The shape of a drop centered in an axisymmetric extensional flow is determined by the viscous stresses that deform the drop and surface tension γ′ that resists the deformation. The ratio of these stresses is given by the capillary number, Ca. When Ca is small enough, the drop attains a steady shape. However, above a threshold value, Cacr, the drop elongates continuously, and no steady shape is attained. When surfactants are present on the drop interface, the surface tension is determined by the surface concentration profile, which varies throughout the deformation process. Initially, the surface tension is given by γeq′, in equilibrium with the uniform surface concentration Γeq′. When the flow is initiated, surfactant is swept toward the drop tips, reducing the surface tension there, and altering the interfacial stress balance tangentially through Marangoni stresses and normally through the Laplace pressure. In this paper, the effects of an insoluble surfactant on drop deformation are studied. In previous work, either a surface equation of state for the surface tension γ′ that is linear in the surface concentration Γ′ was used, an approximation that is valid only for dilute Γ′, or Γ′ sufficiently dilute for the linear approximation to be valid were studied. In this paper, a nonlinear surface equation of state that accounts for surface saturation and nonideal interactions among the surfactant molecules is adopted. The linear framework results are recovered for Γ′ that are sufficiently dilute. As Γ′ is increased, the effects of saturation and surfactant interactions are probed at constant initial Γeq′ and at constant initial γeq′. Finally, the case of strong intersurfactant cohesion is treated with a first-order surface phase transformation model. At moderate surface concentrations, these nonlinear phenomena strongly alter the steady drop deformations and Cacr relative to the uniform surface tension and linear equation of state results.

A drop in an axisymmetric extensional ow is studied using boundary integral methods to understand the effects of a monolayer-forming surfactant on a strongly deforming interface. Surfactants occupy area, so there is an upper bound to the surface concentration that can be adsorbed in a monolayer, Γ∞. The surface tension is a highly nonlinear function of the surface concentration Γ because of this upper bound. As a result, the mechanical response of the system varies strongly with Γ for realistic material parameters. In this work, an insoluble surfactant is considered in the limit where the drop and external fluid viscosities are equal.For Γ<Γ∞, surface convection sweeps surfactant toward the drop poles. When surface diffusion is negligible, once the stable drop shapes are attained, the interface can be divided into stagnant caps near the drop poles, where Γ is non-zero, and tangentially mobile regions near the drop equator, where the surface concentration is zero. This result is general for any axisymmetric fluid particle. For Γ near Γ∞, the stresses resisting accumulation are large in order to prevent the local concentration from reaching the upper bound. As a result, the surface is highly stressed tangentially while Γ departs only slightly from a uniform distribution. For this case, Γ is never zero, so the tangential surface velocity is zero for the steady drop shape.This observation that Γ dilutes nearly uniformly for high surface concentrations is used to derive a simplified form for the surface mass balance that applies in the limit of high surface concentration. The balance requires that the tangential flux should balance the local dilatation in order that the surface concentration profile will remain spatially uniform. Throughout the drop evolution, this equation yields results in agreement with the full solution for moderate deformations, and underscores the dominant mechanism at high deformation. The simplified balance reduces to the stagnant interface condition at steady state.Drop deformations vary non-monotonically with concentration; for Γ<Γ∞, the reduction of the surface tension near the poles leads to higher deformations than the clean interface case. For Γ near Γ∞, however, Γ dilutes nearly uniformly, resulting in higher mean surface tensions and smaller deformations. The drop contribution to the volume averaged stress tensor is also calculated and shown to vary non-monotonically with surface concentration.

No abstract

No abstract

No abstract