Molecular dynamics simulations of surfactant adsorption at oil/water interface under shear flow

Molecular dynamics simulations of surfactant adsorption at oil/water interface under shear flow

Ying Rena,b,*, Qiang Zhanga,c, Ning Yanga,b, Ji Xua,b, Jialin Liua,d, Ruixin Yanga,c, Christian Kunkelmanne, Eduard Schreinere, Christian Holtzee, Kerstin Mülheimse, Bernd Sachwehf

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• Adsorption kinetics of surfactants under shear were studied via non-equilibrium MD simulations. • Mechanisms of emulsion droplets with dynamic interfacial structure in mixing devices were discussed. • Structures of emulsion droplets in high-shear mixers are jointly determined by both the interfacial level and the device level. • Coupling between two mesoscale phenomena were implemented in computer simulations with promising results.


Surfactants are extensively used in many chemical products to improve their stability, appearance, texture, and rheology. Precise control of the emulsion droplet size distribution, which depends on the characteristics of the surfactant used, is important for target-oriented product design. A complete understanding of the structures and dynamics of emulsion droplets at the reactor level requires coupling of two mesoscale physical constraints, that at the interfacial level, i.e., smaller than a single droplet (Mesoscale-1), and that at the device level, i.e., larger than a single droplet (Mesoscale-2). In this work, the structures and adsorption kinetics of Mesoscale-1 surfactant molecules were studied via coarse-grained molecular dynamics. A non-equilibrium model that could introduce stable shear flow into the simulation box was used to investigate the interfacial structures at the droplet interface under different shear rates. The configurations of the surfactant molecules and adsorption amounts were compared with those obtained without flow. The adsorption kinetics for different shear rates were compared to determine the effects of hydrodynamic interactions. The dominant mechanisms governing the dynamic structures can thus be summarized as maximization of the adsorption density at the interface and minimization of flow resistance in the bulk phase (water and/or oil molecules). A scheme for coupling between Mesoscale-1 and Mesoscale-2 is proposed. This method is promising for the incorporation of interfacial structure effects into the hydrodynamics at the reactor device level for the manipulation of chemical products.