Skip to main content
SpringerLink
Log in

Tribological Properties of 1-Alkenes on Copper Foils: Effect of Low-Coordination Surface Sites

  • Original Paper
  • Published:
Tribology Letters Aims and scope Submit manuscript

Abstract

It has been suggested from molecular dynamics simulations that low-coordination-number sites are produced at a sliding metal–metal interface, but, because of their instability, they may rapidly relax to increase their coordination number. The possible presence of such low-coordination sites on the surface is tested by exploiting the observation that the desorption temperatures of 1-alkenes on copper increase with both the number of carbons atoms in the 1-alkenes and the surface roughness. Thus, 1-alkenes desorb from a Cu(111) single crystal, with relatively few low-coordination sites, at temperatures between 60 and 100 K lower than from a polycrystalline copper foil. The decrease in friction after impinging a flux of various 1-alkenes on a copper foil, while rubbing in an ultrahigh vacuum tribometer, correlates very well with the corresponding 1-alkene coverages on a copper foil, estimated using the desorption kinetics. This suggests either that rubbing does not result in the formation of lower-coordination sites or that they relax sufficiently rapidly that they do not influence the surface chemistry of 1-alkenes. Surface analyses indicate that shear at the interface causes carbon to diffuse into the subsurface region to form a tribofilm.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Furlong, O., Miller, B., Tysoe, W.: Shear-induced surface-to-bulk transport at room temperature in a sliding metal–metal interface. Tribol. Lett. 41(1), 257–261 (2011). doi:10.1007/s11249-010-9711-4

    Article  CAS  Google Scholar 

  2. Furlong, O.J., Miller, B.P., Kotvis, P., Tysoe, W.T.: Low-temperature, shear-induced tribofilm formation from dimethyl disulfide on copper. ACS Appl. Mater. Interfaces 3(3), 795–800 (2011). doi:10.1021/am101149p

    Article  CAS  Google Scholar 

  3. Furlong, O., Miller, B., Tysoe, W.T.: Shear-induced boundary film formation from dialkyl sulfides on copper. Wear 274–275, 183–187 (2012). doi:10.1016/j.wear.2011.08.022

    Article  Google Scholar 

  4. Karthikeyan, S., Kim, H.J., Rigney, D.A.: Velocity and strain-rate profiles in materials subjected to unlubricated sliding. Phys. Rev. Lett. 95(10) (2005). doi:10.1103/PhysRevLett.95.106001

  5. Emge, A., Karthikeyan, S., Kim, H.J., Rigney, D.A.: The effect of sliding velocity on the tribological behavior of copper. Wear 263, 614–618 (2007). doi:10.1016/j.wear.2007.01.095

    Article  CAS  Google Scholar 

  6. Karthikeyan, S., Agrawal, A., Rigney, D.A.: Molecular dynamics simulations of sliding in an Fe–Cu tribopair system. Wear 267(5–8), 1166–1176 (2009). doi:10.1016/j.wear.2009.01.032

    Article  CAS  Google Scholar 

  7. Kim, H.J., Kim, W.K., Falk, M.L., Rigney, D.A.: MD simulations of microstructure evolution during high-velocity sliding between crystalline materials. Tribol. Lett. 28(3), 299–306 (2007). doi:10.1007/s11249-007-9273-2

    Article  Google Scholar 

  8. Janssens, T., Clausen, B., Hvolbæk, B., Falsig, H., Christensen, C., Bligaard, T., Nørskov, J.: Insights into the reactivity of supported Au nanoparticles: combining theory and experiments. Top. Catal. 44(1), 15–26 (2007). doi:10.1007/s11244-007-0335-3

    Article  CAS  Google Scholar 

  9. Jenks, C.J., Bent, B.E., Bernstein, N., Zaera, F.: Evidence for an unusual coordination geometry for ethylene on Cu(110). Surf. Sci. 277(3), L89–L94 (1992). doi:10.1016/0039-6028(92)90761-t

    Article  CAS  Google Scholar 

  10. Kubota, J., Kondo, J.N., Domen, K., Hirose, C.: IRAS Studies of adsorbed ethene (C2H4) on clean and oxygen-covered Cu(110) surfaces. J. Phys. Chem. 98(31), 7653–7656 (1994). doi:10.1021/j100082a042

    Article  CAS  Google Scholar 

  11. Fuhrmann, D., Wacker, D., Weiss, K., Hermann, K., Witko, M., Woll, C.: The adsorption of small hydrocarbons on Cu(111): a combined He-atom scattering and x-ray absorption study for ethane, ethylene, and acetylene. J. Chem. Phys. 108(6), 2651–2658 (1998)

    Article  CAS  Google Scholar 

  12. Linke, R., Becker, C., Pelster, T., Tanemura, M., Wandelt, K.: Adsorption of ethene on Cu(111). Surf. Sci. 377(1–3), 655–658 (1997). doi:10.1016/s0039-6028(96)01475-6

    Article  Google Scholar 

  13. Tang, J.C., Feng, X.S., Shen, J.F., Fujikawa, T., Okazawa, T.: Multiple-scattering analysis of the structure of ethylene adsorbed on the Cu(100) surface. Phys. Rev. B 44(23), 13018–13025 (1991)

    Article  CAS  Google Scholar 

  14. Venugopal, V., Vattuone, L., Kravchuk, T., Smerieri, M., Savio, L., Jupille, J., Rocca, M.: Dynamics of ethene adsorption on clean and C-contaminated Cu(410). J. Phys. Chem. C 113(49), 20875–20880 (2009). doi:10.1021/jp9047924

    Article  CAS  Google Scholar 

  15. Kravchuk, T., Venugopal, V., Vattuone, L., Burkholder, L., Tysoe, W.T., Smerieri, M., Rocca, M.: Ethene adsorption and decomposition on the Cu(410) surface. J. Phys. Chem. C 113(49), 20881–20889 (2009). doi:10.1021/jp904794n

    Article  CAS  Google Scholar 

  16. Kravchuk, T., Vattuone, L., Burkholder, L., Tysoe, W.T., Rocca, M.: Ethylene decomposition at undercoordinated sites on Cu(410). J. Am. Chem. Soc. 130(38), 12552–12553 (2008). doi:10.1021/ja802105z

    Article  CAS  Google Scholar 

  17. Miller, B., Furlong, O.J., Tysoe, W.T.: The desorption and reaction of 1-alkenes and 1-alkynes on Cu(100) and copper foils. Surf. Sci. (in press) (2013). doi:10.1016/j.susc.2013.04.007

  18. Wetterer, S.M., Lavrich, D.J., Cummings, T., Bernasek, S.L., Scoles, G.: Energetics and kinetics of the physisorption of hydrocarbons on Au(111). J. Phys. Chem. B 102(46), 9266–9275 (1998). doi:10.1021/jp982338+

    Article  CAS  Google Scholar 

  19. Firment, L.E., Somorjai, G.A.: Surface structures of normal paraffins and cyclohexane monolayers and thin crystals grown on the (111) crystal face of platinum. A low-energy electron diffraction study. J. Chem. Phys. 66(7), 2901–2913 (1977)

    Article  CAS  Google Scholar 

  20. Tait, S.L., Dohnalek, Z., Campbell, C.T., Kay, B.D.: n-alkanes on Pt(111) and on C(0001)/Pt(111): chain length dependence of kinetic desorption parameters. J. Chem. Phy. 125(23) (2006). doi:10.1063/1.2400235

  21. Lei, R.Z., Gellman, A.J., Koel, B.E.: Desorption energies of linear and cyclic alkanes on surfaces: anomalous scaling with length. Surf. Sci. 554(2–3), 125–140 (2004). doi:10.1016/j.suse.2003.12.058

    Article  CAS  Google Scholar 

  22. Bishop, A.R., Girolami, G.S., Nuzzo, R.G.: Structural models and thermal desorption energetics for multilayer assemblies of the n-alkanes on Pt(111). J. Phys. Chem. B 104(4), 754–763 (2000). doi:10.1021/jp9926488

    Article  CAS  Google Scholar 

  23. Chesters, M.A., McCash, E.M.: A fourier-transform reflection-absorption infrared spectroscopic study of alkyne adsorption on Cu(111). J. Electron Spectrosc. Relat. Phenom. 44(1), 99–108 (1987). doi:10.1016/0368-2048(87)87011-1

    Article  CAS  Google Scholar 

  24. Toomes, R.L., Lindsay, R., Baumgartel, P., Terborg, R., Hoeft, J.T., Koebbel, A., Schaff, O., Polcik, M., Robinson, J., Woodruff, D.P., Bradshaw, A.M., Lambert, R.M.: Structure determination of propyne and 3,3,3-trifluoropropyne on Cu(111). J. Chem. Phys. 112(17), 7591–7599 (2000)

    Article  CAS  Google Scholar 

  25. Valcárcel, A., Ricart, J.M., Illas, F., Clotet, A.: Theoretical interpretation of the IR spectrum of propyne on Cu(111). J. Phys. Chem. B 108(47), 18297–18305 (2004). doi:10.1021/jp047103e

    Article  Google Scholar 

  26. Sohn, Y., Wei, White, J.M.: 1-Phenyl-1-propyne on Cu(111):  TOFMS TPD, XPS, UPS, and 2PPE studies. Langmuir 23(24), 12185–12191 (2007). doi:10.1021/la702241m

  27. Miller, B., Kotvis, P., Furlong, O., Tysoe, W.: Relating molecular structure to tribological chemistry: borate esters on copper. Tribol. Lett. 49(1), 21–29 (2013). doi:10.1007/s11249-012-0038-1

    Article  CAS  Google Scholar 

  28. Mroczkowski, S., Lichtman, D.: Calculated auger yields and sensitivity factors for KLL–NOO transitions with 1–10 kV primary beams. J. Vac. Sci. Technol., A 3(4), 1860–1865 (1985)

    Article  CAS  Google Scholar 

  29. Redhead, P.A.: Thermal desorption of gases. Vacuum 12, 9 (1962)

    Google Scholar 

  30. Fichthorn, K.A., Miron, R.A.: Thermal desorption of large molecules from solid surfaces. Phys. Rev. Lett. 89(19) (2002). doi:10.1103/PhysRevLett.89.196103

  31. Fichthorn, K.A., Becker, K.E., Miron, R.A.: Molecular simulation of temperature-programmed desorption. Catal. Today 123(1–4), 71–76 (2007). doi:10.1016/j.cattod.2006.12.003

    Article  CAS  Google Scholar 

  32. Clark, A.: The Theory of Adsorption and Catalysis. Academic Press, New York (1970)

    Google Scholar 

  33. Miller, B.P., Furlong, O.J., Tysoe, W.T.: The kinetics of shear-induced boundary film formation from dimethyl disulfide on copper. Tribol. Lett. 49(1), 39–46 (2013). doi:10.1007/s11249-012-0040-7

    Article  CAS  Google Scholar 

  34. Saji, S., Kadokura, T., Anada, H., Notoya, K., Takano, N.: Solid solubility of carbon in copper during mechanical alloying. Mater. Trans., JIM 39(7), 778–781 (1998)

    CAS  Google Scholar 

  35. Yamane, T., Okubo, H., Hisayuki, K., Oki, N., Konishi, M., Komatsu, M., Minamino, Y., Koizumi, Y., Kiritani, M., Kim, S.J.: Solid solubility of carbon in copper mechanically alloyed. J. Mater. Sci. Lett. 20(3), 259–260 (2001). doi:10.1023/a:1006701708039

    Article  CAS  Google Scholar 

  36. Marques, M.T., Correia, J.B., Conde, O.: Carbon solubility in nanostructured copper. Scripta Materialia 50(7), 963–967 (2004). doi:http://dx.doi.org/10.1016/j.scriptamat.2004.01.016

    Google Scholar 

Download references

Acknowledgments

We gratefully acknowledge the Chemistry Division of the National Science Foundation under Grant Number CHE-9213988 and the Office of Naval Research for support of this work.

Author information

Authors and Affiliations

  1. Department of Chemistry and Laboratory for Surface Studies, University of Wisconsin–Milwaukee, Milwaukee, WI, 53211, USA

    Brendan P. Miller & Wilfred T. Tysoe

  2. INFAP/CONICET, Universidad. Nacional de San Luis, Ejército de los Andes 950, 700, San Luis, Argentina

    Octavio J. Furlong

Authors
  1. Brendan P. Miller
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Octavio J. Furlong
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Wilfred T. Tysoe
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Wilfred T. Tysoe.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Miller, B.P., Furlong, O.J. & Tysoe, W.T. Tribological Properties of 1-Alkenes on Copper Foils: Effect of Low-Coordination Surface Sites. Tribol Lett 51, 357–363 (2013). https://doi.org/10.1007/s11249-013-0168-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11249-013-0168-0

Keywords

Search

Navigation