The forces between colloidal particles at a decane-water interface, in the presence of low concentrations of a monovalent salt (NaCl) and of the surfactant sodium dodecylsulfate (SDS) in the aqueous subphase, have been studied using laser tweezers. In the absence of electrolyte and surfactant, particle interactions exhibit a long-range repulsion, yet the variation of the interaction for different particle pairs is found to be considerable. Averaging over several particle pairs was hence found to be necessary to obtain reliable assessment of the effects of salt and surfactant. It has previously been suggested that the repulsion is consistent with electrostatic interactions between a small number of dissociated charges in the oil phase, leading to a decay with distance to the power -4 and an absence of any effect of electrolyte concentration. However, the present work demonstrates that increasing the electrolyte concentration does yield, on average, a reduction of the magnitude of the interaction force with electrolyte concentration. This implies that charges on the water side also contribute significantly to the electrostatic interactions. An increase in the concentration of SDS leads to a similar decrease of the interaction force. Moreover the repulsion at fixed SDS concentrations decreases over longer times. Finally, measurements of threebody interactions provide insight into the anisotropic nature of the interactions. The unique time-dependent and anisotropic interactions between particles at the oil-water interface allow tailoring of the aggregation kinetics and structure of the suspension structure.2

The controlled generation of 2D aggregate networks is studied experimentally using micrometer-sized polystyrene latex particles attached to the oil-water interface. Starting from an initially crystalline monolayer, appropriate combinations of carefully added electrolyte and surfactant enable control over both the fractal dimension and the kinetics of aggregation. Remarkably, the colloidal crystals formed upon first spreading remain stable, even for days, when substantial amounts of electrolyte are added to the aqueous phase. Pressure-area isotherms reveal a slow time evolution of the electrostatic dipole-dipole interaction. When the electrostatic interaction has been sufficiently weakened, aggregation proceeds in well-defined, reproducible manner. The aggregation process is analyzed using quantitative video microscopy. The evolution of the cluster size distribution and its moments is characterized, and static and dynamic scaling exponents are derived to identify the nature of the aggregation process. In the range of concentrations studied here, the kinetics all agree with a "fast", diffusion-limited cluster type of aggregation. However, the fractal dimension strongly depends on the composition of the aqueous subphase. Rather dense structures are found when only electrolyte is used, whereas more open structures are obtained when even small amounts of surfactant are added. It is suggested that this structural dependency is related to the effect of surfactant on the contact angle and its consequences for the anisotropic nature of the capillary interactions.

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The interfacial rheological properties of stable and weakly aggregated two-dimensional suspensions are studied experimentally using a magnetic rod interfacial rheometer. Particle monolayers with well controlled structures were prepared. Charged polystyrene particles create two-dimensional colloidal crystals at the water-decane interface over a wide range of concentrations. Under similar conditions a predominantly liquid structure is obtained at the water-air interface for the same particles. The addition of appropriate combinations of the anionic surfactant sodiumdodecylsulfate (SDS) and sodium chloride (NaCl) to the aqueous subphase leads to a destabilization of these monolayers with the formation of fractal aggregates at low concentrations and a heterogeneous gel forming as the surface coverage is increased. After the structures have been built up a reproducible structure can be obtained, of which the interfacial rheological properties can be investigated using a magnetic rod stress rheometer. In all cases, numerical calculations were used to assess the importance of instrumental artifacts and the effect of the coupling between surface and subphase flows. The rheology of aggregated suspensions was compared to the reference case of a colloidal crystal. The two-dimensional aggregated suspensions display rheological features which are similar to their three-dimensional counterparts. These include an elastic response with small linearity limits, a power law dependence on surface coverage and a dependence on the strength of attraction. The results shed some light on the possible role of interfacial rheology on the stability of particle laden high interface systems. Additionally, the 2D suspensions could present fundamental insights in the rheological properties of dense colloidal suspensions.