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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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▪ Abstract  Microstructure in an immiscible polymer blend consists of the size, shape, and orientation of the phases. Blends exhibit many interesting behaviors, including enhanced elasticity at small strains, drop-size hysteresis, enhanced shear thinning, and stress relaxation curves whose shapes are sensitive to deformation history. These behaviors are directly related to changes in the microstructure, which result from phase deformation, coalescence, retraction, and different types of breakup. These phenomena are reviewed, together with models that describe them. Rheological measurements can probe the microstructure because microstructure contributes directly to stress through interfacial tension. Rheo-optical experiments also provide important insights. Droplet theories explain most of the phenomena for Newtonian phases at low concentrations. Behaviors at high volume fractions or with strongly non-Newtonian phases are less well understood.

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