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Adhesion-dependent negative friction coefficient on chemically modified graphite at the nanoscale

Nature Materials volume 11, pages 1032–1037 (2012)Cite this article

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Abstract

From the early tribological studies of Leonardo da Vinci to Amontons’ law, friction has been shown to increase with increasing normal load. This trend continues to hold at the nanoscale, where friction can vary nonlinearly with normal load1,2. Here we present nanoscale friction force microscopy (FFM) experiments for a nanoscale probe tip sliding on a chemically modified graphite surface in an atomic force microscope (AFM). Our results demonstrate that, when adhesion between the AFM tip and surface is enhanced relative to the exfoliation energy of graphite, friction can increase as the load decreases under tip retraction. This leads to the emergence of an effectively negative coefficient of friction in the low-load regime. We show that the magnitude of this coefficient depends on the ratio of tip–sample adhesion to the exfoliation energy of graphite. Through both atomistic- and continuum-based simulations, we attribute this unusual phenomenon to a reversible partial delamination of the topmost atomic layers, which then mimic few- to single-layer graphene. Lifting of these layers with the AFM tip leads to greater deformability of the surface with decreasing applied load. This discovery suggests that the lamellar nature of graphite yields nanoscale tribological properties outside the predictive capacity of existing continuum mechanical models.

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Figure 1: Friction as a function of load and adhesive force.
Figure 2: Friction coefficient, α, as a function of the magnitude of the pull-off force, |LC|, and work of adhesion, W.
Figure 3: Load-dependent stick-slip measurements.
Figure 4: Molecular dynamics and FEM simulations of friction between an AFM tip and graphite surface during tip retraction.
Figure 5: Schematic representation of approach–retract hysteresis in the deformation of several surface and subsurface layers.

References

  1. Derjaguin, B. V., Muller, V. M. & Toporov, Yu. P. Effect of contact deformations on the adhesion of particles. J. Colloid Interface Sci. 53, 314–326 (1975).

    Article  CAS  Google Scholar 

  2. Johnson, K. L., Kendall, K. & Roberts, A. D. Surface energy and the contact of elastic solids. Proc. R. Soc. Lond. A 324, 301–313 (1971).

    Article  CAS  Google Scholar 

  3. Prelas, G. A., Popovici, G. & Bigelow, L. K. Handbook of Industrial Diamonds and Diamond Films (Marcel Dekker, 1998).

    Google Scholar 

  4. Dresselhaus, M. S. & Dresselhaus, G. Intercalation compounds of graphite. Adv. Phys. 51, 1–186 (2002).

    Article  CAS  Google Scholar 

  5. Geim, A. K. Graphene: Status and prospects. Science 324, 1530–1534 (2009).

    Article  CAS  Google Scholar 

  6. Allen, M. J., Tung, V. C. & Kaner, R. B. Honeycomb carbon: A review of graphene. Chem. Rev. 110, 132–145 (2010).

    Article  CAS  Google Scholar 

  7. Filleter, T. et al. Friction and dissipation in epitaxial graphene films. Phys. Rev. Lett. 102, 086102 (2009).

    Article  CAS  Google Scholar 

  8. Filleter, T. & Bennewitz, R. Structural and frictional properties of graphene films on SiC(0001) studied by atomic force microscopy. Phys. Rev. B 81, 155412 (2010).

    Article  Google Scholar 

  9. Lee, C. et al. Frictional characteristics of atomically thin sheets. Science 328, 76–80 (2010).

    Article  CAS  Google Scholar 

  10. Dienwiebel, M. et al. Superlubricity of graphite. Phys. Rev. Lett. 92, 126101 (2004).

    Article  Google Scholar 

  11. Lee, H., Lee, N., Seo, Y., Eom, J. & Lee, S. Comparison of frictional forces on graphene and graphite. Nanotechnology 20, 325701 (2009).

    Article  Google Scholar 

  12. Marchon, B., Carrazza, J., Heinemann, H. & Somorjai, G. A. TPD and XPS studies of O2, CO2, and H2O adsorption on clean polycrystalline graphite. Carbon 26, 507–514 (1988).

    Article  CAS  Google Scholar 

  13. Wang, S., Zhang, Y., Abidi, N. & Cabrales, L. Wettability and surface free energy of graphene films. Langmuir 25, 11078 (2009).

    Article  CAS  Google Scholar 

  14. Socoliuc, A., Bennewitz, R., Gnecco, E. & Meyer, E. Transition from stick-slip to continuous sliding in atomic friction: Entering a new regime of ultralow friction. Phys. Rev. Lett. 92, 134301 (2004).

    Article  CAS  Google Scholar 

  15. Lantz, M. A., O’Shea, S. J., Hoole, A. C. F. & Welland, M. E. Lateral stiffness of the tip and tip-sample contact in frictional force microscopy. Appl. Phys. Lett. 70, 970–972 (1996).

    Article  Google Scholar 

  16. Carpick, R. W., Ogletree, D. F. & Salmeron, M. Lateral stiffness: A new nanomechanical measurement for the determination of shear strengths with friction force microscopy. Appl. Phys. Lett. 70, 1548–1550 (1997).

    Article  CAS  Google Scholar 

  17. Dong, Y., Perez, D., Voter, A. F. & Martini, A. The roles of statics and dynamics in determining transitions between atomic friction regimes. Tribol. Lett. 42, 99–107 (2011).

    Article  Google Scholar 

  18. Zacharia, R., Ulbricht, H. & Hertel, T. Interlayer cohesive energy of graphite from thermal desorption of polyaromatic hydrocarbons. Phys. Rev. B 69, 155406 (2004).

    Article  Google Scholar 

  19. Hasegawa, M., Nishidate, K. & Iyetomi, H. Energetics of interlayer binding in graphite: The semiempirical approach revisited. Phys. Rev. B 76, 115424 (2007).

    Article  Google Scholar 

  20. Spanu, L., Sorella, S. & Galli, G. Nature and strength of interlayer binding in graphite. Phys. Rev. Lett. 103, 196401 (2009).

    Article  Google Scholar 

  21. Grierson, D. S., Flater, E. E. & Carpick, R. W. Accounting for the JKR–DMT transition in adhesion and friction measurements with atomic force microscopy. J. Adhesion Sci. Technol. 19, 291–311 (2005).

    Article  CAS  Google Scholar 

  22. Mo, Y., Turner, K. T. & Szlufarska, I. Friction laws at the nanoscale. Nature 457, 1116–1119 (2009).

    Article  CAS  Google Scholar 

  23. Smolyanitsky, A., Killgore, J. P. & Tewary, V. K. Effect of elastic deformation on frictional properties of few-layer graphene. Phys. Rev. B 85, 035412 (2012).

    Article  Google Scholar 

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Acknowledgements

The authors thank F. Sharifi for providing invaluable insights regarding this work, and K. Steffens for XPS measurements. We further thank R. Carpick, C. Righi and J. Killgore for stimulating discussions. N. Faralli created the rendering software used to visualize the molecular dynamics simulations. Z.D. acknowledges support under the Cooperative Research Agreement between the University of Maryland and the National Institute of Standards and Technology Center for Nanoscale Science and Technology, Award 70NANB10H193, through the University of Maryland. This research was performed while A.S. held a National Research Council Postdoctoral Research Associateship at NIST. Q.L. and X-Q.F. acknowledge support from the National Natural Science Foundation of China (11272177), the Thousand Young Talents Program (20121770071) and the 973 Program 2010CB631005, 2012CB934101 and 2013CB933003.

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Authors and Affiliations

  1. Center for Nanoscale Science and Technology, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA

    Zhao Deng & Rachel J. Cannara

  2. Maryland NanoCenter, University of Maryland, College Park, Maryland 20742, USA

    Zhao Deng

  3. Material Measurement Laboratory, National Institute of Standards and Technology, Boulder, Colorado 80305, USA

    Alex Smolyanitsky

  4. Department of Engineering Mechanics, Center for Nano and Micro Mechanics, Applied Mechanics Laboratory, School of Aerospace, Tsinghua University, Beijing 100084, China

    Qunyang Li & Xi-Qiao Feng

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  1. Zhao Deng
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  2. Alex Smolyanitsky
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  3. Qunyang Li
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  4. Xi-Qiao Feng
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  5. Rachel J. Cannara
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Contributions

Z.D. performed the experiments. Z.D. and R.J.C. analysed the data. A.S. devised and performed the molecular dynamics simulations. Q.L. devised and performed the finite element simulations. X-Q.F. provided guidance for the FE simulations of Q.L. R.J.C. supervised the project. Z.D., A.S., Q.L. and R.J.C. discussed results, composed the manuscript, and contributed to revisions.

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Correspondence to Rachel J. Cannara.

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The authors declare no competing financial interests.

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Deng, Z., Smolyanitsky, A., Li, Q. et al. Adhesion-dependent negative friction coefficient on chemically modified graphite at the nanoscale. Nature Mater 11, 1032–1037 (2012). https://doi.org/10.1038/nmat3452

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