Surfactant reorientation under shear: dynamic surface tension and droplet deformation

Abstract

Surfactants are amphiphilic molecules that are generally anisotropic rather than spherical. Their orientation is therefore governed by the interplay between shear-induced reorientation, thermal rotational diffusion, and energetic alignment with the interface. The relative importance of these processes is characterized by the rotational Peclet number, $Pe_r$. We show that this microscopic coupling between flow and surfactant orientation can give rise to new macroscopic interfacial phenomena, including a shear-dependent effective surface tension and non-trivial droplet deformation. To investigate this mechanism, we develop a phase-field model that incorporates both the surfactant concentration and its local average orientation (polarization field). Using perturbation theory, we derive an analytical expression for the effective surface tension, which depends not only on the surfactant concentration but also on the local shear rate. We then employ a hybrid numerical method to study the deformation of a surfactant-covered droplet under imposed shear flow. For small $Pe_r$, droplet deformation can be accurately captured by a modified Taylor and Maffettone-Minale theories. For large $Pe_r$, shear-induced reorientation strongly distorts the surfactant polarization, and the droplet deformation progressively approaches that of a pure (surfactant-free) droplet.