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Multilayers of sodium salt of poly(4-styrene sulfonate) (PSS) and poly(diallyl dimethyl ammonium) chloride (PDADMAC) have been built layer by layer (LbL) both at the solid/aqueous interface (solid supported) and the air/aqueous interface (liquid supported). For the solid-supported multilayers, the adsorption kinetics and the complex shear modulus were measured using a dissipative quartz crystal microbalance and a null ellipsometer. A bubble tensiometer was used to measure the adsorption kinetics and the elasticity modulus of the liquid-supported multilayers. At the solid/aqueous interface, adsorption kinetics changes with the number of adsorbed layers. However, at the air/aqueous interface, PSS dynamics were the same for all adsorbed layers except the first. Conversely, the adsorption kinetics of PDADMAC at the air/water surface differed between those layers close to the interface and those far from it. Multilayers grow at the air/water interface by an intrinsic-charge-compensation process, whereas, for the same ionic strengths, solid-supported layers deposit by the extrinsic-charge-compensation process. No significant differences were found between the recoverable dilational storage modulus of the liquid-supported multilayers and the real part of the shear modulus of the solid-supported ones built at the same ionic strength. The values of the modulus are in the MPa range, which corresponds to gel-like films. This result is in agreement with the strong hydration degree of the LbL films calculated from ellipsometry measurements.

We describe the dynamic behavior of both surface and bulk of mixed aqueous solutions of surfactants and polymers of opposite electrical charges. We evidence the importance of the point of equivalence of charges (EP), which occurs well before precipitation in our systems. Close to EP, an adsorption barrier, possibly due to charge reversal, starts to build up at the surface. In the bulk, the surfactant not only screens the polymer charges but is likely to start binding to the polymer chains.

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The structure and the interaction potential of monolayers of charged polystyrene microparticles at fluid interfaces have been studied by optical microscopy. Microparticles of different sizes have been studied over a broad range of surface particle densities. The structural characterization is based on the analysis of images obtained by digital optical microscopy. From the experimental images, radial distribution functions, hexagonal bond order correlation functions, and temporal orientational correlation functions have been calculated for different monolayer states at both the air/water and oil/water interfaces. The interaction potential has been calculated from the structure factor using integral equations within the hypernetted chain closure relationship. For particles trapped at the oil-water interface, it was found that, upon increasing the surface coverage, a freezing transition occurs, that leads to the formation of a 2D crystalline structure. We have studied the freezing densities of particle monolayers at the oil/water interface and compared them with Monte Carlo simulation results reported by H. Löwen. In contrast, at the air-water interface, freezing is inhibited due to the formation of particle aggregates.

We address a systematic study of the three-phase contact angle, θ, of microparticles at flat fluid-liquid interfaces by using different experimental methods. We measured the dependence of θ not only on the particle chemical composition and size, but also on the solvent used to spread the microparticles onto the fluid interface. We found a non-expected and non-regular dependence of θ with size, chemical nature and spreading solvent used for the different particles studied. We propose that these dependences are due to porosity/roughness of the particles that allows the adsorption of the spreading solvent onto the solid particle surface. This conclusion is supported by the values of the line tensions estimated for the different systems.