Adsorption dynamics of hydrophobically modified polymers at an air-water interface

Abstract.

Using surface-tension measurements, we study the brush-limited adsorption dynamics of a range of amphiphilic polymers, PAAH-\(\alpha\)-\({\rm C}_{n}\) composed of a poly(acrylic acid) backbone, PAAH, grafted with a fraction \(\alpha\) of alkyl moieties, containing either n = 8 or n = 12 carbon atoms, at pH conditions where the PAAH backbone is not charged. At short times, the surface tension decreases more sharply as the degree of grafting increases, while, at long times, the adsorption dynamics becomes logarithmic in time and is slower as the degree of grafting increases. This logarithmic behavior at long times indicates the building of a free-energy barrier which grows over time. To account for the observed surface tension evolution with the degree of grafting we propose a scenario, where the free-energy barrier results from both the deformation of the incoming polymer coils and the deformation of the adsorbed brush. Our model involves only two fitting parameters, the monomer size and the area needed for one molecule during adsorption and is in agreement with the experimental data. We obtain a reasonable value for the monomer size and find an area per adsorbed polymer chain of the order of 1 nm2, showing that the polymer chains are strongly stretched as they adsorb.

Graphical abstract

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

References

  1. 1

    G.J. Fleer, M.A. Cohen-Stuart, J.M.H.M. Scheutjens, T. Cosgrove, B. Vincent, Polymers at Interfaces (Chapman & Hall, 1993)

  2. 2

    V. Aguié-Béghin, E. Leclerc, M. Daoud, R. Douillard, J. Colloid Interface Sci. 214, 143 (1999)

    ADS  Article  Google Scholar 

  3. 3

    G. Peng, J.-U. Sommer, A. Blumen, Eur. Phys. J. B 8, 73 (1999)

    ADS  Article  Google Scholar 

  4. 4

    A. Hambardzumyan, V. Aguié-Béghin, M. Daoud, R. Douillard, Langmuir 20, 756 (2004)

    Article  Google Scholar 

  5. 5

    A. Johner, J.F. Joanny, Macromolecules 23, 5299 (1990)

    ADS  Article  Google Scholar 

  6. 6

    B.A. Noskov, S.-Y. Lin, G. Loglio, R.G. Rubio, R. Miller, Langmuir 22, 2647 (2006)

    Article  Google Scholar 

  7. 7

    P. Ramírez, A. Stocco, J. Muñoz, R. Miller, J. Colloid Interface Sci. 378, 135 (2012)

    ADS  Article  Google Scholar 

  8. 8

    C. Marques, J.F. Joanny, L. Leibler, Macromolecules 21, 1051 (1988)

    ADS  Article  Google Scholar 

  9. 9

    G. Volet, C. Amiel, L. Auvray, Macromolecules 36, 3327 (2003)

    ADS  Article  Google Scholar 

  10. 10

    C. Barentin, P. Muller, J.F. Joanny, Macromolecules 31, 2198 (1998)

    ADS  Article  Google Scholar 

  11. 11

    C. Ligoure, L. Leibler, J. Phys. 51, 1313 (1990)

    Article  Google Scholar 

  12. 12

    F. Millet, P. Perrin, M. Merlange, J.-J. Benattar, Langmuir 18, 8824 (2002)

    Article  Google Scholar 

  13. 13

    F. Millet, J. Benattar, P. Perrin, Phys. Rev. E 60, 2045 (1999)

    ADS  Article  Google Scholar 

  14. 14

    F. Millet, M. Nedyalkov, B. Renard, P. Perrin, F. Lafuma, J.-J. Benattar, Langmuir 15, 2112 (1999)

    Article  Google Scholar 

  15. 15

    F. Millet, J.-J. Benattar, P. Perrin, Macromolecules 34, 7076 (2001)

    ADS  Article  Google Scholar 

  16. 16

    C.M. Marques, J.F. Joanny, Macromolecules 23, 268 (1990)

    ADS  Article  Google Scholar 

  17. 17

    P. Brandani, P. Stroeve, Macromolecules 36, 9502 (2003)

    ADS  Article  Google Scholar 

  18. 18

    Y. Huang, M.M. Santore, Langmuir 18, 2158 (2002)

    Article  Google Scholar 

  19. 19

    O. Théodoly, M. Jacquin, P. Muller, S. Chhun, Langmuir 25, 781 (2009)

    Article  Google Scholar 

  20. 20

    A. Stocco, K. Tauer, S. Pispas, R. Sigel, J. Colloid Interface Sci. 355, 172 (2011)

    ADS  Article  Google Scholar 

  21. 21

    M.G. Muñoz, F. Monroy, F. Ortega, R.G. Rubio, D. Langevin, Langmuir 16, 1094 (2000)

    Article  Google Scholar 

  22. 22

    M.J. Skaug, J.N. Mabry, D.K. Schwartz, J. Am. Chem. Soc. 136, 1327 (2014)

    Article  Google Scholar 

  23. 23

    L. Aricov, H. Petkova, D. Arabadzhieva, A. Iovescu, E. Mileva, K. Khristov, G. Stinga, C.-F. Mihailescu, D. Florin Anghel, R. Todorov, Colloids Surf. Physicochem. Eng. Asp. 505, 138 (2016)

    Article  Google Scholar 

  24. 24

    J.F. Douglas, H.E. Johnson, S. Granick, Science 262, 2010 (1993)

    ADS  Article  Google Scholar 

  25. 25

    C. Monteux, C. R. Phys. 15, 775 (2014)

    ADS  Article  Google Scholar 

  26. 26

    D.G. Dalgleish, Trends Food Sci. Technol. 8, 1 (1997)

    Article  Google Scholar 

  27. 27

    A.E. Cárdenas-Valera, A.I. Bailey, Colloids Surf. Physicochem. Eng. Asp. 97, 1 (1995)

    Article  Google Scholar 

  28. 28

    P. Perrin, N. Monfreux, F. Lafuma, Colloid Polym. Sci. 277, 89 (1999)

    Article  Google Scholar 

  29. 29

    P. Perrin, F. Lafuma, J. Colloid Interface Sci. 197, 317 (1998)

    ADS  Article  Google Scholar 

  30. 30

    A.F.H. Ward, L. Tordai, Recl. Trav. Chim. Pays-Bas 71, 572 (1952)

    Article  Google Scholar 

  31. 31

    K.T. Wang, I. Iliopoulos, R. Audebert, Polym. Bull. 20, 577 (1988)

    Article  Google Scholar 

  32. 32

    Y. Rotenberg, L. Boruvka, A.W. Neumann, J. Colloid Interface Sci. 93, 169 (1983)

    ADS  Article  Google Scholar 

  33. 33

    F. Petit-Agnely, I. Iliopoulos, J. Phys. Chem. B 103, 4803 (1999)

    Article  Google Scholar 

  34. 34

    M. Rubinstein, R.H. Colby, Polymer Physics (Oxford University Press, 2003)

  35. 35

    F. Horkay, I. Tasaki, P.J. Basser, Biomacromolecules 1, 84 (2000)

    Article  Google Scholar 

  36. 36

    F. Schosseler, F. Ilmain, S.J. Candau, Macromolecules 24, 225 (1991)

    ADS  Article  Google Scholar 

  37. 37

    Z. Mao, S.B. Sinnott, J. Phys. Chem. B 105, 6916 (2001)

    Article  Google Scholar 

  38. 38

    K. Shinoda, T. Yamaguchi, R. Hori, Bull. Chem. Soc. Jpn. 34, 237 (1961)

    Article  Google Scholar 

Download references

Author information

Affiliations

Authors

Corresponding author

Correspondence to C. Monteux.

Electronic supplementary material

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Trégouët, C., Mikhailovskaya, A., Salez, T. et al. Adsorption dynamics of hydrophobically modified polymers at an air-water interface. Eur. Phys. J. E 41, 101 (2018). https://doi.org/10.1140/epje/i2018-11711-y

Download citation

Keywords

  • Polymers: From Adsorption to Translocation - Topical Issue in Memoriam Loïc Auvray (1956-2016)