Acta Mechanica Solida Sinica

, Volume 24, Issue 2, pp 101–116 | Cite as

The unique properties of the solid-like confined liquid films: A large scale molecular dynamics simulation approach

  • Fengchao Wang
  • Yapu Zhao


The properties of the confined liquid are dramatically different from those of the bulk state, which were reviewed in the present work. We performed large-scale molecular dynamics simulations and full-atom nonequilibrium molecular dynamics simulations to investigate the shear response of the confined simple liquid as well as the n-hexadecane ultrathin films. The shear viscosity of the confined simple liquid increases with the decrease of the film thickness. Apart from the well-known ordered structure, the confined n-hexadecane exhibited a transition from 7 layers to 6 in our simulations while undergoing an increasing shear velocity. Various slip regimes of the confined n-hexadecane were obtained. Viscosity coefficients of individual layers were examined and the results revealed that the local viscosity coefficient varies with the distance from the wall. The individual n-hexadecane layers showed the shear-thinning behaviors which can be correlated with the occurrence of the slip. This study aimed at elucidating the detailed shear response of the confined liquid and may be used in the design and application of micro- and nano-devices.

Key words

confined liquid solid-like shear-thinning slip large scale molecular dynamics simulation 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. [1]
    White, F.M., Fluid Mechanics. New York: McGraw-Hill, 1994.Google Scholar
  2. [2]
    Granick, S., Motions and relaxations of confined liquids. Science, 1991, 253: 1374–1379.CrossRefGoogle Scholar
  3. [3]
    Horn, R.G. and Israelachvili, J.N., Direct measurement of structural forces between two surfaces in a non-polar liquid. Journal of Chemical Physics, 1981, 75: 1400–1411.CrossRefGoogle Scholar
  4. [4]
    Heuberger, H., Zach, M. and Spencer, N.D., Density fluctuations under confinement: when is a fluid not a fluid? Science, 2001, 292: 905–908.CrossRefGoogle Scholar
  5. [5]
    Gee, M.L., McGuiggan, P.M., Israelachvilil, J.N. and Homola, A.M., Liquid to solidlike transitions of molecularly thin films under shear. Journal of Chemical Physics, 1990, 93: 1895–1906.CrossRefGoogle Scholar
  6. [6]
    Zhu, Y.X. and Granick, S., Superlubricity: a paradox about confined fluids resolved. Physical Review Letters, 2004, 93: 096101.CrossRefGoogle Scholar
  7. [7]
    Bhushan, B., Israelachvili, J.N. and Landman, U., Nanotribology: friction, wear and lubrication at the atomic scale. Nature, 1995, 374: 607–616.CrossRefGoogle Scholar
  8. [8]
    Demirel, A.L. and Granick, S., Origins of solidification when a simple molecular fluid is confined between two plates. Journal of Chemical Physics, 2001, 115: 1498–1512.CrossRefGoogle Scholar
  9. [9]
    Mukhopadhyay, A., Bae, S.C., Zhao, J. and Granick, S., How confined lubricants diffuse during shear. Physical Review Letters, 2004, 93: 236105.CrossRefGoogle Scholar
  10. [10]
    Karniadakis, G., Beskok, A. and Aluru, N., Microflows and Nanoflows: Fundamentals and Simulation. New York: Springer, 2005.zbMATHGoogle Scholar
  11. [11]
    Yuan, Q.Z. and Zhao, Y.P., Hydroelectric voltage generation based on water-filled single-walled carbon nanotubes. Journal of the American Chemical Society, 2009, 131: 6374–6376.CrossRefGoogle Scholar
  12. [12]
    Qin, X.C., Yuan, Q.Z., Zhao, Y.P., Xie, S.B. and Liu, Z.F., Measurement of the rate of water translocation through carbon nanotubes. Nano Letters, 2011, Scholar
  13. [13]
    McGuiggan, P.M., Gee, M.L., Yoshizawa, H., Hirz, S.J. and Israelachvili, J.N., Friction studies of polymer lubricated surfaces. Macromolecules, 2007, 40(6): 2126–2133.CrossRefGoogle Scholar
  14. [14]
    Lim, R., Li, S.F.Y. and O’Shea, S.J., Solvation forces using sample-modulation atomic force microscopy. Langmuir, 2002, 18: 6116–1624.CrossRefGoogle Scholar
  15. [15]
    Patil, S., Mater, G., Oral, A. and Hoffmann, P.M., Solid or liquid? solidification of a nanoconfined liquid under nonequilibrium conditions. Langmuir, 2006, 22: 6485–6488.CrossRefGoogle Scholar
  16. [16]
    Cui, S.T., Gupta, S.A., Cummings, P.T. and Cochran, H.D., Molecular dynamics simulations of the rheology of normal decane, hexadecane, and tetracosane. Journal of Chemical Physics, 1996, 105: 1214–1220.CrossRefGoogle Scholar
  17. [17]
    Gao, J.P., Luedtke, W.D. and Landman, U., Origins of solvation forces in confined films. Journal of Physical Chemistry B, 1997, 101: 4013–4023.CrossRefGoogle Scholar
  18. [18]
    Israelachvili, J.N., Intermolecular and Surface Forces. San Diego: Academic Press, 1992.Google Scholar
  19. [19]
    Yin, J. and Zhao, Y.P., Hybrid QM/MM simulation of the hydration phenomena of dipalmitoylphosphatidylcholine headgroup. Journal of Colloid and Interface Science, 2009, 329: 410–415.CrossRefGoogle Scholar
  20. [20]
    Yang, C.Y. and Zhao, Y.P., Influences of hydration force and elastic strain energy on stability of solid film in very thin solid-on-liquid structure. Journal of Chemical Physics, 2004, 120: 5366–5376.CrossRefGoogle Scholar
  21. [21]
    Yamada, S., Layering transitions and tribology of molecularly thin films of poly(dimethylsiloxane). Langmuir, 2003, 19: 7399–7405.CrossRefGoogle Scholar
  22. [22]
    Jabbarzadeh, A., Harrowell, P. and Tanner, R.I., Very low friction state of a dodecane film confined between mica surfaces. Physical Review Letters, 2005, 94: 126103.CrossRefGoogle Scholar
  23. [23]
    Jabbarzadeh, A., Harrowell, P. and Tanner, R.I., Crystal bridge formation marks the transition to rigidity in a thin lubrication film. Physical Review Letters, 2006, 96: 206102.CrossRefGoogle Scholar
  24. [24]
    Bureau, L., Rate effects on layering of a confined linear alkane. Physical Review Letters, 2007, 99: 225503.CrossRefGoogle Scholar
  25. [25]
    Cui, S.T., McCabe, C., Cummings, P.T. and Cochran, H.D., Molecular dynamics study of the nano-rheology of n-dodecane confined between planar surfaces. Journal of Chemical Physics, 2003, 118: 8941–8944.CrossRefGoogle Scholar
  26. [26]
    Reiner, M., The Deborah number. Physics Today, 1964, 17: 62.CrossRefGoogle Scholar
  27. [27]
    Landau, L.D. and Lifshitz, E.M., Theory of Elasticity. Oxford: Butterworth-Heinemann, 1999.zbMATHGoogle Scholar
  28. [28]
    Kumacheva, E. and Klein, J., Simple liquids confined to molecularly thin layers. II. Shear and frictional behavior of solidified films. Journal of Chemical Physics, 1998, 108: 7010–7022.CrossRefGoogle Scholar
  29. [29]
    Khan, S.H., Matei, G., Patil, S. and Hoffmann, P.M., Dynamic solidification in nanoconfined water films. Physical Review Letters, 2010, 105: 106101.CrossRefGoogle Scholar
  30. [30]
    Bureau, L., Nonlinear rheology of a nanoconfined simple fluid. Physical Review Letters, 2010, 104: 218302.CrossRefGoogle Scholar
  31. [31]
    Granick, S., Bae, S.C., Kumar, S. and Yu, C., Confined liquid controversies near closure? Physics, 2010, 3: 73.CrossRefGoogle Scholar
  32. [32]
    Huang, D.M., Sendner, C., Horinek, D., Netz, R.R. and Bocquet, L., Water slippage versus contact angle: a quasiuniversal relationship. Physical Review Letters, 2008, 101: 226101.CrossRefGoogle Scholar
  33. [33]
    Granick, S., Lee, H. and Zhu, Y., Slippery questions of stick when fluid flows past surfaces. Nature Materials, 2003, 2: 221–227.CrossRefGoogle Scholar
  34. [34]
    De Gennes, P.G., On fluid/wall slippage. Langmuir, 2002, 18: 3413–3414.CrossRefGoogle Scholar
  35. [35]
    Thompson, P.A. and Troian, S.M., A general boundary condition for liquid flow at solid surfaces. Nature, 1997, 389: 360–362.CrossRefGoogle Scholar
  36. [36]
    Lauga, E., Apparent slip due to the motion of suspended particles in flows of electrolyte solutions. Langmuir, 2004, 20: 8924–8930.CrossRefGoogle Scholar
  37. [37]
    Schmatko, T., Hervet, H. and Leger, L., Friction and slip at simple fluid-solid interfaces: the roles of the molecular shape and the solid-liquid interaction. Physical Review Letters, 2005, 94: 244501.CrossRefGoogle Scholar
  38. [38]
    Vinogradova, O.I., Slippage of water over hydrophobic surfaces. International Journal of Mineral Processing, 1999, 56: 31–60.CrossRefGoogle Scholar
  39. [39]
    Jabbarzadeh, A., Atkinson, J.D. and Tanner, R.I., Wall slip in the molecular dynamics simulation of thin films of hexadecane. Journal of Chemical Physics, 1999, 110: 2612–2620.CrossRefGoogle Scholar
  40. [40]
    Jabbarzadeh, A., Atkinson, J.D. and Tanner, R.I., Effect of the wall roughness on slip and rheological properties of hexadecane in molecular dynamics simulation of Couette shear flow between two sinusoidal walls. Physical Review E, 2000, 61: 690–699.CrossRefGoogle Scholar
  41. [41]
    Pit, R., Hervet, H. and Leger, L., Direct experimental evidence of slip in hexadecane: solid interfaces. Physical Review Letters, 2000, 85: 980–983.CrossRefGoogle Scholar
  42. [42]
    Zhu, Y.X. and Granick, S., Rate-dependent slip of Newtonian liquid at smooth surfaces. Physical Review Letters, 2001, 87: 096105.CrossRefGoogle Scholar
  43. [43]
    Plimpton, S., Fast parallel algorithms for short-range molecular-dynamics. Journal of Computational Physics, 1995, 117: 1–19.CrossRefGoogle Scholar
  44. [44]
    Berendsen, H.J.C., Grigera, J.R. and Straatsma, T.P., The missing term in effective pair potentials. Journal of Physical Chemistry, 1987, 91: 6269–6271.CrossRefGoogle Scholar
  45. [45]
    Hoover, W.G., Canonical dynamics: equilibrium phase-space distributions. Physical Review A, 1985, 31: 1695–1697.CrossRefGoogle Scholar
  46. [46]
    Stuart, S.J., Tutein, A.B. and Harrison, J.A., A reactive potential for hydrocarbons with intermolecular interactions. Journal of Chemical Physics, 2000, 112: 6472–6486.CrossRefGoogle Scholar
  47. [47]
    Halicioglu, T. and Pound, G.M., Calculation of potential energy parameters from crystalline state properties. Physica Status Solidi A: Applied Research, 1975, 30: 619–623.CrossRefGoogle Scholar
  48. [48]
    Dauberosguthorpe, P., Roberts, V.A., Osguthorpe, D.J., Wolff, J., Genest, M. and Hagler, A.T., Structure and energetics of ligand binding to proteins: escherichia coli dihydrofolate reductase-trimethoprim, a drug-receptor system. Proteins-Structure Function and Genetics, 1988, 4: 31–47.CrossRefGoogle Scholar
  49. [49]
    Ardekani, A.M. and Joseph, D.D., Instability of stationary liquid sheets. Proceedings of the National Academy of Sciences of the United States of America, 2009, 106: 4992–4996.CrossRefGoogle Scholar
  50. [50]
    De Gennes, P.G., Brochard-Wyart, F. and Quere, D., Capillarity and Wetting Phenomena. New York: Springer, 2004.CrossRefGoogle Scholar
  51. [51]
    Brochard-Wyart, F., Raphael, E. and Vovelle, L., Démouillage en régime inertiel: apparitions d’ondes capillaries. Comptes Rendus de l’Académie des Sciences, 1995, 321: 367–370.Google Scholar
  52. [52]
    Wang, F.C., Feng, J.T. and Zhao, Y.P., The head-on colliding process of binary liquid droplets at low velocity: High-speed photography experiments and modeling. Journal of Colloid and Interface Science, 2008, 326: 196–200.CrossRefGoogle Scholar
  53. [53]
    Yuan, Q.Z. and Zhao, Y.P., Precursor film in dynamic wetting, electrowetting and electro-elasto-capillarity. Physical Review Letters, 2010, 104: 246101.CrossRefGoogle Scholar
  54. [54]
    Li, J., AtomEye: an efficient atomistic configuration viewer. Modelling and Simulation in Materials Science and Engineering, 2003, 11: 173–177.CrossRefGoogle Scholar
  55. [55]
    Jabbarzadeh, A. and Tanner, R.I., Crystallization of alkanes under quiescent and shearing conditions. Journal of Non-Newtonian Fluid Mechanics, 2009, 160: 11–21.CrossRefGoogle Scholar
  56. [56]
    Drummond, C., Alcantar, N. and Israelachvili, J., Shear alignment of confined hydrocarbon liquid films. Physical Review E, 2002, 66: 011705.CrossRefGoogle Scholar
  57. [57]
    Martini, A., Roxin, A., Snurr, R.Q., Wang, Q. and Lichter, S., Molecular mechanisms of liquid slip. Journal of Fluid Mechanics, 2008, 600: 257–269.CrossRefGoogle Scholar
  58. [58]
    Doi, M. and Edwards, S.F., The Theory of Polymer Dynamics. Oxford: Calderon Press, 1986.Google Scholar
  59. [59]
    Yin, J., Zhao, Y.P. and Zhu, R.Z., Molecular dynamics simulation of barnacle cement. Materials Science and Engineering A, 2005, 409: 160–166.CrossRefGoogle Scholar
  60. [60]
    Berker, A., Chynoweth, S., Klomp, U.C. and Michopoulos, Y., Non-equilibrium molecular dynamics (NEMD) simulations and the rheological properties of liquid n-hexadecane. Journal of the Chemical Society-Faraday Transactions, 1992, 88: 1719–1725.CrossRefGoogle Scholar
  61. [61]
    Thompson, P.A., Robbins, M.O. and Grest, G.S., Structure and shear response in nanometer thick films. Israel Journal of Chemistry, 1995, 35: 93–106.CrossRefGoogle Scholar
  62. [62]
    Wohlfarth, C. and Wohlfahrt, B., Pure Organic Liquids. New York: Springer, 2002.Google Scholar

Copyright information

© The Chinese Society of Theoretical and Applied Mechanics and Technology 2011

Authors and Affiliations

  1. 1.State Key Laboratory of Nonlinear MechanicsInstitute of Mechanics, Chinese Academy of SciencesBeijingChina

Personalised recommendations