Excitation of relaxation oscillations at a curved interface under the conditions of an internal problem

The oscillatory mode of solutal Marangoni convection during the absorption of a surfactant from a homogeneous external solution into a water droplet is studied numerically. This is caused by the effect of gravity, which promotes the sedimentation of surfactant molecules in an aqueous medium. This version of oscillatory convection arising under the conditions of an internal problem was recently discovered experimentally. In the present paper, we consider the case of a chemically inert system, in which there are no reactions. The effects of interfacial deformation are assumed to be insignificant and thus they are neglected. The mathematical model includes the Navier-Stokes equations written in the Hele-Shaw and Boussinesq approximations, and the equations of surfactant transport in the system. We assume that the characteristic time of surfactant adsorption is shorter than the time of its diffusion in both solutions, which makes it possible to ignore the formation of a surface phase. The boundary value problem includes the equilibrium condition of the system, which takes into account different values of the chemical potential in the phases. It is shown that a water droplet is a surfactant accumulator that diffuses from the organic phase. The problem is solved in dimensional form using the COMSOL Multiphysics package and based on a set of physical constants for acetic acid which, like many other members of the carboxylic acid family, has the properties of surfactant in water. It was found that direct numerical simulation of the system is able to reproduce the relaxation oscillations observed in the experiment only under the additional phenomenological assumption of non-Newtonian rheology of the interface, which was previously proposed for the external problem. The physical mechanism which may be responsible for the delayed onset of Marangoni instability is discussed. We demonstrate that periodic oscillations are generated inside the drop due to the competition between the Marangoni effect and the gravity-dependent convective instability of the solution. Using direct numerical simulation, we identified the structures of convective motion at the interface and in its neighborhood, determined the flow intensity as a function of time, and obtained the range of change in the oscillation period.