The effects of surfactants on drop deformation and breakup

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Abstract
The effects of surface-active agents on drop deformation and breakup in extensional flows at low Reynolds numbers are described. In this free-boundary problem, determination of the interfacial velocity requires knowledge of the distribution of surfactant, which, in turn, requires knowledge of the interfacial velocity field. We account for this explicit coupling of the unknown drop shape and the evolving surfactant distribution. An analytical result valid for nearly spherical distortions is presented first. Finite drop deformation is studied numerically using the boundary-integral method in conjunction with the time-dependent convective–diffusion equation for surfactant transport. This procedure accurately follows interfacial tension variations, produced by non-uniform surfactant distribution, on the evolving interface. The numerical method allows for an arbitrary equation of state relating interfacial tension to the local concentration of surfactant, although calculations are presented only for the common linear equation of state. Also, only the case of insoluble surfactant is studied.The analytical and numerical results indicate that at low capillary numbers the presence of surfactant causes larger deformation than would occur for a drop with a constant interfacial tension equal to the initial equilibrium value. The increased deformation occurs owing to surfactant being swept to the end of the drop where it acts to locally lower the interfacial tension, which therefore requires increased deformation to satisfy the normal stress balance. However, at larger capillary numbers and finite deformations, this convective effect competes with ‘dilution’ of the surfactant due to interfacial area increases. These two different effects of surface-active material are illustrated and discussed and their influence on the critical capillary number for breakup is presented.