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Direct Impact of Nonequilibrium Aggregates on the Structure and Morphology of Pdadmac/SDS Layers 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 Physical Chemistry, Lund University, P.O. Box 124, S-221 00 Lund, Sweden
§ Department of Chemistry, Durham University, South Road, DH1 3LE Durham, United Kingdom
Chemical Faculty, St. Petersburg State University, Universitetsky pr. 2, 198904 St. Petersburg, Russia
Institute of Chemistry, Eötvös Loránd University, Budapest 112, P.O. Box 32, H-1518 Hungary
*Tel: +33 476 207 097. E-mail: [email protected]
*Tel: +36 204 890 440. E-mail: [email protected]
Cite this: Langmuir 2014, 30, 29, 8664–8674
Publication Date (Web):July 2, 2014
Copyright © 2014 American Chemical Society

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    Abstract Image

    We discuss different nonequilibrium mechanisms by which bulk aggregates directly modify, and can even control, the interfacial structure and morphology of an oppositely charged polyelectrolyte/surfactant (P/S) mixture. Samples are categorized at the air/water interface with respect to the dynamic changes in the bulk phase behavior, the bulk composition, and the sample history using complementary surface-sensitive techniques. First, we show that bulk aggregates can spontaneously interact with the adsorption layer and are retained in it and that this process occurs most readily for positively charged aggregates with an expanded structure. In this case, key nonequilibrium issues of aggregate dissociation and spreading of surface-active material at the interface have a marked influence on the macroscopic interfacial properties. In a second distinct mechanism, aggregates inherently become trapped at the interface during its creation and lateral flocculation occurs. This irreversible process is most pronounced for aggregates with the lowest charge. A third mechanism involves the deposition of aggregates at interfaces due to their transport under gravity. The specificity of this process at an interface depends on its location and is mediated by density effects in the bulk. The prevalence of each mechanism critically depends on a number of different factors, which are outlined systematically here for the first time. This study highlights the sheer complexity by which aggregates can directly impact the interfacial properties of a P/S mixture. Our findings offer scope for understanding seemingly mysterious irreproducible effects which can compromise the performance of formulations in wide-ranging applications from foams to emulsions and lubricants.

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