Influence of fluorination on barrier properties of polymers: Insights from Monte Carlo simulations of eicosanes + methane

Regular Article


Fluorination is widely used to improve the resistance and physical properties of polymers that are cheap to manufacture. This process improves the resistance properties of unfluorinated materials. This study examines the effects of varying the degree of fluorination on the clustering and absorption behaviour of methane n-eicosane. Monte Carlo simulations were performed for several different pressure values, at ambient temperature, to determine the uptake of methane into the eicosanes. The density of the pure eicosanes, simulated at ambient conditions, compared favourably with experimental data for the relevant polymers. The spatial configurations resulting from the absorption simulations were analysed to determine the clustering behaviour of absorbed methane. Both the prevalence of cluster formation in general, and the occurrence of specific cluster topologies of various sizes were considered. Cyclic clusters had a tendency to become more prevalent in unfluorinated eicosanes as the gas pressure was increased, while the presence of fluorine atoms on the eicosane backbone appeared to inhibit the formation of such clusters.

Graphical abstract


Soft Matter: Polymers and Polyelectrolytes 


  1. 1.
    R.J. Lagow, J.L. Margrave, Prog. Inorg. Chem. 26, 162 (1979)Google Scholar
  2. 2.
    J. Jagur-Grodzinski, Prog. Polym. Sci. 17, 361 (1992)CrossRefGoogle Scholar
  3. 3.
    J.P. Hobbs, M. Anand, Eng. Plast. 5, 247 (1992)Google Scholar
  4. 4.
    A.P. Kharitonov, J. Fluorine Chem. 103, 123 (2000)CrossRefGoogle Scholar
  5. 5.
    A.P. Kharitonov, R. Taege, G. Ferrier, V.V. Teplyakov, D.A. Syrtsova, G.H.J. Koops, J. Fluorine Chem. 126, 251 (2005)CrossRefGoogle Scholar
  6. 6.
    A.P. Kharitonov, DSc Thesis, Chernogolovka, Russia (2005)Google Scholar
  7. 7.
    V.G. Nazarov, Surface Modification of Polymers (Moscow State University Printing, Moscow, 2008)Google Scholar
  8. 8.
    A.P. Kharitonov, L.N. Kharitonova, R. Taege, G. Ferrier, E. Durand, A. Tressaud, L'Actualite Chim. N. 301/302, 130 (2006)Google Scholar
  9. 9.
    R. Taege, G. Ferrier, A.P. Kharitonov, European Patent Application EP1609815 A1, Publ. December 28 (2005)Google Scholar
  10. 10.
    P.A.B. Carstens, S.A. Marais, C.J. Thompson, J. Fluorine Chem. 104, 97 (2000)CrossRefGoogle Scholar
  11. 11.
    R. Taege, G. Ferrier, Eur. Coat. J. 5-6, 36 (2006)Google Scholar
  12. 12.
    Z. Hruska, International Conference on Fluorine in Coatings---IV, Brussels, Paper 34 (2001)Google Scholar
  13. 13.
    A. Tressaud, E. Durand, C. Labrugère, A.P. Kharitonov, L.N. Kharitonova, J. Fluorine Chem. 128, 378 (2007)CrossRefGoogle Scholar
  14. 14.
    R.J. Lagow, J.L. Margrave, J. Polym. Sci., Pol. Lett. Ed. 12, 177 (1974)CrossRefGoogle Scholar
  15. 15.
    A.P. Kharitonov, Prog. Org. Coat. 61, 192 (2008)CrossRefGoogle Scholar
  16. 16.
    E. Johansson, P. Ahlström, in Lecture Notes in Computer Science, edited by B. Kågström, E. Elmroth, J. Dongarra, J. Waśniewski, Vol. 4699 (Springer, Berlin, 2007) p. 59Google Scholar
  17. 17.
    E. Johansson, K. Bolton, D. Theodorou, P. Ahlström, J. Chem. Phys. 126, 224902 (2007)ADSCrossRefGoogle Scholar
  18. 18.
    E.L. Johansson, PhD Thesis, Chalmers University of Technology, Göteborg (2007)Google Scholar
  19. 19.
    M. Lasich, E.L. Johansson, D. Ramjugernath, Mol. Simul. 39, 367 (2013)CrossRefGoogle Scholar
  20. 20.
    G. Dlubek, K. Saarinenen, H.M. Fretwell, J. Polym. Sci. B Polym. Phys. 36, 1513 (1998)ADSCrossRefGoogle Scholar
  21. 21.
    Y. Chen, Q.L. Liu, M. Zhu, Q.G. Zhang, J.Y. Wu, J. Membrane Sci. 348, 204 (2010)CrossRefGoogle Scholar
  22. 22.
    M. Rahmati, H. Modarress, R. Gooya, Polymer 53, 1939 (2012)CrossRefGoogle Scholar
  23. 23.
    P. Memari, V. Lachet, B. Rousseau, Polymer 51, 4978 (2010)CrossRefGoogle Scholar
  24. 24.
    P. Memari, V. Lachet, M.-H. Klopffer, B. Flaconnèche, B. Rousseau, J. Membrane Sci. 390-391, 194 (2012)CrossRefGoogle Scholar
  25. 25.
    T. Li, D.O. Kildsig, K. Park, J. Controlled Release 48, 57 (1997)CrossRefGoogle Scholar
  26. 26.
    A.K. Rappe, C.J. Casewit, K.S. Colwell, W.A. Goddard III, W.M. Skiff, J. Am. Chem. Soc. 114, 10024 (1992)CrossRefGoogle Scholar
  27. 27.
    D.W. van Krevelen, Properties of Polymers: Their Correlation with Chemical Structure, Their Numerical Estimation and Prediction from Additive Group Contributions (Elsevier, Amsterdam, 1990)Google Scholar
  28. 28.
    R.L. June, A.T. Bell, D.N. Theodorou, J. Phys. Chem. 95, 8866 (1991)CrossRefGoogle Scholar
  29. 29.
    B. Ameduri, Chem. Rev. 109, 6632 (2009)CrossRefGoogle Scholar
  30. 30.
    P.J. Rae, D.M. Dattelbaum, Polymer 45, 7615 (2004)CrossRefGoogle Scholar
  31. 31.
    N. Metropolis, A.W. Rosenbluth, M.N. Rosenbluth, A.H. Teller, E. Teller, J. Chem. Phys. 21, 1087 (1953)ADSCrossRefGoogle Scholar
  32. 32.
    M.G. Martin, Mol. Simul. 39, 1212 (2013)CrossRefGoogle Scholar
  33. 33.
    Y. Chen, Q.L. Liu, A.M. Zhu, Q.G. Zhang, J.Y. Wu, J. Membrane Sci. 348, 204 (2010)CrossRefGoogle Scholar
  34. 34.
    I.R. McDonald, Mol. Phys. 23, 41 (1972)ADSCrossRefGoogle Scholar
  35. 35.
    A.Z. Panagiotopoulos, Mol. Phys. 61, 813 (1987)ADSCrossRefGoogle Scholar
  36. 36.
    A.Z. Panagiotopoulos, N. Quirke, M. Stapleton, D.J. Tildesley, Mol. Phys. 63, 527 (1988)ADSCrossRefGoogle Scholar
  37. 37.
    I. Langmuir, J. Am. Chem. Soc. 40, 1361 (1918)CrossRefGoogle Scholar
  38. 38.
    F.H. Stillinger, J. Chem. Phys. 38, 1486 (1963)ADSCrossRefGoogle Scholar
  39. 39.
    A.G. Kalinichev, J.D. Bass, J. Phys. Chem. A 101, 9720 (1997)CrossRefGoogle Scholar
  40. 40.
    J.E. Lennard-Jones, Proc. Phys. Soc. 43, 461 (1931)ADSCrossRefGoogle Scholar
  41. 41.
    M.D. Hanwell, D.E. Curtis, D.C. Lonie, T. Vandermeersch, E. Zurel, G.R. Hutchison, J. Cheminformatics 4, 17 (2012)CrossRefGoogle Scholar
  42. 42.
    W.L. Jorgensen, J.D. Madura, C.J. Swenson, J. Am. Chem. Soc. 106, 6638 (1984)CrossRefGoogle Scholar
  43. 43.
    M.G. Martin, J.I. Siepmann, J. Phys. Chem. B 102, 2569 (1998)CrossRefGoogle Scholar
  44. 44.
    U.W. Gedde, Polymer Physics, 1st edition (Chapman and Hall, London, 1995)Google Scholar
  45. 45.
    F. Sarrasin, P. Memari, M.H. Klopffer, V. Lachet, C. Taravel Condat, B. Rousseau, E. Espuche, J. Membr. Sci. 490, 380 (2015)CrossRefGoogle Scholar
  46. 46.
    N. von Solms, N. Zecchin, A. Rubin, S.I. Anderson, E.H. Stenby, Eur. Polym. J. 41, 341 (2005)CrossRefGoogle Scholar
  47. 47.
    V. Stannett, J. Membrane Sci. 3, 97 (1978)CrossRefGoogle Scholar

Copyright information

© EDP Sciences, SIF, Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  1. 1.Thermodynamics Research Unit, School of EngineeringUniversity of KwaZulu-NatalDurbanSouth Africa

Personalised recommendations