tribol. Lett. 26, 85–91 (2007)
Mu, Z., Zhou, F., Zhang, S., Liang, Y., Liu, W.: Effect of the functional groups in ionic liquid molecules on the friction and wear behavior of aluminum alloy in lubricated aluminum-on-steel contact. Tribol. Int. 38, 725–731 (2005)
Ji, Q., Honma, I., Paek, S.M., Akada, M., Hill, J.P., Vinu, A., Ariga, K.: Layer-by-layer films of graphene and ionic liquids for highly selective gas sensing. Angew. Chem. 122, 9931–9933 (2010)
Shen, J., Hu, Y., Li, C., Qin, C., Shi, M., Ye, M.: Layer-by-layer self-assembly of graphene nanoplatelets. Langmuir 25, 6122–6128 (2009)
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This work was supported by National Natural Science Foundation of China (Grants 11172300 and 21373249).
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Fan, X., Wang, L. & Li, W. In Situ Fabrication of Low-Friction Sandwich Sheets Through Functionalized Graphene Crosslinked by Ionic Liquids. Tribol Lett 58, 12 (2015). https://doi.org/10.1007/s11249-015-0485-6
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DOI: https://doi.org/10.1007/s11249-015-0485-6