We study the effect of surfactants on the dynamics of a drop-interface coalescence using full three-dimensional direct numerical simulations. We employ a hybrid interface-tracking/level-set method, which takes into account Marangoni stresses that arise from surface tension gradients, interfacial and bulk diffusion, and sorption kinetic effects. We validate our predictions against the experimental data of Blanchette and Bigioni [Nat. Phys. 2(4):254-257 (2006)] and perform a parametric study that demonstrates the delicate interplay between the flow fields and those associated with the surfactant bulk and interfacial concentrations. The results of this work unravel the crucial role of the Marangoni stresses in the flow physics of coalescence with particular attention paid to their influence on neck reopening dynamics in terms of stagnation-point inhibition, and near-neck vorticity generation. We demonstrate that surfactant-laden cases feature a rigidifying effect on the interface compared to the surfactant-free case, a mechanism that underpins the observed surfactant-induced phenomena.
We experimentally study steady Marangoni-driven surfactant transport on the interface of a deep water layer. Using hydrodynamic measurements, and without using any knowledge of the surfactant physico-chemical properties, we show that sodium dodecyl sulphate and Tergitol 15-S-9 introduced in low concentrations result in a flow driven by adsorbed surfactant. At higher surfactant concentration, the flow is dominated by the dissolved surfactant. Using Camphoric acid, whose properties are {\it a priori} unknown, we demonstrate this method's efficacy by showing its spreading is adsorption dominated.
In this work, we study the effect of insoluble surfactants on the three-dimensional rim-driven retraction dynamics of thin water sheets in air. We employ an interface-tracking/level-set method to ensure the full coupling between the surfactant-induced Marangoni-stresses, interfacial diffusion, and inertia. Our findings are contrasted with the (Newtonian) dynamics of a liquid sheet edge finding that the surfactant concentration can prevent, or delay, the breakup of the rim. Our simulations use the fastest growing Rayleigh-Plateau instability to drive droplet detachment from the fluid sheet (rim…
We study the effect of insoluble surfactants on the wave dynamics of vertically-falling liquid films. We use three-dimensional numerical simulations and employ a hybrid interface-tracking/level-set method, taking into account Marangoni stresses induced by gradients of interfacial surfactant concentration. Our numerical predictions for the evolution of the surfactant-free, three-dimensional wave topology are validated against the experimental work of Park & Nosoko (2003). The addition of surfactants is found to influence significantly the development of horseshoe-shaped waves. At low Marangoni …
We study the effect of insoluble surfactants on the spatio-temporal evolution of turbulent jets. We use three-dimensional numerical simulations and employ an interface-tracking/level-set method that accounts for surfactant-induced Marangoni stresses. The present study builds on our previous work (Constante et al., 2021, J. Fluid Mech., 922, A6) in which we examined in detail the vortex-surface interaction in the absence of surfactants. Numerical solutions are obtained for a wide range of Weber and elasticity numbers in which vorticity production is generated by surface deformation and surfacta…
We derive a general integrodifferential equation for the transient behaviour of small-amplitude capillary waves on the planar surface of a viscous fluid in the presence of the Marangoni effect. The equation is solved for an insoluble surfactant solution in concentration below the critical micelle concentration (cmc) undergoing convective-diffusive surface transport. The special case of a diffusion-driven surfactant is considered near the the critical damping wavelength. The Marangoni effect is shown to contribute to the overall damping mechanism and a first-order term correction to the critica…
We present a realization of a fast interfacial Marangoni microswimmer by a half-spherical alginate capsule at the air-water interface, which diffusively releases water-soluble spreading molecules (weak surfactants such as polyethylene glycol (PEG)), which act as "fuel" by modulating the air-water interfacial tension. For a number of different fuels, we can observe symmetry breaking and spontaneous propulsion although the alginate particle and emission are isotropic. The propulsion mechanism is similar to soap or camphor boats, which are, however, typically asymmetric in shape or emission to se…
In the present study we analytically investigate the deformation and bulk rheology of a dilute emulsion of surfactant-laden droplets suspended in a linear flow. We use an asymptotic approach to predict the effect of surfactant distribution on the deformation of a single droplet as well as the effective shear and extensional viscosity for the dilute emulsion. The non-uniform distribution of surfactants due to the bulk flow results in the generation of a Marangoni stress which affects both the deformation as well as the bulk rheology of the suspension. The present analysis is done for the limiti…
We study the effect of surfactant on the dynamics of a bubble bursting through an interface. We perform fully three-dimensional direct numerical simulations using a hybrid interface-tracking/level-set method accounting for surfactant-induced Marangoni stresses, sorption kinetics, and diffusive effects. We select an initial bubble shape corresponding to a large Laplace number and a vanishingly small Bond number in order to neglect gravity, and isolate the effects of surfactant on the flow. Our results demonstrate that the presence of surfactant affects the dynamics of the system through Marango…
The motion of a viscous droplet in unbounded Poiseuille flow under the combined influence of bulk-insoluble surfactant and linearly varying temperature field aligned in the direction of imposed flow is studied analytically. Neglecting fluid inertia, thermal convection and shape deformation, asymptotic analysis is performed to obtain the velocity of a force-free surfactant-laden droplet. The present study is focused on two limiting situations of surfactant transport: (i) small surface Peclet number, and (ii) high surface Peclet number. Thermocapillary-induced Marangoni stress, strength of which…
We consider the spreading dynamics of some insoluble surface-active species along an aqueous interface. The model includes both diffusion, Marangoni convection and first-order reaction kinetics. An exact solution of the nonlinear transport equations is derived in the regime of large Schmidt number, where viscous effects are dominant. We demonstrate that the variance of the surfactant distribution increases linearly with time, providing an unambiguous definition for the enhanced diffusion coefficient observed in the experiments. The model thus presents new insight regarding the actuation of cam…
We study the dynamics of surfactants spreading on gels, paying particular attention to the pattern formation accompanying the flow. The latter results from gel-cracking, promoted by Marangoni stresses, and resemble starbursts.
Surfactant distribution heterogeneities at a fluid/fluid interface trigger the Marangoni effect, i.e. a bulk flow due to a surface tension gradient. The influence of surfactant solubility in the bulk on these flows remains incompletely characterized. Here we study Marangoni flows sustained by injection of hydrosoluble surfactants at the air/water interface. We show that the flow extent increases with a decrease of the critical micelle concentration, i.e. the concentration at which these surfactants self-assemble in water. We document the universality of the surface velocity field and predict s…
The sedimentation of a surfactant-laden deformable viscous drop acted upon by an electric field is considered theoretically. The convection of surfactants in conjunction with the the combined effect electrohydrodynamic flow and sedimentation leads to a locally varying surface tension, which subsequently alters the drop dynamics via the interplay of Marangoni, Maxwell and hydrodynamic stresses. Assuming small capillary number and small electric Reynolds number, we employ a regular perturbation technique to solve the coupled system of governing equations. It is shown that when a leaky dielectric…
Marangoni propulsion is a form of locomotion wherein an asymmetric release of surfactant by a body located at the surface of a liquid leads to its directed motion. We present in this paper a mathematical model for Marangoni propulsion in the viscous regime. We consider the case of a thin rigid circular disk placed at the surface of a viscous fluid and whose perimeter has a prescribed concentration of an insoluble surfactant, to which the rest of its surface is impenetrable. Assuming a linearized equation of state between surface tension and surfactant concentration, we derive analytically the …
Using numerical simulations, we investigate the effects of Marangoni stresses induced by surfactants on the effective slip length of liquid-infused surfaces (LIS) with transverse grooves. The surfactants are assumed soluble in the external liquid shearing the surface and can adsorb onto the interfaces. Two different adsorption models are used: a classical Frumkin model and a more advanced model that better describes the decrease of surface tension for minuscule concentrations. The simulations show that LIS may face even more severe effects of surfactants than previously investigated superhydro…
Guided by computation, we theoretically calculate the steady flow driven by Marangoni stress due to surfactant introduced on a fluid interface at a constant rate. Two separate extreme cases, where the surfactant dynamics is dominated by the adsorbed phase or the dissolved phase are considered. We focus on the case where the size of the surfactant source is much smaller than the size of the fluid domain, and the resulting Marangoni stress overwhelms viscous forces so that the flow is strongest in a boundary layer close to the interface. We derive the resulting flow in a region much larger than …
Electric modification of mode competition in viscous films with insoluble surfactants on vertical fibers
School of Astronautics, Beihang University（航空航天大学，北京航空航天大学）；Aircraft and Propulsion Laboratory, Ningbo Institute of Technology, Beihang University（飞机与推进实验室，宁波理工学院，北京航空航天大学）
Experimental observations indicate that chemically active droplets suspended in a surfactant-laden fluid can self-propel spontaneously. The onset of this motion is attributed to a symmetry-breaking Marangoni instability resulting from the nonlinear advective coupling of the distribution of surfactant to the hydrodynamic flow generated by Marangoni stresses at the droplet's surface. Here, we use weakly nonlinear analysis to characterize the self-propulsion near the instability threshold and the influence of the droplet's deformability. We report that in vicinity of the threshold, deformability …
The Marangoni effect refers to fluid flow induced by a gradient in surface tension at a fluid-fluid interface. We determine the full three-dimensional Marangoni flow generated by a non-uniform surface tension profile at the interface of a self-propelled spherical emulsion droplet. For all flow fields inside, outside, and at the interface of the droplet, we give analytical formulas. We also calculate the droplet velocity vector $\mathbf{v}^D$, which describes the swimming kinematics of the droplet, and generalize the squirmer parameter $β$, which distinguishes between different swimmer types ca…
Interface-resolved direct numerical simulations are performed to examine the combined effects of soluble surfactant and viscoelasticity on the structure of a bubbly turbulent channel flow. The incompressible flow equations are solved fully coupled with the FENE-P viscoelastic model and the equations governing interfacial and bulk surfactant concentrations. The latter coupling is achieved through a non-linear equation of state which relates the surface tension to the surfactant concentration at the interface. The two-fluid Navier-Stokes equations are solved using a front-tracking method, augmen…
When surface-active molecules are released at a liquid interface, their spreading dynamics is controlled by Marangoni flows. Though such Marangoni spreading was investigated in different limits, exact solutions remain very few. Here we consider the spreading of an insoluble surfactant along the interface of a deep fluid layer. For two-dimensional Stokes flows, it was recently shown that the non-linear transport problem can be exactly mapped to a complex Burgers equation [Crowdy, SIAM J. Appl. Math. 81, 2526 (2021)]. We first present a very simple derivation of this equation. We then provide fu…
When two liquids with different surface tensions come into contact, the liquid with lower surface tension spreads over the other. This Marangoni-driven spreading has been studied for various geometries and surfactants, but the dynamics of the binary geometry (drop-drop) has hardly been quantitatively investigated, despite its relevance for drop encapsulation applications. Here we use laser-induced fluorescence (LIF) to temporally resolve the distance $L(t)$ over which a low-surface-tension drop spreads over a miscible high-surface-tension drop. $L(t)$ is measured for various surface tension di…
In the minutes immediately preceeding the rupture of a soap bubble, distinctive and repeatable patterns can be observed. These quasi-stable transient structures are associated with the instabilities of the complex Marangoni flows on the curved thin film in the presence of a surfactant solution. Here, we report a generalised Cahn-Hilliard-Swift-Hohenberg model derived using asymptotic theory which describes the quasi-elastic wrinkling pattern formation and the consequent coarsening dynamics in a curved surfactant-laden thin film. By testing the theory against experiments on soap bubbles, we fin…
Surface coatings and patterning technologies are essential for various physicochemical applications. In this Letter, we describe key parameters to achieve uniform particle coatings from binary solutions: First, multiple sequential Marangoni flows, set by solute and surfactant simultaneously, prevent non-uniform particle distributions and continuously mix suspended materials during droplet evaporation. Second, we show the importance of particle-surface interactions that can be established by surface-adsorbed macromolecules. To achieve a uniform deposit in a binary mixture, a small concentration…
The dynamics of wetting and dewetting is largely determined by the velocity field near the contact lines. For water drops it has been observed that adding surfactant decreases the dynamic receding contact angle even at a concentration much lower than the critical micelle concentration (CMC). To better understand why surfactants have such a drastic effect on drop dynamics, we constructed a dedicated a setup on an inverted microscope, in which an aqueous drop is held stationary while the transparent substrate is moved horizontally. Using astigmatism particle tracking velocimetry, we track the 3D…
The wetting properties of multi-component liquids are crucial to numerous industrial applications. The mechanisms that determine the contact angles for such liquids remain poorly understood, with many intricacies arising due to complex physical phenomena, for example due to the presence of surfactants. Here, we consider two-component drops that consist of mixtures of vicinal alkane diols and water. These diols behave surfactant-like in water. However, the contact angles of such mixtures on solid substrates are surprisingly large. We experimentally reveal that the contact angle is determined by…
The dynamics of ligaments retracting under the action of surface tension occurs in a multitude of natural and industrial applications, such as inkjet printing and atomisation. We perform fully three-dimensional, two-phase direct numerical simulations of the retraction dynamics with soluble surfactants. A full parametric study is performed using a hybrid interface-tracking/level-set method, which is utilised to treat the interface; this method is capable of capturing faithfully the topological transitions that are a feature of the flow over a certain range of ligament aspect ratios and Ohnesorg…
We investigate the dynamics of an insoluble surfactant on the surface of a thin viscous fluid spreading inward to fill a surfactant-free region. During the initial stages of surfactant self-healing, Marangoni forces drive an axisymmetric ridge inward to coalesce into a growing central distension; this is unlike outward-spreading, in which the ridge decays. In later dynamics, the distension slowly decays and the surfactant concentration equilibrates. We present results from experiments in which we simultaneously measure the surfactant concentration (using fluorescently-tagged lipids) and the fl…
Interfacial tension gradients drive flow along liquid-liquid interfaces in a process known as the Marangoni effect. Such gradients can be caused by surfactants, which has been extensively studied in the literature. Less is known of its nanoscale properties, where molecular interfaces display properties separate from bulk liquid matter such as interfacial viscosity. In this report we study the molecular solutal Marangoni effect using molecular dynamics simulations. We show that molecular interfacial effects are important and should be accounted for in nanofluidic regimes. Hydrodynamic models ca…
Superhydrophobic surfaces (SHSs) have the potential to achieve large drag reduction for internal and external flow applications. However, experiments have shown inconsistent results, with many studies reporting significantly reduced performance. Recently, it has been proposed that surfactants, ubiquitous in flow applications, could be responsible, by creating adverse Marangoni stresses. Yet, testing this hypothesis is challenging. Careful experiments with purified water show large interfacial stresses and, paradoxically, adding surfactants yields barely measurable drag increases. This suggests…
Recently, an active microswimmer was constructed where a micron-sized droplet of bromine water was placed into a surfactant-laden oil phase. Due to a bromination reaction of the surfactant at the interface, the surface tension locally increases and becomes non-uniform. This drives a Marangoni flow which propels the squirming droplet forward. We develop a diffusion-advection-reaction equation for the order parameter of the surfactant mixture at the droplet interface using a mixing free energy. Numerical solutions reveal a stable swimming regime above a critical Marangoni number M but also stopp…
The motion of a viscous drop is investigated when the interface is fully covered with a stagnant layer of surfactant in an arbitrary unsteady Stokes flow for the low surface Péclet number limit. The effect of the interfacial slip coefficient on the behavior of the flow field is also considered. The hydrodynamic problem is solved by the solenoidal decomposition method and the drag force is computed in terms of Faxen's laws using a perturbation ansatz in powers of the surface Péclet number. The analytical expressions for the migration velocity of the drop are also obtained in powers of the surfa…
In this study we attempt to explore the consequences of surfactant coating on the electrohydrodynamic manipulation of a drop motion in a plane Poiseuielle flow. In addition we consider bulk insoluble surfactants and a linear dependency of the surface tension on the surfactant concentration. Subsequently a double asymptotic perturbation method is used in terms of small electric Reynolds number and capillary number in the limit of a diffusion-dominated surfactant transport mechanism. Also going beyond the widely employed axisymmetric framework, the coupled system of governing differential equati…
