Oriented Assembly of Anisotropic Particles by Capillary Interactions

Particles situated at fluid interfaces occur in nature, with the particles ranging from pollen to insects which walk on water. Particles at interfaces are exploited in classical applications like Pickering emulsions, in which particles stabilize emulsions, and froth flotation, in which ore particle adsorption to fluid interfaces is used to separate and recover metal ores. Particles at interfaces also occur in emerging applications in which nanomaterials are organized at interfaces. The assembly of particles into ordered structures via capillary interactions is studied. Early work in this field focused primarily on spherical particles that distort fluid interfaces and create excess area. The particles assembled by capillary interactions which occur because the excess area created by the particles decreases as the particles approach each other. Here, particles with shape anisotropy are studied. Such particles create undulations with excess area that can be locally elevated at certain locations around the particle. The local elevation of excess area makes these sites locations for preferred assembly. Hence, particles orient and aggregate in preferred orientations. Such self assembly is often termed directed assembly. Three key issues in directed assembly are means of controlling the object orientation, alignment, and the sites for preferred assembly, including means of promoting registry of features on particles. Each of these issues is addressed in detail in for the example of a right circular cylinder using analysis, experiment and numerics. A series of other shapes are then studied to illustrate the generality of the concepts developed

Droplet Deformation in an Extensional Flow: The Role of Surfactant Physical Chemistry

Surfactant-induced Marangoni effects strongly alter the stresses exerted along fluid particle interfaces. In low gravity processes, these stresses can dictate the system behavior. The dependence of Marangoni effects on surfactant physical chemistry is not understood, severely impacting our ability to predict and control fluid particle flows. A droplet in an extensional flow allows the controlled study of stretching and deforming interfaces. The deformations of the drop allow both Marangoni stresses, which resist tangential shear, and Marangoni elasticities, which resist surface dilatation, to develop. This flow presents an ideal model system for studying these effects. Prior surfactant-related work in this flow considered a linear dependence of the surface tension on the surface concentration, valid only at dilute surface concentrations, or a non-linear framework at concentrations sufficiently dilute that the linear approximation was valid. The linear framework becomes inadequate for several reasons. The finite dimensions of surfactant molecules must be taken into account with a model that includes surfaces saturation. Nonideal interactions between adsorbed surfactant molecules alter the partitioning of surfactant between the bulk and the interface, the dynamics of surfactant adsorptive/desorptive exchange, and the sensitivity of the surface tension to adsorbed surfactant. For example, cohesion between hydrocarbon chains favors strong adsorption. Cohesion also slows the rate of desorption from interfaces, and decreases the sensitivity of the surface tension to adsorbed surfactant. Strong cohesive interactions result in first order surface phase changes with a plateau in the surface tension vs surface concentration. Within this surface concentration range, the surface tension is decoupled from surface concentration gradients. We are engaged in the study of the role of surfactant physical chemistry in determining the Marangoni stresses on a drop in an extensional flow in a numerical and experimental program. Using surfactants whose dynamics and equilibrium behavior have been characterized in our laboratory, drop deformation will be studied in ground-based experiment. In an accompanying numerical study, predictive drop deformations will be determined based on the isotherm and equation of state determined in our laboratory. This work will improve our abilities to predict and control all fluid particle flows