R. von Klitzing

Complexes of surfactants with oppositely charged polymers at surfaces and in bulk

Addition of surfactants to aqueous solutions of polyelectrolytes carrying an opposite charge causes the spontaneous formation of complexes in the bulk phase in certain concentration ranges. Under some conditions, compact monodisperse multichain complexes are obtained in the bulk. The size of these complexes depends on the mixing procedure and it can be varied in a controlled way from nanometers up to micrometers. The complexes exhibit microstructures analogous to those of the precipitates formed at higher concentrations. In other cases, however, the bulk complexes are large, soft and polydisperse. In most cases, the dispersions are only kinetically stable and exhibit pronounced non-equilibrium features. Association at air-water interfaces readily occurs, even at very small concentrations. When the surfactant concentration is small, the surface complexes are usually made of a surfactant monolayer to which the polymer binds and adsorbs in a flat-like configuration. However, under some conditions, thicker layers can be found, with bulk complexes sticking to the surface. The association at solid-water interfaces is more complex and depends on the specific interactions between surfactants, polymers and the surface. However, the behaviour can be understood if distinctions between hydrophilic surfaces and hydrophobic surfaces are made. Note that the behaviour at air-water interfaces is closer to that of hydrophobic than that of hydrophilic solid surfaces. The relation between bulk and surface complexation will be discussed in this review. The emphasis will be given to the results obtained by the teams of the EC-funded Marie Curie RTN SOCON.

Effect of ionic strength and type of ions on the structure of water swollen polyelectrolyte multilayers

This study addresses the effect of ionic strength and type of ions on the structure and water content of polyelectrolyte multilayers. Polyelectrolyte multilayers of poly(sodium-4-styrene sulfonate) (PSS) and poly(diallyl dimethyl ammonium chloride) (PDADMAC) prepared at different NaF, NaCl and NaBr concentrations have been investigated by neutron reflectometry against vacuum, H(2)O and D(2)O. Both thickness and water content of the multilayers increase with increasing ionic strength and increasing ion size. Two types of water were identified, void water which fills the voids of the multilayers and does not contribute to swelling but to a change in scattering length density and swelling water which directly contributes to swelling of the multilayers. The amount of void water decreases with increasing salt concentration and anion radius while the amount of swelling water increases with salt concentration and anion radius. This is interpreted as a denser structure in the dry state and larger ability to swell in water (sponge) for multilayers prepared from high ionic strengths and/or salt solution of large anions. No exchange of hydration water or replacement of H by D was detected even after eight hours incubation time in water of opposing isotopic composition.

Confinement of linear polymers, surfactants, and particles between interfaces

The review addresses the effect of geometrical confinement on the structure formation of colloidal dispersions like particle suspensions, (non)micellar surfactant solutions, polyelectrolyte solutions and mixed dispersions. The dispersions are entrapped either between two fluid interfaces (foam film) in a Thin Film Pressure Balance (TFPB) or between two solid interfaces in a Colloidal Probe Atomic Force Microscope (Colloidal Probe AFM) or a Surface Force Apparatus (SFA). The oscillating concentration profile in front of the surface leads to an oscillating force during film thinning. It is shown that the characteristic lengths like the distance between particles, the distance between micelles, or the mesh size of the polymer network remain the same during the confining process. The influence of different parameters like ionic strength, molecular structure, and the properties of the outer surfaces on the structure formation are reported. The confinement of mixed dispersions might lead to phase separation and capillary condensation, which in turn causes a pronounced attraction between the two opposing film surfaces.

The effect of polymer charge density and charge distribution on the formation of multilayers

Polyelectrolyte multilayers which are built up by alternating adsorption of polyanions and polycations from aqueous solutions at a solid interface are investigated by reflectometry and ellipsometry. Below a degree of charge of about 70% the adsorption stops after a certain number of dipping cycles and no multilayer formation occurs. This indicates an electrostatically driven adsorption process. Below a charge density of 70% an adsorption can take place if the charged segments are combined as a block of the polymer.