Trade Off between Hydrodynamic and Thermodynamic Forces at the Liquid-Liquid Interface.

Viscous fingering (VF) instability has been investigated in the case of a partially miscible binary system by nonlinear numerical simulations. Partially miscible fluid systems offer the possibility of phase separation coupled with VF instability. The thermodynamics of such systems are governed by the Margules parameter (interaction parameter) as well as the fluid concentrations. Kinetics of the decomposition is also influenced by dynamical parameters such as the viscosity of the fluid, which incidentally also affects the hydrodynamic forces. Here, we explore the effects of concentration and Margules parameter in order to ascertain the trade-offs incurred between hydrodynamic and thermodynamic effects at the interface as well as the thermodynamics of the bulk. Based on the Gibb's free energy versus concentration curve, we select concentrations (i) outside spinodal and binodal regions, (ii) within binodal but outside the spinodal, and (iii) within the spinodal curve. We solve the modified Cahn-Hilliard-Hele-Shaw equation employing the COMSOL Multiphysics software. Applying high-resolution numerical simulations, we show a strong dependence of the thermodynamic forces on the concentration of the mixtures. Rapid phase separation and hence a faster rate of droplet formation have been found when the concentration lies inside the spinodal region. Further, we have investigated the correlation between the fractal dimension and dynamics of the system. The spatiotemporal studies presented in this work clearly illustrate the competition between hydrodynamic and thermodynamic forces and provide insights on the kinetics of decomposition and growth of interfacial instabilities.