The effect of surfactants on drop deformation and on the rheology of dilute emulsions in Stokes flow

The effect of an insoluble surfactant on the transient deformation and asymptotic shape of a spherical drop that is subjected to a linear shear or extensional flow at vanishing Reynolds number is studied using a numerical method. The viscosity of the drop is equal to that of the ambient fluid, and the interfacial tension is assumed to depend linearly on the local surfactant concentration. The drop deformation is affected by non-uniformities in the surface tension due to the surfactant molecules convection-diffusion. The numerical procedure combines the boundary-integral method for solving the equations of Stokes flow, and a finite-difference method for solving the unsteady convection-diffusion equation for the surfactant concentration over the evolving interface. The parametric investigations address the effect of the ratio of the vorticity to the rate of strain of the incident flow, the Peclet number expressing the ability of the surfactant to diffuse, the elasticity number expressing the sensitivity of the surface tension to Variations in surfactant concentration, and the capillary number expressing the strength of the incident flow. At small and moderate capillary numbers, the effect of a surfactant in a non-axisymmetric flow is found to be similar to that in axisymmetric straining flow studied by previous authors. The accumulation of surfactant molecules at the tips of an elongated drop decreases the surface tension locally and promotes the deformation, whereas the dilution of the surfactant over the main body of the drop increases the surface tension and restrains the deformation. At large capillary numbers, the dilution of the surfactant and the rotational motion associated with the vorticity of the incident how work synergistically to increase the critical capillary number beyond which the drop exhibits continuous elongation. The numerical results establish the regions of validity of the small-deformation theory developed by previous authors, and illustrate the influence of the surfactant on the flow kinematics and on the rheological properties of a dilute suspension. Surfactants have a stronger effect on the rheology of a suspension than on the deformation of the individual drops.