Abstract
In this paper we present the findings of our investigations using molecular dynamics, on molecularly thin films of n-octane confined between topographically smooth solid surfaces. We focus on the effect of increasing solid surface-methylene unit energetic affinity and the effect of increasing pressure (normal load) of the film in inducing liquid-solid phase transitions. We observed an abrupt transition in the structural features of the film at a critical value of the characteristic energy that quantified the affinity between solid surfaces and methylene units. This energetically driven transition was evident from the discontinuous increase of intermolecular order, a precipitous extension of the octane molecules and freezing of molecular migration and rotation. Increasing pressure had a similar effect in inducing a liquid-solid phase transition. The characteristics of the transition showed that it is a mild first order transition from a highly ordered liquid to a poorly organized solid. These findings demonstrate that the solidification of nanoscopically thin films of linear alkanes is a general phenomenon (driven either energetically or by increasing pressure), and does not require the aid of commensurate surface topography.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Alder, B.J. and T.E. Wainwright, Phys. Rev., 127, 359 (1962).
Allen, M.P. and D.J. Tildesley, Computer Simulation of Liquids, p. 292, Oxford Publ., 1989.
van Alsten, J. and S. Granick, Phys. Rev. Lett., 61, 2570 (1988).
Andrea, T.A., W.C. Swope, and H.C. Anderson, J Chem. Phys., 79, 4576 (1983).
Bitsanis, I., J.J. Magda, M. Tirrell, and H.T. Davis, J. Chem. Phys., 87, 1733 (1987).
Bitsanis, I., S.A. Somers, H.T. Davis, and M. Tirrell, J. Chem. Phys., 93, 3427 (1990).
Bitsanis, I.A. and C. Pan, J. Chem. Phys., 99, 5520 (1993).
Chan, D.Y. and R.G. Horn, J. Chem. Phys., 83, 5311 (1985).
Denn, M.M., Ann. Rev. Fluid Mech., 22, 13 (1990).
Edberg, R., D.J. Evans, and R.J. Moriss, J. Chem. Phys., 84, 6933 (1986).
Fixmann, M., J. Chem. Phys., 69, 1527 (1978).
Granick, S., Science, 253, 1374 (1991).
Gupta, S., D.C. Koopman, G.B. Westermann-Clark, and I.A. Bitsanis, J. Chem. Phys., 100, 8444 (1994).
Gupta, S., G.B. Westermann-Clark, and I. Bitsanis, J. Chem. Phys., 98, 634 (1993).
Hamza, A.V. and R.J. Madix, Surf. Sci., 179, 25 (1987).
Hentske, R., B.L. Schurmann, and J.P. Rabe, J. Chem. Phys., 92, 6213 (1992).
Homola, A.M., H.V. Nguyen, and G. Hadziioannou, J. Chem. Phys., 94, 2346 (1991).
Homola, A.M., G.B. Street, and C.M. Mate, MRS Bulletin, XV(3), 45 (1990).
Israelachvili, J.N., and D. Tabor, Proc. R. Soc. London Ser. A, 331, 19 (1972).
Israelachvili, J.N. and G.E. Adams, J. Chem. Soc. Faraday Trans., 174, 975 (1978).
Israelachvili, J.N., P.M. McGuiggan, and A.M. Homola, Science, 240, 189 (1988).
van Kampen, N.G., Stochastic Processes in Physics and Chemistry, North Holland Publ., 1981.
van Kampen, N.G., Appl. Sci. Res., 37, 67 (1981).
Koopman, D.C., S. Gupta, R.K. Ballamudi, G.B. Westermann-Clark, and I.A. Bitsanis, Chem. Eng. Sci, 49, 2907 (1994).
Knudstrup, T.K., I.A. Bitsanis, and G.B. Westermann-Clark, Langmuir (1994) (accepted).
Magda, J.J., M. Tirrell, and H.T. Davis, J. Chem. Phys., 83, 1888 (1985).
Mayer, J.E. and W.W. Wood, J. Chem. Phys., 42, 4268 (1965).
Mongomery Jr., J.A., S.L. Holmgren, and D. Chandler, J. Chem. Phys., 73, 3688 (1980).
Nicholson, D. and N.G. Parsonage, Computer Simulation and the Statistical Mechanics of Adsorption, Academic Press, 1982.
Nikolov, A.D. and D.T. Wasan, J. Coll. Inter. Sci., 133, 1 (1989); 133, 13 (1989).
Nikolov, A.D., D.T. Wasan, N.D. Denkov, P.A. Kralchesvky, and I.B. Ivanov, Prog. Coll. Pol. Sci., 82, 1 (1990).
Padilla, P. and S. Toxvaerd, J. Chem Phys., 94, 5650 (1991).
Peanasky, J., L.L. Cai, and S. Granick, Macromolecules 1994 (in print).
Rabe, J.P. and S. Buchholz, Phys. Rev. Lett., 66, 2096 (1991).
Rigby, D. and R.J. Roe, J. Chem. Phys., 87, 7285 (1987).
Ryckaert, J.P. and A. Bellemans, Faraday Discuss. Chem. Soc., 66, 95 (1978).
Ryckaert, J.P., G. Ciccotti, and H.L.C. Berendsen, J. Comput. Phys., 23, 327 (1977).
Schoen, M., J.H. Cushman, D.J. Diestler, and C.L. Rhykerd Jr., J. Chem. Phys., 88, 1394 (1988).
Tabor D. and R.H.S. Winterton, Proc. R. Soc. London Ser. A, 312, 543 (1969).
Thompson, P.A. and M.O. Robbins, Phys. Rev. A, 41, 6830 (1990).
Thompson, P.A., G.S. Grest, and M.O. Robbins, Phys. Rev. Lett., 68, 3448 (1992).
Toxvaerd, S.J., J. Chem. Phys., 93, 4290 (1990).
Weber, T.A., J. Chem. Phys., 69, 2347 (1978); 70, 4277 (1979).
Xia, T.K., J. Quyang, M.W. Ribarsky, and U. Landman, Phys. Rev. Lett., 69, 1967 (1992).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Ballamudi, R.K., Bitsanis, I.A. Structural transitions at solid-liquid interfaces. Adsorption 2, 69–76 (1996). https://doi.org/10.1007/BF00127100
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00127100