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.
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G.J. Fleer, M.A. Cohen-Stuart, J.M.H.M. Scheutjens, T. Cosgrove, B. Vincent, Polymers at Interfaces (Chapman & Hall, 1993)
V. Aguié-Béghin, E. Leclerc, M. Daoud, R. Douillard, J. Colloid Interface Sci. 214, 143 (1999)
G. Peng, J.-U. Sommer, A. Blumen, Eur. Phys. J. B 8, 73 (1999)
A. Hambardzumyan, V. Aguié-Béghin, M. Daoud, R. Douillard, Langmuir 20, 756 (2004)
A. Johner, J.F. Joanny, Macromolecules 23, 5299 (1990)
B.A. Noskov, S.-Y. Lin, G. Loglio, R.G. Rubio, R. Miller, Langmuir 22, 2647 (2006)
P. Ramírez, A. Stocco, J. Muñoz, R. Miller, J. Colloid Interface Sci. 378, 135 (2012)
C. Marques, J.F. Joanny, L. Leibler, Macromolecules 21, 1051 (1988)
G. Volet, C. Amiel, L. Auvray, Macromolecules 36, 3327 (2003)
C. Barentin, P. Muller, J.F. Joanny, Macromolecules 31, 2198 (1998)
C. Ligoure, L. Leibler, J. Phys. 51, 1313 (1990)
F. Millet, P. Perrin, M. Merlange, J.-J. Benattar, Langmuir 18, 8824 (2002)
F. Millet, J. Benattar, P. Perrin, Phys. Rev. E 60, 2045 (1999)
F. Millet, M. Nedyalkov, B. Renard, P. Perrin, F. Lafuma, J.-J. Benattar, Langmuir 15, 2112 (1999)
F. Millet, J.-J. Benattar, P. Perrin, Macromolecules 34, 7076 (2001)
C.M. Marques, J.F. Joanny, Macromolecules 23, 268 (1990)
P. Brandani, P. Stroeve, Macromolecules 36, 9502 (2003)
Y. Huang, M.M. Santore, Langmuir 18, 2158 (2002)
O. Théodoly, M. Jacquin, P. Muller, S. Chhun, Langmuir 25, 781 (2009)
A. Stocco, K. Tauer, S. Pispas, R. Sigel, J. Colloid Interface Sci. 355, 172 (2011)
M.G. Muñoz, F. Monroy, F. Ortega, R.G. Rubio, D. Langevin, Langmuir 16, 1094 (2000)
M.J. Skaug, J.N. Mabry, D.K. Schwartz, J. Am. Chem. Soc. 136, 1327 (2014)
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)
J.F. Douglas, H.E. Johnson, S. Granick, Science 262, 2010 (1993)
C. Monteux, C. R. Phys. 15, 775 (2014)
D.G. Dalgleish, Trends Food Sci. Technol. 8, 1 (1997)
A.E. Cárdenas-Valera, A.I. Bailey, Colloids Surf. Physicochem. Eng. Asp. 97, 1 (1995)
P. Perrin, N. Monfreux, F. Lafuma, Colloid Polym. Sci. 277, 89 (1999)
P. Perrin, F. Lafuma, J. Colloid Interface Sci. 197, 317 (1998)
A.F.H. Ward, L. Tordai, Recl. Trav. Chim. Pays-Bas 71, 572 (1952)
K.T. Wang, I. Iliopoulos, R. Audebert, Polym. Bull. 20, 577 (1988)
Y. Rotenberg, L. Boruvka, A.W. Neumann, J. Colloid Interface Sci. 93, 169 (1983)
F. Petit-Agnely, I. Iliopoulos, J. Phys. Chem. B 103, 4803 (1999)
M. Rubinstein, R.H. Colby, Polymer Physics (Oxford University Press, 2003)
F. Horkay, I. Tasaki, P.J. Basser, Biomacromolecules 1, 84 (2000)
F. Schosseler, F. Ilmain, S.J. Candau, Macromolecules 24, 225 (1991)
Z. Mao, S.B. Sinnott, J. Phys. Chem. B 105, 6916 (2001)
K. Shinoda, T. Yamaguchi, R. Hori, Bull. Chem. Soc. Jpn. 34, 237 (1961)
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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
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DOI: https://doi.org/10.1140/epje/i2018-11711-y