Linear viscoelastic behavior of perfluorooctyl sulfonate micelles: effects of counter-ions |
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Authors: | Hiroshi Watanabe Tomohiro Sato Kunihiro Osaki Mutsuo Matsumoto Dobrin P Bossev Cathy E McNamee Masaru Nakahara |
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Institution: | (1) Institute for Chemical Research Kyoto University Uji, Kyoto 611-0011, Japan, JP |
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Abstract: | Linear viscoelastic behavior was investigated for aqueous solutions of perfluorooctyl sulfonate (C8F17SO−
3; abbreviated as FOS) micelles having a mixture of tetraethylammonium (N+(C2H5)4; TEA) and lithium (Li+) ions as the counter-ions. The solutions had the same FOS concentration (0.1 mol l−1) and various Li+ fractions in the counter-ions, φLi = 0−0.6, and the FOS micelles in these solutions formed threads which further organized into dendritic networks. At T ≤ 15 °C,
the terminal relaxation time τ and the viscosity η, governed by thermal scission of the networks, increased with increasing
φLi up to 0.55. A further increase of φLi resulted in decreases of τ and η and in broadening of the relaxation mode distribution. These rheological changes are discussed
in relation to the role of TEA ions in thermal scission: Previous NMR studies revealed that only a fraction of TEA ions were
tightly bound to the FOS micellar surfaces and these bound ions stabilized the thread/network structures. The concentration
of non-bound TEA ions, CTEA
*, decreased and finally vanished on increasing φLi up to φLi
* ≅ 0.6, and the concentration of the bound TEA ions significantly decreased on a further increase of φLi. The non-bound TEA ions appeared to catalyze the thermal scission of the FOS threads, and the observed increases of τ and
η for φLi < 0.55 were attributed to the decrease of CTEA
*. On the other hand, the decreases of τ and η as well as the broadening of the mode distribution, found for φLi > 0.55 (where CTEA
* ≅ 0), were related to destabilization of the FOS threads/networks due to a shortage of the bound TEA ions and to the existence
of concentrated Li+ ions. Viscoelastic data of pure FOSTEA and FOSTEA/FOSLi/TEACl solutions lent support to these arguments for the role of TEA
ions in the relaxation of FOSTEA/FOSLi solutions.
Received: 12 October 1999/Accepted: 1 November 1999 |
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Keywords: | Perfluorooctyl sulfonate threadlike micelles Dendritic network Thermal scission Non-bound tetraethylammonium counter-ion Catalyst for scission |
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