Staff Publications

Staff Publications

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    'Staff publications' is the digital repository of Wageningen University & Research

    'Staff publications' contains references to publications authored by Wageningen University staff from 1976 onward.

    Publications authored by the staff of the Research Institutes are available from 1995 onwards.

    Full text documents are added when available. The database is updated daily and currently holds about 240,000 items, of which 72,000 in open access.

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Record number 344443
Title Modeling of confinement-induced phase transitions for surfactant layers on amphiphilic surfaces
Author(s) Leermakers, F.A.M.; Koopal, L.K.; Lokar, W.J.; Ducker, W.A.
Source Langmuir 21 (2005)24. - ISSN 0743-7463 - p. 11534 - 11545.
DOI https://doi.org/10.1021/la051569m
Department(s) Physical Chemistry and Colloid Science
Publication type Refereed Article in a scientific journal
Publication year 2005
Keyword(s) dodecylammonium chloride solutions - interacting chain molecules - range hydrophobic forces - variable-charge surfaces - long-range - adsorbed layer - ionic surfactants - proximal adsorption - mica surfaces - nonionic surfactants
Abstract A self-consistent field model is used to consider a solution of positively charged surfactants up to its critical micellization concentration adsorbing onto two surfaces in close proximity. Each surface mimics a polystyrene sulfonate interface; that is, hydrophobic properties are combined with a (fixed) negative charge. We observe large and sudden changes in adsorption as a function of separation, which are not normally considered when interpreting surface force measurements. The parameters are chosen such that the adsorbed surfactant layer is of a monolayer type when the surfaces are far apart. A typical interaction curve is presented for a fixed surfactant chemical potential, which is extracted from the set of adsorption isotherms each with a fixed slit width. When the slit width approaches the thickness of the two surfactant layers, a first-order phase transition takes place, which is driven by the unfavorable hydrophobic-water contacts. At the transition, the average orientation of the surfactants switches from a high concentration of tails at the surface to a bilayer configuration where tail profiles from both sides merge in the center. The headgroups are pulled slightly away from the surface. The interaction force jumps from a weak electrostatic repulsion at large distances (two effectively positively charged surface layers repel each other) to a strong electrostatic attraction at short distances (the central surfactant bilayer is attracted to the oppositely charged surfaces). The amount of adsorbed surfactants tend to decrease with decreasing distance between the surfaces but suddenly increases at the transition. Because of this, we anticipate that in surface force experiments, for example, there is a hysteresis associated with this transition: the forces and also the adsorbed amounts depend not only on the distance between the surfaces but also on the history if nonsufficient equilibration times are implemented.
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