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Dynamic Adsorption of Weakly Interacting Polymer/Surfactant Mixtures at the Air/Water Interface

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Institut Laue-Langevin, 6 rue Jules Horowitz, BP 156, 38042 Grenoble Cedex 9, France
Department of Chemistry, Durham University, South Road, Durham DH1 3LE, United Kingdom
Cite this: Langmuir 2012, 28, 34, 12479–12492
Publication Date (Web):July 2, 2012
Copyright © 2012 American Chemical Society

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    The dynamic adsorption of polymer/surfactant mixtures containing poly(ethylene oxide) (PEO) with either tetradecyltrimethylammonium bromide (C14TAB) or sodium dodecyl sulfate (SDS) has been studied at the expanding air/water interface created by an overflowing cylinder, which has a surface age of 0.1–1 s. The composition of the adsorption layer is obtained by a new approach that co-models data obtained from ellipsometry and only one isotopic contrast from neutron reflectometry (NR) without the need for any deuterated polymer. The precision and accuracy of the polymer surface excess obtained matches the levels achieved from NR measurements of different isotopic contrasts involving deuterated polymer, and requires much less neutron beamtime. The PEO concentration was fixed at 100 ppm and the electrolyte concentration at 0.1 M while the surfactant concentration was varied over three orders of magnitude. For both systems, at low bulk surfactant concentrations, adsorption of the polymer is diffusion-controlled while surfactant adsorption is under mixed kinetic/diffusion control. Adsorption of PEO is inhibited once the surfactant coverage exceeds 2 μmol m–2. For PEO/C14TAB, polymer adsorption drops abruptly to zero over a narrow range of surfactant concentration. For PEO/SDS, inhibition of polymer adsorption is much more gradual, and a small amount remains adsorbed even at bulk surfactant concentrations above the cmc. The difference in behavior of the two mixtures is ascribed to favorable interactions between the PEO and SDS in the bulk solution and at the surface.

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    Supplementary information on the following topics: determination of the optimum footprint for use in NR measurements, further settings of NR experiments, fitting NR data, validation of negligible isotope effects in the co-modelling approach, PEO/C14TAB co-modelling using the linear function to represent the surfactant, PEO/SDS co-modelling using the cubic function to represent the surfactant, static PEO/SDS data, and Volmer adsorption isotherm for static data PEO/SDS data. This information is available free of charge via the Internet at

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