Dominique Langevin

Influence of interfacial rheology on foam and emulsion properties.

Foams and emulsions are stabilized by surfactant monolayers that adsorb at the air-water and oil-water interfaces, respectively. As a result of monolayer adsorption, the interfaces become viscoelastic. We will describe experiments showing that foaming, emulsification, foam and emulsion stability, are strongly dependent upon the value of compression elasticity and viscosity. This will include excited surface wave devices for the measurement of surface viscoelasticity and thin film videointerferometry for the study of model films between air bubbles and emulsion drops.

Complexation of oppositely charged polyelectrolytes and surfactants in aqueous solutions. A review

Addition of surfactants to aqueous solutions of polyelectrolytes causes the spontaneous formation of complexes in a certain range of concentrations. In some conditions, compact monodisperse multichain complexes are obtained (short surfactant chain length and polymer rigid enough). The size of the complexes can be varied in controlled way from nanometers up to micrometers, but depends on the mixing procedure, whereas the shape of the complexes depends on the polymer backbone rigidity. These complexes exhibit microstructures analogue to that of the precipitates formed at higher concentrations. In most cases, however, the complexes are large, soft and polydisperse.

On the origin of the remarkable stability of aqueous foams stabilised by nanoparticles: link with microscopic surface properties

We have performed a quantitative study of the coarsening of foams stabilised by partially hydrophobic silica nanoparticles. We have used a variety of techniques: optical and electron microscopy, microfluidics, and multiple light scattering. Using earlier studies of planar particle monolayers, we have been able to correlate the interfacial properties and the macroscopic temporal evolution of the foam. This has shed light on the origin of the absence of coarsening of particle-stabilised foams. Such particle-stabilised foams appear to be the only known foam system where coarsening is inhibited by surface elasticity.

Particle-stabilised foams: an interfacial study

In an attempt to elucidate the remarkable stability of foams generated from dispersions of partially hydrophobic nanoparticles (fumed silica), we present investigations into the static and dilational properties of the gas–liquid interfaces of such dispersions. By relating the dynamic surface tension γ(t) and the dilational elasticity E measured using an oscillating bubble device, we confirm that the Gibbs stability criterion E > γ/2 against foam coarsening is fulfilled. We complement these studies using ellipsometry and Brewster angle microscopy, which provide evidence for a pronounced adsorption barrier for the particles and a network-like structure in the interface at sufficiently high concentrations. We observe this structure also in freely suspended films drawn from the same particle dispersions.

Aqueous foams stabilized solely by particles

Foams are dispersions of bubbles in liquids, often water. They are frequently stabilized by surfactant or polymer, but like Pickering emulsions, they can be also stabilized solely by particles. If the particles have a moderate hydrophobicity, the foams can be extremely stable (lifetimes of the order of years). Due to technical preparation difficulties, very few studies can be found in the literature to date. We will discuss the origin of these difficulties. We will also describe experiments using partially hydrophobic fumed silica particles, in which the foam properties were correlated with the properties of spread and adsorbed layers of these particles at the air–water interface. These combined experiments allowed us to define the conditions necessary to stop bubble disproportionation.

Time evolution of aqueous foams: drainage and coarsening

We report new results on drainage and coarsening of aqueous foams. We show that these two effects can strongly interfere, enhancing the drainage velocity. Without coarsening, we have performed free-drainage experiments, in which local drainage rates are measured by electrical conductivity and by light scattering techniques. We have investigated the roles of the bubble size, of the surface and bulk rheology and of the liquid fraction. The results show that changing these foam parameters can induce transitions between different drainage regimes. The results are analysed in terms of two dimensionless numbers describing the balance between surface and bulk dissipation.

Link between surface elasticity and foam stability

We have measured the surface dilational elastic moduli of bubbles immersed in water and soap bubbles in air. The short time response was obtained by submitting the bubbles to a rapid expansion after which the surface tension evolution was monitored, using either image analysis or pressure measurements. It was possible with this method to measure directly the Gibbs elasticity. The longer time response was obtained by submitting the bubbles to low frequency oscillations. Experiments were performed with solutions of non-ionic surfactants, C12E6, C12G2, their 1:1 mixture, Pluronic F-68 and 127 and the surface elastic moduli were compared with the stability of foams made with these surfactants. The foams evolve with time, first by Ostwald ripening, controlled by the low frequency elasticity, and then by bubbles coalescence, controlled by the high frequency elasticity.

Unusually stable liquid foams.

Obtaining stable liquid foams is an important issue in view of their numerous applications. In some of these, the liquid foam in itself is of interest, in others, the liquid foam acts as a precursor for the generation of solid foam. In this short review, we will make a survey of the existing results in the area. This will include foams stabilised by surfactants, proteins and particles. The origin of the stability is related to the slowing down of coarsening, drainage or coalescence, and eventually to their arrest. The three effects are frequently coupled and in many cases, they act simultaneously and enhance one another. Drainage can be arrested if the liquid of the foam either gels or solidifies. Coalescence is slowed down by gelified foam films, and it can be arrested if the films become very thick and/or rigid. These mechanisms are thus qualitatively easy to identify, but they are less easy to model in order to obtain quantitative predictions. The slowing down of coarsening requests either very thick or small films, and its arrest was observed in cases where the surface compression modulus was large. The detail of the mechanisms at play remains unclear.

Polyelectrolyte and surfactant mixed solutions. Behavior at surfaces and in thin films

Dilute mixed solutions of non-surface active anionic polymers (polyacrylamide and polystyrene sulfonate, xanthan) and various surfactants have been studied with several methods: surface tension, ellipsometry, X-ray and neutron reflectivity, thin film balance, surface and bulk rheology. A strong synergistic lowering of the surface tension is found with cationic surfactants in the concentration range where no appreciable complexation of surfactant and polymer occurs in the bulk solution (as seen from viscosity measurements). Despite appreciable differences between surface tension behaviour, the adsorbed layer is very similar for all the polymers: their thickness is small and the polymer chains are stretched along the surface. The surface tension behaviour of these polymers with non-ionic surfactants is also different. When the polymers are confined in thin films, the forces between surfaces are similar, and independent of surfactant nature: oscillatory forces are measured, which reflect the existence of a polymer network with a well defined mesh size. The connection of foam stability with surface and bulk complexation is far from clear.

Viscoelastic properties of silica nanoparticle monolayers at the air-water interface

We have investigated the rheological behaviour of silica nanoparticle layers at the air-water interface. Both compressed and deposited layers have been studied in Langmuir troughs and with a bicone rheometer. The compressed layers are more homogeneous and rigid, and the elastic response to continuous, step and oscillatory compression are similar, provided the compression is fast enough and relaxation is prevented. The deposited layers are less rigid and more viscoelastic. Their shear moduli deduced from the oscillatory uniaxial compression are much smaller than those deduced from pure shear deformation suggesting that the effective shear rate is smaller than expected in the compression measurements.