2. Cahn/de Gennes model for two-component two-phase flow

For a system with two components and two immiscible phases, the free energy functional is written as (Cahn Reference Cahn1977; De Gennes Reference De Gennes1985)

(2.1)\begin{equation} \mathcal{F}(\phi,\boldsymbol{\nabla}\phi)= \int_\varOmega \left[f(\phi) + \kappa(\nabla \phi)^{2} \right] {\rm d}\varOmega + \int_{S} \varGamma(\phi)\,{\rm d} S,\quad \forall\ \boldsymbol x \in \varOmega \cup S, \end{equation}

where the bulk free energy density $f(\phi )$ as a function of the composition $\phi$ has two local minima (equilibrium states) at $\phi _{e}^{\delta }$ and $\phi _{e}^{\alpha }$ to model two immiscible fluids. The composition $\phi$ is space $\boldsymbol x$ and time $t$ dependent defined on the bulk domain $\varOmega$ and the solid substrate $S$. Typical examples for the free energy density are double-well potential (Jacqmin Reference Jacqmin2000), obstacle potential (Nestler, Garcke & Stinner Reference Nestler, Garcke and Stinner2005) or the regular solution model (Wang et al. Reference Wang, Choudhury, Selzer, Mukherjee and Nestler2012). The interface tension $\gamma _{\alpha \delta }$ of the immiscible liquids is calculated by

(2.2)\begin{equation} \gamma_{\alpha\delta}=\int_{{X}} \left[{\rm \Delta} f+ \kappa(\nabla \phi)^{2} \right]{\rm d} X, \end{equation}

where the excess energy density ${\rm \Delta} f$ is defined as $f(\phi )-f(\phi _{e}^{\alpha })-\mu ^{e}(\phi -\phi _{e}^{\alpha })$, $\mu ^{e}$ representing the chemical potential at equilibrium, and $X$ traces the integration path from the bulk of the droplet to the surrounding bulk region.

The second part of (2.1) describes the wall free energy whose density $\varGamma (\phi )$ is an interpolation over the individual interfacial tensions:

(2.3)\begin{equation} \varGamma(\phi)= \gamma_{\alpha S} h(\phi) + \gamma_{\delta S} [1-h(\phi)],\quad \forall\ \boldsymbol x \in S, \end{equation}

where the interpolation function $h(\phi )$ fulfils $h(\phi _{e}^{\alpha })=1$ and $h(\phi _{e}^{\delta })=0$. By this interpolation, the liquid–substrate interfacial energy is $\gamma _{\alpha S}$, when the liquid composition is $\phi =\phi _{e}^{\alpha }$; and the surrounding–substrate interfacial energy is $\gamma _{\delta S}$, when the surrounding composition is $\phi =\phi _{e}^{\delta }$. Various formulations for $h(\phi )$ have been used in previous literature (Carlson et al. Reference Carlson, Do-Quang and Amberg2009; Diewald et al. Reference Diewald, Kuhn, Blauwhoff, Heier, Becker, Werth, Horsch, Hasse and Müller2016; Xu Reference Xu2016; Wu et al. Reference Wu, Wang, Selzer and Nestler2019b). Apart from the interpolation concept over individual interfacial tensions, a second-order polynomial has been used (Cahn Reference Cahn1977; De Gennes Reference De Gennes1985):

(2.4)\begin{equation} \varGamma(\phi)=a_{0} + a_{1} \phi+\frac{a_{2}}{2}\phi^{2},\quad \forall\ \boldsymbol x \in S. \end{equation}

Here, $a_{0}$, $a_{1}$ and $a_{2}$ depict the attractive and repulsive interactions between the liquid and the substrate. A significant difference between (2.3) and (2.4) is that in the former case, the effective interfacial energies $\gamma _{\delta S}$ and $\gamma _{\alpha S}$ are independent of surface composition. While in the latter case, $\gamma _{\alpha S}$ and $\gamma _{\delta S}$ depend on the surface composition $\phi _{S}^{a}$ ($a = \alpha$, $\delta$), which is determined by a series of partial differential equations resulting from the joint equilibrium of the bulk and the surface as

(2.5a,b)\begin{equation} 2\kappa \nabla^{2} \phi = f^\prime(\phi) \quad \forall \boldsymbol x\in\varOmega;\quad 2\kappa \boldsymbol{\nabla} \phi \boldsymbol{\cdot} \boldsymbol n =\varGamma^\prime(\phi) \quad \forall\ \boldsymbol x\in S, \end{equation}

where $\boldsymbol n$ is the normal vector of the solid substrate. After simplification, we obtain the following implicit equation for the surface composition $\phi _{S}^{a}$:

(2.6)\begin{equation} 2\sqrt{\kappa {\rm \Delta} f}=\varGamma^\prime(\phi),\quad \forall\ \boldsymbol x \in\varOmega\cap S, \end{equation}

where the left-hand side is typically a ‘W’-shaped curve (see supplementary figure S1 available at https://doi.org/10.1017/jfm.2023.561) and the right-hand side is a linear function of $\phi$ if (2.4) is applied. The intersection of the two curves $2\sqrt {\kappa {\rm \Delta} f}$ and $\varGamma ^\prime (\phi )$ determines the surface composition $\phi _{S}^{\alpha }$ and $\phi _{S}^{\delta }$ (see figure S1). In this way, the interfacial energies have two contributions: one is the wall free energy density $\varGamma (\phi _{S}^{a})$ ($a=\alpha$, $\delta$) and the other one is the excess free energy which is calculated by an integration from the surface composition $\phi _{S}^{a}$ to the bulk composition $\phi _{e}^{a}$. This result is in contrast to the independence of the interfacial energies on the surface composition if (2.3) is applied. The interfacial energies with the excess free energy at the solid–liquid interface represent a large difference of Cahn's approach from Jacqmin's wetting model (Jacqmin Reference Jacqmin2000). For fluids with three components, the variation of the wettabilities due to the occurrence of the surface composition is much more complex than the binary case and is examined in the following.

3. Model of ternary fluids

We consider a fluid mixture consisting of three components, of which the compositions are denoted by $\boldsymbol \phi = (\phi _{1}(\boldsymbol x, t), \phi _{2}(\boldsymbol x, t), \phi _{3}(\boldsymbol x, t))$. The compositions are space $\boldsymbol x$ and time $t$ dependent and are restricted within the Gibbs simplex $G=\{ \boldsymbol {\phi }\in \mathbb {R}^{3}:\sum _{j=1}^{3}\phi _{j}=1, \phi _{j}\geq 0 \}$ in accordance with the assumption of incompressible fluids. This constraint results from the definition of the volume concentration $\phi _{i}=v_{i}^{o}/v_{m}$, where $v_{i}^{o}$ and $v_{m}$ are the molar volumes of the $i$ component and the mixture, respectively. By the Flory–Huggins model (Flory Reference Flory1953), the free energy density of the system is formulated as a function of temperature $T$ and composition $\boldsymbol \phi$ as

(3.1)\begin{equation} f(\boldsymbol\phi,T)= (R_{g}T/v_{m}) \left(\sum_{j=1}^{3} \frac{\phi_{j}\ln \phi_{j}}{N_{j}}+ \sum_{j< k}\chi_{jk} \phi_{j} \phi_{k}+\sum_{j< k< l}\chi_{jkl}\phi_{j}\phi_{k}\phi_{l}\right),\quad \forall\ \boldsymbol x \in \varOmega, \end{equation}

where the first logarithm term denotes entropy contribution and the last two polynomial terms are related to the enthalpy of the mixture. The Flory–Huggins parameters $\chi _{jk}$ depict the double interaction between species $j$ and $k$, while $\chi _{jkl}$ scales the more complex triple interaction between all three species $j$, $k$ and $l$ (Zhang et al. Reference Zhang, Wu, Wang, Guo and Nestler2021). Especially for distinct polymer species, the entropy of the mixture can be altered by the degree of polymerization $N_{j}$ which, otherwise, is set to unity for very small molecular species, such as water or metal. In this work, the selection criteria for the interaction parameters $\chi _{jk}$ and $\chi _{jkl}$, the temperature $T$ as well as $N_{j}$ are made to model two different situations:

1. (S1) Two phases consisting of component 1 and component 2 are completely miscible, forming an $\alpha$ phase droplet, like water–alcohol or water–coffee. Meanwhile, the $\alpha$ phase is immiscible with the component-3-rich $\delta$ phase, like vapour. For two phases in equilibrium, as demonstrated in figures 1(I) and 1(II), there are two local minima in the free energy landscape. These two free energy minima states respectively represent the droplet of $\alpha$ phase and the $\delta$ surrounding phase. The equilibrium compositions $\boldsymbol \phi _{{e}}^{\alpha }=( \phi _{1}^{\alpha }, \phi _{2}^{\alpha }, \phi _{3}^{\alpha })$, $\boldsymbol \phi _{e}^{\delta }=(\phi _{1}^{\delta }, \phi _{2}^{\delta }, \phi _{3}^{\delta })$ between the immiscible $\alpha$ and $\delta$ phases are defined by the common tangent construction as

   (3.2)\begin{gather} \boldsymbol\mu^{e}\equiv(\mu_{1}^{e},\mu_{2}^{e},\mu_{3}^{e}) = \left.\frac{\partial f}{\partial \boldsymbol\phi}\right\rvert_{\boldsymbol\phi=\boldsymbol \phi_{e}^{\alpha}} =\left.\frac{\partial f}{\partial \boldsymbol\phi}\right\rvert_{\boldsymbol\phi=\boldsymbol \phi_{e}^{\delta}}; \end{gather}
   (3.3)\begin{gather}f(\boldsymbol \phi_{e}^{\alpha})-f(\boldsymbol \phi_{e}^{\delta})= \langle \boldsymbol\mu^{e}, \boldsymbol \phi_{e}^{\alpha}-\boldsymbol \phi_{e}^{\delta} \rangle, \quad \forall\ \boldsymbol x \in \varOmega. \end{gather}
   Here, $\mu _{i}^{e}$, $i=1, 2, 3$, denotes the equilibrium chemical potential of component $i$ and $\langle \ \rangle$ is the dot product operator. Equations (3.2) and (3.3) are solved by the Newton iteration method and the equilibrium compositions are illustrated by the black solid lines in figure 1. The difference of figure 1(I) from figure 1(II) is that the miscibility of components 1 and 2 is symmetric with respect to the composition of $\phi _{2}=0.5$. In this case, the component 1 and 2 molecules have high similarity and their interaction with component 3 is identical. Figure 1(II) represents another case, where components 1 and 2 have different interaction parameters or degrees of polymerization ($N_{i}$). Consequently, the miscibility shifts to the side of the component-2-rich phase in figure 1(II).

2. (S2) Three phases consisting of the three components 1, 2 and 3 are immiscible with each other (Zhang, Wang & Nestler Reference Zhang, Wang and Nestler2022a), for instance, a water–oil–vapour system. In this case, three local minima on the free energy landscape manifest the equilibrium compositions in each immiscible phase, as depicted by the black dots in the phase diagram of figure 1(III). For convenience, component 1-, 2- and 3-rich phases are called $\alpha$, $\beta$ and $\delta$ phases, respectively.

Figure 1.

Free energy density landscapes and phase diagram. (I,II) Miscible ternary system. The parameters for (I) are $(N_{1}, N_{2}, N_{3}) = (2, 2, 1)$, $(\chi _{1},\chi _{2},\chi _{3}, \chi _{123})=(0.5, 3.5, 3.5, 1.5)$ and $T=2$. The parameters for (II) are $(N_{1}, N_{2}, N_{3}) = (5, 1, 1)$, $(\chi _{1},\chi _{2},\chi _{3}, \chi _{123})=(0.5, 6.0, 4.5, 1.5)$ and $T=2$. The black solid lines depict the binodal composition in the phase consisting of components 1 and 2 ($\alpha$ phase) and in the component-3-rich phase ($\delta$ phase). The dashed lines show the spinodal curves. (III) Immiscible ternary system with the simulation parameters $(N_{1}, N_{2}, N_{3}) = (1, 1, 1)$, $(\chi _{1},\chi _{2},\chi _{3}, \chi _{123})=(2.5, 2.5, 2.5, 4.0)$ and $T=2$. The equilibrium compositions in $\alpha$ (component-1-rich), $\beta$ (component-2-rich) and $\delta$ (component-3-rich) phases are illustrated by the black circles at the left, right and top positions, respectively. Colour legend: red for high free energy density values and blue for low values.

4. Bulk and surface thermodynamics

The free energy functional of the system reads

(4.1)\begin{equation} \mathcal{F}(\boldsymbol\phi, \boldsymbol{\nabla} \boldsymbol\phi) =\int_\varOmega \left[f(\boldsymbol\phi, T) + \sum_{j=1}^{3} \kappa_{j} (\nabla \phi_{j})^{2} \right] {\rm d}\varOmega + \int_{S} \varGamma(\boldsymbol\phi)\,{\rm d} S,\quad \forall\ \boldsymbol x \in \varOmega \cup S. \end{equation}

Here, $\kappa _{i}$ stands for the gradient energy coefficient. Considering an $a$–$b$ interface ($a=\alpha$, $\beta$, $\delta$, $b=\alpha$, $\beta$, $\delta$, $a\neq b$),

(4.2)\begin{equation} \delta \mathcal{F}/\delta \boldsymbol\phi=\boldsymbol \mu^{e},\quad \forall\ \boldsymbol x \in \varOmega. \end{equation}

Substituting (4.1) into (4.2) yields the following coupled ordinary differential equations:

(4.3)\begin{equation} \mu_{i}^{e} = \partial f/\partial \phi_{i}-2\kappa_{i} \nabla^{2}\phi_{i},\quad \forall\ \boldsymbol x \in \varOmega,\quad i=1,2,3. \end{equation}

An integration of (4.3) with the condition that the composition gradient vanishes at the boundary leads to

(4.4)\begin{equation} \sum_{j=1}^{K}\kappa_{j} \left(\nabla\phi_{j}\right)^{2}={\rm \Delta} f,\quad \forall\ \boldsymbol x \in \varOmega, \end{equation}

where the excess energy density ${\rm \Delta} f=f(\boldsymbol \phi )-f(\boldsymbol \phi _{e}^{a})- \boldsymbol \mu ^{{e}}\boldsymbol {\cdot }(\boldsymbol \phi - \boldsymbol \phi _{e}^{a})=f(\boldsymbol \phi )-f(\boldsymbol \phi _{e}^{b})- \boldsymbol \mu ^{{e}}\boldsymbol {\cdot }(\boldsymbol \phi - \boldsymbol \phi _{e}^{b})$ and $K$ is the total number of components in the system. Note that the equilibrium chemical potentials are generally not zero, as shown in the phase diagram. This is in contrast to the conventional way of a double-well potential for two-phase flow (Jacqmin Reference Jacqmin2000) and a multi-well potential (He et al. Reference He, Li, Huang, Hu, Li and Wang2020) for multiphase flow, where the chemical potential is zero at equilibrium. The integration of the equilibrium equation leads to a new potential in the form of $f(\boldsymbol \phi )-\sum _{j=1}^{K}\mu _ {j}^{e}\phi _{j}$. Based on the Euler formulation for one-component phase (Sundman, Lukas & Fries Reference Sundman, Lukas and Fries2007), we write its generalization for a system with $\varLambda$ phase and $K$ component as $\sum _{\nu =1}^{\varLambda }(f-\sum _{j=1}^{K}\mu _{j}^{e} \phi _{j})v^{\nu }=0$ due to the additive property of extensive variables, where $v^{\nu }$ is the molar volume of the respective phase $\nu$. Because of incompressibility, the summation of the molar volume is constant, $\sum _{\nu =1}^{\varLambda } v^{\nu }=\text {constant}$. This leads to a necessary condition for the phase equilibrium $f-\sum _{j=1}^{K}\mu _{j}^{e} \phi _{j}=\text {constant}$. This result motivates us to define a thermodynamic potential $P\equiv f-\sum _{j=1}^{K}\mu _{j} \phi _{j}$, which is the Legendre transformation of the chemical potential. Here, the chemical potential for the $j$th component $\mu _{j}$ is not necessary to be $\mu _{j}^{e}$. The thermodynamic potential characterizes the phase state away from the equilibrium. The significance of the thermodynamic potential is its contribution to the capillary force together with the Kortweg stress.

The minimization of the free energy functional at the substrate $S$ requires that

(4.5)\begin{equation} \delta \mathcal{F}/\delta \phi_{i}=0,\quad \forall\ \boldsymbol x \in S,\quad i=1,2,3. \end{equation}

With the expression for the free energy functional, the equilibrium condition at the substrate is rewritten as (see supplementary section S.II.3)

(4.6)\begin{equation} 2 \kappa_{i} \boldsymbol{\nabla}\phi_{i}\boldsymbol{\cdot} \boldsymbol{n}-\partial_{\phi_{i}}\varGamma= 0,\quad \forall\ \boldsymbol x \in S \quad i=1,2,3. \end{equation}

The joint equilibrium of bulk and substrate, as a result of (4.4) and (4.6), determines the surface composition $\boldsymbol \phi _{S}^{a}$ ($a = \alpha$, $\beta$, $\delta$), which is analogous to (2.6) for the binary system. The details for the surface composition of the ternary system are discussed in the following section for the validation of the model.

5. Interfacial tension and wall free energy density

The interfacial tension of an $a$–$b$ interface ($a=\alpha$, $\beta$, $\delta$, $b=\alpha$, $\beta$, $\delta$, $a\neq b$) is the excess free energy across the interface, which is expressed as

(5.1)\begin{equation} \gamma_{ab} = \int_{X}\left[f(\boldsymbol\phi)-f(\boldsymbol\phi_{e}^{a})- \boldsymbol\mu^{e}\boldsymbol{\cdot}(\boldsymbol \phi-\boldsymbol \phi_{e}^{a}) + \sum_{{j=1}}^{K} \kappa_{j}\left( \nabla\phi_{j}\right)^{2}\right] {\rm d} X. \end{equation}

The integral path $X$ is achieved by minimizing the interfacial tension $\gamma _{ab}$. With the bulk equilibrium condition, the surface tension is rewritten as

(5.2)\begin{equation} \gamma_{ab}=\int_{\boldsymbol\phi_{e}^{a}}^{\boldsymbol\phi_{e}^{b}} 2\sqrt{{\rm \Delta} f}\,{\rm d} s,\end{equation}

where ${\rm d} s=\sqrt {\sum _{j=1}^{K}\kappa _{j} ({\rm d}\phi _{j})^{2}}$. The path integral starts from one equilibrium composition ${\boldsymbol \phi _{e}^{a}}=(\phi _{1}^{a},\phi _{2}^{a}, \phi _{3}^{a})$ to the other one ${\boldsymbol \phi _{e}^{b}}=(\phi _{1}^{b},\phi _{2}^{b},\phi _{3}^{b})$ by minimizing the interfacial tension.

The interfacial tension between an $a$ phase ($a=\alpha$, $\beta$, $\delta$) and the substrate $S$ has two contributions. One is the excess free energy due to the presence of the surface composition, which leads to a non-uniform composition from $\boldsymbol \phi _{S}^{a}$ to $\boldsymbol \phi _{e}^{a}$. The second part is the wall free energy $\varGamma (\boldsymbol \phi _{S}^{a})$, which depends on the composition on the substrate. Thus, the interfacial tension is expressed as

(5.3)\begin{equation} \gamma_{aS } =\varGamma(\boldsymbol \phi_{S}^{a}) + \int^{\boldsymbol\phi_{e}^{a}}_{{\boldsymbol\phi_{S}^{a} }} 2\sqrt{{\rm \Delta} f}\,{\rm d} s . \end{equation}

The wall free energy density is assumed to be described by a second-order polynomial function with coefficients $g_{ij}$ as

(5.4)\begin{equation} \varGamma (\boldsymbol \phi) = \sum_{i=1}^{K} \sum_{j=1}^{K} g_{ij} \phi_{i}^{j-1},\quad \forall\ \boldsymbol x \in S.\end{equation}

Here, the parameters $g_{i2}$ represent an attraction of the liquid by the solid; the parameters $g_{i3}$ depict a certain reduction of the liquid–liquid attractive interactions near the surface (De Gennes Reference De Gennes1985). The constants $g_{i1}$ are reference values for the wall free energy and make no contribution to the contact angle.

6. Kinetics equation

The compositions in the domain $\varOmega$ and at the substrate $S$ both evolve with time to minimize the free energy functional. There are different types of kinetics equations, such as Cahn–Hilliard and Allen–Cahn. In this work, we adopt the Cahn–Hilliard model for the time evolution of the composition $\boldsymbol \phi$ in $\varOmega$ until the time $T{t}$. In § 9, we consider the droplet wetting coupling with evaporation. The diffusion mechanism in the evaporation process can be more conveniently described by the Cahn–Hilliard model, in comparison with the Allen–Cahn approach. The diffusion equation for the composition $\phi _{i}$ reads

(6.1)\begin{equation} \partial{t}\phi_{i}={-}\boldsymbol{\nabla} \boldsymbol{\cdot} \boldsymbol j_{i} =\boldsymbol{\nabla}\boldsymbol{\cdot} (L_{i} \boldsymbol{\nabla} \mu_{i}). \end{equation}

The contribution of $\boldsymbol {\nabla }\mu _{j}$ to the time evolution of $\phi _{i}$ ($j\neq i$) will be introduced by considering the Gibbs–Duhem relation. In comparison with the diffusion flux in terms of the composition gradient $\boldsymbol j_ {i}=- D_{i}\boldsymbol {\nabla } \phi _{i}$, the mobility $L_{i}$ is expressed as $L_{i}=D_{i} \phi _{i} v_{m}/(R_{g}T)$. The parameter $D_{i}$ denotes the diffusivity of component $i$. From the Gibbs–Duhem relation $\sum _{j=1}^{K}\phi _{j} \boldsymbol {\nabla } \mu _{j}=0$, we derive the chemical potential gradient for the multicomponent system as

(6.2)\begin{equation} \boldsymbol{\nabla} \mu_{i}=\sum_{j=1}^{K}(\delta_{ij}-\phi_{j})\boldsymbol{\nabla}\mu_{j}, \end{equation}

where $\delta _{ij}$ stands for the Kronecker delta. Thus, we have the generalized diffusion equation for a multicomponent system:

(6.3)\begin{equation} \partial{t}\phi_{i} = \boldsymbol{\nabla} \boldsymbol{\cdot} \left[\sum_{j=1}^{K} {\mathsf{M}}_{ij} \boldsymbol{\nabla}\left(\partial f/\partial \phi_{j}- 2 \kappa_{j} \nabla^{2}\phi_{j} \right)\right],\quad \forall\ (\boldsymbol x,t)\in \varOmega \times [0, T{t}], \end{equation}

where the mobility is expressed as

(6.4)\begin{equation} {\mathsf{M}}_{ij}=D_{i}\phi_{i}(\delta_{ij}-\phi_{j})v_{m}/R_{g} T. \end{equation}

Note that the mobility is composition-dependent, which is in contrast to the constant mobility (Kim Reference Kim2007; Boyer et al. Reference Boyer, Lapuerta, Minjeaud, Piar and Quintard2010). This dependency results from the diffusion equation plus the Gibbs–Duhem relation. A constant mobility and composition-dependent mobility can lead to different physical mechanisms for the time evolution of the equation as well as distinct energy dissipation laws (Cahn, Elliott & Novick-Cohen Reference Cahn, Elliott and Novick-Cohen1996; Abels, Garcke & Grün Reference Abels, Garcke and Grün2012). From the aspect of thermodynamic consistency, the mobility $\boldsymbol{\mathsf{M}}=({\mathsf{M}}_{ij})\in \mathbb {R}^{K\times K}$ must be positive semi-definite to fulfil the energy dissipation law (supplementary material, S.7).

On the substrate $S$, we introduce the following evolution equation based on the surface equilibrium condition (4.6):

(6.5)\begin{equation} \tau_{i}\partial{t}{\phi_{i}}=2 \kappa_{i}\boldsymbol{\nabla} \phi_{i} \boldsymbol{\cdot}\boldsymbol n-\partial_{\phi_{i}} \varGamma +\lambda,\quad \forall\ (\boldsymbol x,t)\in S \times [0, T{t}], \end{equation}

where $\tau _{i}$ is a relaxation parameter. When the time $t\rightarrow \infty$, the surface equilibrium condition (4.6) is reached. To ensure the constraint $\sum _{j=1}^{K}\phi _{j}=1$, a Lagrange multiplier $\lambda =-(1/K)\sum _{j=1}^{K} (\delta \mathcal {F}/\delta \phi _{j})$ has been added to the kinetic evolution for the surface composition.

Depending on the Péclet number, the convection may play a non-negligible role in the mass transfer. In this case, the Cahn–Hilliard model is modified as

(6.6)\begin{equation} \partial{t}\phi_{i} + \boldsymbol{\nabla} \boldsymbol{\cdot}(\boldsymbol{u}\phi_{i})= \boldsymbol{\nabla} \boldsymbol{\cdot} \left[\sum_{j=1}^{K} {\mathsf{M}}_{ij} \boldsymbol{\nabla}\left(\partial f/\partial \phi_{j}- 2 \kappa_{j} \nabla^{2}\phi_{j} \right)\right],\quad \forall\ (\boldsymbol x,t)\in \varOmega \times [0, T{t}], \end{equation}

where $\boldsymbol {u}$ is the convection velocity of the fluid. No-slip boundary condition is assumed for the fluid velocity on the solid substrate $S$. Hence, the evolution equation for the composition on the substrate $S$, equation (6.5), is not altered. However, it should be noted that a slip boundary condition on the substrate may be considered when the slip length is known. We refer to Huang & Wang (Reference Huang and Wang2018) for a discussion on the effect of the slip boundary condition on the solid substrate.

We focus on the fluid flow induced by the surface tension force which is formulated as (S.II.4)

(6.7)\begin{equation} \boldsymbol f_{s}={-}\sum_{j=1}^{K-1} \phi_{j} \boldsymbol{\nabla} (\mu_{j}-\mu_{K}),\quad \forall\ (\boldsymbol x,t)\in \varOmega \times [0, T{t}], \end{equation}

where the chemical potential is defined by the variational approach as $\mu _{j}\equiv \partial f/\partial \phi _{j}-2\kappa _{j} \nabla ^{2}\phi _{j}$.

With the surface tension force, the incompressible Navier–Stokes equation for the convection velocity $\boldsymbol {u}$ reads

(6.8)\begin{gather} \boldsymbol{\nabla}\boldsymbol{{\cdot} }\boldsymbol{u} = 0; \end{gather}

(6.9)\begin{gather}\rho \left(\partial{t} \boldsymbol{u} + \boldsymbol{u} \boldsymbol{\cdot} \boldsymbol{\nabla} \boldsymbol{u}\right) = \boldsymbol f_{s} -\boldsymbol{\nabla} p + \boldsymbol{\nabla}\boldsymbol{\cdot} \left[\eta (\boldsymbol{\nabla} \boldsymbol{u}+ \boldsymbol{\nabla} \boldsymbol{u}^{{\rm T}})\right], \quad \forall\ (\boldsymbol x,t)\in \varOmega \times [0, T{t}]. \end{gather}

The parameters $\rho$, $\eta$ and $p$ denote the fluid density, viscosity and pressure, respectively. The evolution equations (6.6), (6.8) and (6.9) effect a decrease of the total energy of the system (S.II.5). By selecting the reference values $x^*$, $\sigma ^*$ and $D^*$ for the length, surface tension and diffusivity, respectively, we have the following dimensionless quantities: $Re$, $We$ and $P\acute {e}$ (Appendix A).

We present some remarks for the divergence free of the velocity when diffusion is considered. At atmospheric pressure and at room temperature, the density of a fluid mixture is almost constant, as supported by many experimental data and theories. For instance, at room temperature and 1 atm, the density of air with 100 % relative humidity is 1.1 times that of dry air with 0 % relative humidity (Picard et al. Reference Picard, Davis, Gläser and Fujii2008). In view of this fact, it is reasonable to assume ${\rm d}\rho /{\rm d} t\approx 0$ for a liquid–gas system at room temperature and 1 atm. By using the materials derivative with a frame moving with the direction of the fluid velocity $\boldsymbol u$, we have the following expression for the total derivative: ${\rm d}\rho /{\rm d} t=\partial \rho /\partial t+\boldsymbol {u}\boldsymbol {\cdot }\boldsymbol {\nabla } \rho$. In comparison with the continuity equation (Landau & Lifshitz Reference Landau and Lifshitz2013), $\partial \rho /\partial t+\boldsymbol {\nabla }\boldsymbol {\cdot } (\rho \boldsymbol {u})=0$, we have $\rho \boldsymbol {\nabla } \boldsymbol {\cdot } \boldsymbol u=-{\rm d}\rho /{\rm d} t$. Since ${\rm d}\rho /{\rm d} t\approx 0$, the divergence free of the velocity is obtained. Note that the diffusion equation is normally written in terms of the volume composition $\boldsymbol {\phi }$ rather than the density $\rho$ (Landau & Lifshitz Reference Landau and Lifshitz2013). When diffusion takes place, we generally have ${\rm d}\phi _{ i}/{\rm d} t\neq 0$, which seems to contradict with ${\rm d}\rho /{\rm d} t=0$. This contradicting point is realized by using $\phi _{2}=1-\phi _{ 1}$ and ${\rm d}\rho /{\rm d} t=(\rho _{1}^{o}-\rho _{2}^{o})\,{\rm d}\phi _{1}/{\rm d} t$, if $\rho =\rho _{1}^{o}\phi _{1} +\rho _{2}^{o}\phi _{2}$ for a binary mixture with $\rho _{1}^{o}\neq \rho _{2}^{o}$. Here, we prefer to interpret $\rho _{1}^{o}$ and $\rho _{2}^{o}$ as partial densities, rather than the densities of pure fluids before mixing. We think that one possible reason is that $\rho _{1}^{o}$ and $\rho _{2}^{o}$ are no longer constant in a mixture but depend on the local volume fraction. The fact is that one cannot measure the local density $\rho _{i}^{o}$, $i=1, 2$, after mixing, while the density of the mixture $\rho$ and the density of the pure phase before the mixing can be measured. When the local volume concentration varies with time in the diffusion process, the partial density $\rho _{i}^{o}$ should change accordingly via the equation of state relating to the partial pressure; but the density of the mixture $\rho$ does not vary.

7. Criterion of the contact angle measurement

For the two-phase wetting problem based on the phase diagrams in figures 1(I) and 1(II), the components $1$ and $2$ are miscible with each other. The two immiscible phases separate themselves by composition $3$. Thus, we select the average composition $3$ in the droplet and in the matrix $\phi _{{int}} = (\phi _{3}^{\alpha } + \phi _{3}^{\delta })/2$ as the criterion for the interface between the immiscible phases, as shown by the blue solid line in figure 2. This interface position almost corresponds to the extreme value between the two immiscible phases along the tie line in the free energy landscape. Specifically, the contact line radius $r_{c}$ and the droplet height $h$ are used to calculate the macroscopic contact angle as $\theta = 2\arctan (h/r_{c}) \times 180^\circ /{\rm \pi}$.

Figure 2.

Sketch for the contact angle.

For the three-phase wetting problem based on the phase diagram in figure 1(III), the interface for the $\alpha$ phase is marked by the locations where $\phi _{{int}} = (\phi _{1}^{\alpha } + \phi _{1}^{\delta })/2$ (blue line), corresponding to the extreme value in the free energy landscape. Here, $\phi _{1}^{\alpha }$ and $\phi _{1}^{\delta }$ are the equilibrium values of $\phi _{1}$ in the $\alpha$ droplet and in the $\delta$ matrix, respectively. Similarly, we obtain the $\beta$–$\delta$ interface with the criterion of $\phi _{{int}} = (\phi _{2}^{\beta } + \phi _{2}^{\delta })/2$ (red line) as well as the $\alpha$–$\beta$ interface (violet line). By fitting the three interfaces with circular arcs, we denote their intersection point as the triple junction, where three dot-dashed tangent lines for each interface define the contact angles $\theta _{ij}^{\prime }$. At the other triple junctions where the two immiscible phases meet the substrate, the dot-dashed tangent lines are plotted at the contact line position and the contact angle $\theta _{ij}$ is estimated by the same method with the help of tangent lines, as shown in figure 2.

9. Evaporation

In this section, we study the evaporation process of a hydrophilic droplet for the symmetric phase diagram. The initial composition inside the droplet $\boldsymbol \phi =(0.4000,0.3937,0.2063)$ corresponds to point $P_{3}$ in figure 3. The wall free energy coefficient is set to be $g_{33}=0.2$ which leads to a static contact angle of $62.4^{\circ }$. The other simulation parameters are identical to the set-up of figure 4. The evaporation behaviour is manipulated by changing the initial composition of component $2$ in the surrounding environment:

(9.1)\begin{equation} \phi_{2}^{\infty}=S_{0}\phi_{2}^{{e}}. \end{equation}

Here, $S_{0}$ stands for the saturation rate and $\phi _{2}^{{e}}=0.0667$ denotes the binodal composition in the matrix which stays in equilibrium with the initial droplet $\phi _{2}^{{drop}}$. On decreasing the saturation value, the droplets present different morphological evolutions, as demonstrated in figure 7(I). When the surrounding saturation rate is greater than a certain value $S_{0}>25\,\%$, the droplet finally reaches the equilibrium with the surrounding and a small droplet remains on the substrate. While a low saturation $S_{0}\leq 25\,\%$ leads to a completely drying out of the droplets. These two typical morphological evolutions are characterized by the variation of the volume with time, as demonstrated in figure 7(II).

Figure 7.

Model validation for multicomponent droplet evaporation. Examples are shown by considering the initial composition $P_{3}$ of the symmetric phase diagram for different saturation rates $S_{0}$. Dark red: $S_{0}=66.7\,\%$; scarlet: $50.0\,\%$; light red: $33.3\,\%$; light blue: $25.0\,\%$; dark blue: $12.5\,\%$. (I) Exemplary simulation snapshots with time evolution: (a) $S_{0}=66.7\,\%$; (b) $S_{0}=50.0\,\%$; (c) $S_{0}=25.0\,\%$. (II) The normalized droplet volume $V/V_{0}$ with time ($V_{0}$, initial droplet volume). (III) The contact base radius $r_{c}$ with time. (IV) The composition of component $2$ inside the droplet $\phi _{2}^{{drop}}$ with time. (V) The composition of component $2$ in the environment $\phi _{2}^{\infty }$ with time. (VI) The log–log plot of the correlation factor $\xi$ in (9.4) changes with $\phi _{2}^{{drop}}$. The results for different saturation rates $S$ follow the scaling law $\xi \sim (\phi _{2}^{{drop}})^{-0.5}$ which is demonstrated in experiments (Kim & Weon Reference Kim and Weon2018). The scaling law is guided by the dashed black line.

We compare the simulation results with an empirical formulation proposed in Kim & Weon (Reference Kim and Weon2018), which is based on the experimental evaporation of coffee droplets. According to the diffusion-limited theory (DLT), the evaporation rate of a dilute droplet is calculated as (Stauber et al. Reference Stauber, Wilson, Duffy and Sefiane2014)

(9.2)\begin{equation} \rho({\rm d} V/{\rm d} t)_{{DLT}} ={-}{\rm \pi} r_{c} D(\phi_{2}^{{drop}}-\phi_{2}^{\infty})g(\theta).\end{equation}

The evaporation rate is scaled by the water diffusivity $D$ as well as by the composition difference of component $2$ between the droplet and the environment ($\phi _{2}^{{drop}}-\phi _{2}^{\infty }$). The latter reflects the $\phi _{2}$ saturation and is the driving force for the evaporation. The wetting effect is considered by a geometric factor $g(\theta )$ as (Stauber et al. Reference Stauber, Wilson, Duffy and Sefiane2014)

(9.3)\begin{equation} g(\theta) = \tan\frac{\theta}{2} + 8 \int_{0}^{\infty} \frac{\cosh^{2}(\theta\zeta)}{\sinh(2{\rm \pi}\theta\zeta)}\tanh[\zeta({\rm \pi}-\theta)]\,{\rm d}\zeta. \end{equation}

As component $2$ inside the droplet gets dried up, the simulated evaporation rate $(\textrm {d} V/\textrm {d} t)_{{Sim}}$ deviates gradually from the theoretical value $(\textrm {d} V/\textrm {d} t)_{{DLT}}$. Their ratio is named as the correlation factor $\xi$:

(9.4)\begin{equation} \xi = \frac{({\rm d} V/{\rm d} t)_{{DLT}}}{({\rm d} V/{\rm d} t)_{{Sim}}}. \end{equation}

Here, $(\textrm {d} V/\textrm {d} t)_{{DLT}}$ is evaluated by using the base radius $r_{c}$ shown in figure 7(III) and the droplet compositions illustrated in figure 7(IV,V). If the droplet evaporation follows the DLT, the correlation factor $\xi$ should keep constant for its entire lifetime. However, the DLT (9.2) is only valid for dilute droplets. As the droplet becomes more concentrated during the evaporation, (9.2) loses its validity. As demonstrated in figure 7(VI) for $\xi$ versus time-dependent $\phi _{2}^{{drop}}$, we observe the scaling law $\xi \sim 1/\sqrt {\phi _{2}^{{drop}}}$, which shows good consistency with the evaporation behaviours of coffee droplets in experiments (Kim & Weon Reference Kim and Weon2018).

Notably, the evaporation phenomenon in figure 7 considers the diffusion of three compositions $\phi _{1}$, $\phi _{2}$ and $\phi _{3}$ in the whole domain (droplet and gas phase). Figure 7(I) shows the evolution of composition $\phi _{3}$; the other two compositions $\phi _{1}$ and $\phi _{2}$ change with time as well (not shown). Because of the symmetry of the phase diagram and the same mobility/diffusivity for all the compositions adopted in the simulation, the components evaporate synchronously and simultaneously as illustrated in figure 7. However, if an asymmetric phase diagram is considered and/or the mobility is set to be distinct for different components, we may have inhomogeneous evaporation rates, which lead to non-uniform composition at the droplet–surrounding interface. The resulting composition gradient gives rise to pronounced interfacial flows, e.g. Marangoni flow. In figure 7, the fluid dynamics is neglected. By considering the complex fluid dynamics of multicomponent evaporation, some other phenomena can be observed, such as Ouzo effect (Diddens et al. Reference Diddens, Tan, Lv, Versluis, Kuerten, Zhang and Lohse2017; Lohse & Zhang Reference Lohse and Zhang2020), pancake structure (Pahlavan et al. Reference Pahlavan, Yang, Bain and Stone2021), precursor film (Wang et al. Reference Wang, Karapetsas, Valluri, Sefiane, Williams and Takata2021), interfacial instability (Keiser et al. Reference Keiser, Bense, Colinet, Bico and Reyssat2017; Baumgartner et al. Reference Baumgartner, Shiri, Sinha, Karpitschka and Cira2022) and Taylor dispersion (Charlier et al. Reference Charlier, Rednikov, Dehaeck, Colinet and Terwagne2022).

10. Fluid statics

For one-component and one-phase fluid, the static pressure plus the kinetic energy is constant for inviscid incompressible fluids. The pressure varies with the velocity of the fluid, which is affected by the boundary condition. When a one-component droplet is present in an immiscible surrounding phase, an interface appears; the pressure inside and outside the droplet is affected by two factors. (i) The first one is the curvature effect known as the Young–Laplace equation, namely $P^*-P_{0}=\gamma _{\alpha \delta }/R$, where $P_{0}$ is a reference value. This relation is also acknowledged as the Gibbs–Thomson effect in materials science. (ii) The second factor is the fluid velocity, as shown by Bernoulli's law. With an increase in the fluid velocity, the pressure deviates from the static pressure, namely $P^*-P_{0}=\frac {1}{2}\rho \boldsymbol u^{2}$. For a multicomponent droplet, besides factors (i) and (ii), the pressure consists of an additional part, which is the thermodynamic pressure $P= f-\sum _{j=1}^{K}\mu _{j} \phi _{j}$. This is also known as the Landau potential, which is derived based on Euler's formulation in thermodynamics. In the thermodynamic equilibrium, the thermodynamic pressure of two phases is the same, as derived by the variational approach. However, when a non-zero mean curvature is present, the thermodynamic pressure deviates from that of the flat interface. The summation of the thermodynamic pressure with $P^*$ has two functions: (a) enforcing the incompressibility in the Navier–Stokes equation (Jacqmin Reference Jacqmin2000), which can be interpreted as an exchange of the kinetic energy with the free energy (potential energy), and (b) the Kortweg stress $-\sum _{ j=1}^{K} 2\kappa _{ j}\boldsymbol {\nabla } \phi _{ j} \otimes \boldsymbol {\nabla } \phi _{j}$ plus the thermodynamic pressure $P= f- \sum _{j=1}^{K}\mu _{ j} \phi _{ j}$ produces the capillary force in the form of $-\sum _{j=1}^{K}\phi _j\boldsymbol {\nabla }\mu _{ j}$, namely

(10.1)\begin{equation} \boldsymbol{\nabla}\boldsymbol{\cdot} \left[\left(f- \sum_{j=1}^{K}\mu_{j} \phi_{j}\right)\boldsymbol{I}-\sum_{j=1}^{K} 2\kappa_{ j}\boldsymbol{\nabla} \phi_{ j} \otimes \boldsymbol{\nabla} \phi_{j}\right]={-} \sum_{j=1}^{K}\phi_{ j}\boldsymbol{\nabla}\mu_{j}. \end{equation}

The left- and right-hand sides are termed the stress and the potential forms of the capillary force, respectively. Given the importance of the thermodynamic pressure, we validate the numerical convergence of its calculation as well as its relation with the mean curvature in this section. We consider the case when the fluid reaches the static state as in the Young–Laplace case. In the static state, the contact angle reaches the Young's contact angle.

We consider the numerical convergence of the Cahn–Hilliard model coupling with the Navier–Stokes equation. For 2-D simulation of the symmetric phase diagram, we vary the resolution of the numerical discretization by changing the space step ${\rm \Delta} x = {\rm \Delta} y$ from $0.5$ to $4.0$, while fixing the values of $N_{x}\times {\rm \Delta} x$ and $R\times {\rm \Delta} x$. The former and the latter values correspond to the physical length of the domain and the physical radius of the droplet, respectively. For instance, we set the radius of the droplet $R=20$ and the domain size $N_{x}=132$ for ${\rm \Delta} x=1.0$. The simulation parameters are $\kappa _{1}=\kappa _{2}=\kappa _{3}=2$, $\tau _{1}=\tau _{2}=\tau _{3}=1$, $D_{1}=D_{2}=D_{3}=1$. The wall free energy density parameters are set with $g_{33}=0.2$ and the rest $g_{ij}=0.0$. The density $\rho$ and viscosity $\eta$ of the fluid are assigned as $1$. As depicted in figure 8(I), both the equilibrium contact angle $\theta$ and the Young–Laplace pressure ${\rm \Delta} P$ converge with the reduction in ${\rm \Delta} x$. Here, the thermodynamic pressure is defined as $P\equiv f(\boldsymbol \phi ^{e})-\sum _{j=1}^{K} \mu _{j}^{e} \phi _{j}^{e}$. For the optimization of simulation accuracy and computational effort, we select ${\rm \Delta} x=1.0$ as a compromise. Another convergence factor for the numerical discretization is the residual $eps$ for solving the Poisson equation in the Navier–Stokes equation via the conjugate gradient method. The simulation results in figure 8(II) demonstrate the convergence of the equilibrium contact angle $\theta$ and the thermodynamic pressure ${\rm \Delta} P$ with decreasing residual $eps$. As a consequence, we choose $eps=10^{-7}$ for our simulation, which presents both high accuracy and convergence speed. For verifying the numerical convergence of the Poisson equation, the space step is chosen to be ${\rm \Delta} x = {\rm \Delta} y = 1.0$.

Figure 8.

The validation of the Navier–Stokes equation on the wetting problem. (I) The convergence of the equilibrium contact angle $\theta$ and the thermodynamic pressure ${\rm \Delta} P$ with increasing mesh fineness ${\rm \Delta} x={\rm \Delta} y$. (II) The convergence of $\theta$ and ${\rm \Delta} P$ with decreasing residual $eps$ for solving the Poisson equation. (III) The Young–Laplace pressure ${\rm \Delta} P$ versus the reciprocal of the radius $1/R$ of the droplet for different compositions $P_{1}$ (square), $P_{2}$ (circle), $P_{3}$ (cross) and $P_{4}$ (triangle) of the symmetric phase diagram shown in figure 1. The dashed line illustrates the theoretical Young–Laplace relationship. (IV) The thermodynamic pressure ${\rm \Delta} P$ versus the curvature $1/R$ for different compositions $P_{1}$ (square), $P_{2}$ (circle), $P_{3}$ (cross) and $P_{4}$ (triangle) of the asymmetric phase diagram shown in figure 5. The dashed, dot-dashed, dotted and solid lines illustrate the theoretical curves from the Young–Laplace equation ${\rm \Delta} P=\gamma _{\alpha \delta }/R$.

Next, we place droplets with different droplet radii $R$ on the substrate for compositions $P_{1}$, $P_{2}$, $P_{3}$ and $P_{4}$ for both the symmetric and the asymmetric phase diagrams. For the symmetric phase diagram, identical simulation parameters to those of § 8.1 are adopted. As shown in figure 8(III), for different droplet compositions marked by square ($P_{1}$), circle ($P_{2}$), cross ($P_{3}$) and triangle ($P_{4}$) symbols, the Young–Laplace pressure ${\rm \Delta} P$ from the phase-field simulation increases linearly with the curvature $1/R$. Compared with the theoretical expression ${\rm \Delta} P=\gamma _{\alpha \delta }/R$ depicted by the dashed line, the slope $\gamma _{\alpha \delta }$ equals the surface tension which is obtained by the path integral shown in figure 4(I) via (2.4). For the asymmetric phase diagram, the adopted simulation parameters are identical to those in § 8.2. As illustrated in figure 8(IV) by square ($P_{1}$), circle ($P_{2}$), cross ($P_{3}$) and triangle ($P_{4}$) symbols, the simulated Young–Laplace pressure is also proportional to $1/R$, but with distinct slopes for different compositions. For comparison with the Young–Laplace theory, we present the theoretical expression ${\rm \Delta} P=\gamma _{\alpha \delta }/R$, which is depicted by the dashed, dot-dashed, dotted and solid lines for compositions $P_{1}$, $P_{2}$, $P_{3}$ and $P_{4}$, respectively. Differing from the the results in figure 8(III), the Young–Laplace curves for different compositions differentiate from each other. This difference is caused by the distinct surface tensions for different compositions in the case of the asymmetric phase diagram, which are obtained by the path integral depicted in figure 5(I) via (2.4). As demonstrated in figure 8(IV), the simulation results quantitatively agree with the Young–Laplace relationship.

11. Fluid dynamics

11.1. Velocity field

In this section, we present the establishment of the equilibrium Young's angle with fluid flow for the symmetric phase diagram. The parameters are identical to those of § 8.1. The Péclet number, the Reynolds number and the Weber number all are set to be 1. As shown in figure 9, a semicircular droplet is initially placed on the substrate, corresponding to a contact angle of $90^{\circ }$, which is far away from its equilibrium value $\theta =63^{\circ }$. Because of the imbalanced interfacial tension at the triple junction, the droplet spreads outwards, which results in the composition changes iterated by the wetting boundary condition (6.5). Despite the no-slip boundary condition, the composition on the substrate is updated according to the gradient descent method via (6.5). The evolution of the composition on the substrate leads to a composition gradient at the bulk region above the surface. Thereafter, the thermodynamic force $\boldsymbol f_{s}= -\sum _{j=1}^{K-1}\phi _{j}\boldsymbol {\nabla }(\mu _{j}-\mu _{K})$ is engendered and propels the fluid flow starting from the triple junction. As can be noticed at $t=2.5$ in figure 9(b), the maximal velocity is observed near the contact line and propagates gradually towards the matrix region, as shown by the black streamlines on the right-hand side of the panels. At $t=150$ and 400, a Marangoni vortex occurs at the interface, the formation of which is demonstrated in the next section. Finally, at $t=1200$, not only does the sessile droplet reach its equilibrium shape with $\theta =63^{\circ }$, but both substrate and bulk regions are thermodynamically stable as well. Consequently, without the thermodynamic force, the fluid flow decays markedly. Although very small velocity (${\sim }10^{-5}$) inside the domain can still be proved by the streamlines, its disappearance is only a matter of time, which is decided by the accuracy of the numerical model, and the relevant parameters in the Navier–Stokes equation, such as the viscosity $\eta$ and density $\rho$.

Figure 9.

A semicircular droplet spreads with fluid flow to its equilibrium shape $\theta =63^{\circ }$. Initial composition $P_{3}$ in the symmetric phase diagram is simulated and the initial droplet radius is $R=40$. The wall energy density parameter is identical to that of figure 8(I). The left half of each panel depicts the pressure, while the right half illustrates the velocity field with black solid streamlines. The colour bars beneath indicate the corresponding magnitudes.

The flow patterns in figure 9 are quite similar to the so-called bulk flow inside the droplet obtained by the sharp interface model (Diddens, Li & Lohse Reference Diddens, Li and Lohse2021). The origin of the present flow is the capillary force (6.9) which is proportional to the gradient of the chemical potential within the framework of the diffuse interface approach. Note that we use the concept of a generalized chemical potential rather than the surface tension for the evolution of the fluid flow. The point is that if the no-slip boundary condition is applied on the substrate, the contact line should not move. When introducing the chemical potential, the movement of the contact line is induced by the non-uniform chemical potential on the substrate, leading to the ‘slip’ effect. When the contact line is moving, the chemical potential is non-uniform in the bulk of the droplet–surrounding as well as at the droplet–surrounding interface, inducing the fluid flow. The chemical potential has two terms, $\mu _{j}=\partial f/\partial \phi _{j}-2\kappa _{j} \nabla ^{2}\phi _{j}$, which is non-local. The former one $\partial f/\partial \phi _{j}$ is responsible for the bulk flow and the latter one $2\kappa _{j} \nabla ^{2}\phi _{j}$ mainly gives rise to the Marangoni flow. The present case has both flows. The competing effect of these two flows results in distinct flow patterns. An enhanced Marangoni flow at the interface can be achieved by imposing a strong dependence of the gradient energy coefficient $\kappa _{j}$ on the composition, which is out of the scope of the current work. The conventional Marangoni flow is induced by the surface tension gradient in the sharp interface concept. In the diffuse interface framework, the surface tension is the excess bulk free energy across the interface plus the gradient energy density. In this way, the gradient of the non-local chemical potential in the diffuse interface should be a more generalized driving force than the surface tension gradient in the sharp interface to account for the natural bulk and interfacial flows.

A difference of the present flow from that of Diddens et al. (Reference Diddens, Li and Lohse2021) is the boundary condition for the convection velocity at the droplet–surrounding interface. Because of the consideration of evaporation in Diddens et al. (Reference Diddens, Li and Lohse2021), the flow velocity in the normal direction $\boldsymbol u\boldsymbol {\cdot }\boldsymbol m$ differs from $\boldsymbol u_{I}\boldsymbol {\cdot }\boldsymbol m$ ($\boldsymbol m$ is the outward normal vector of droplet surface), where $\boldsymbol u_{I}$ is the interface velocity. The compensation is the diffusive flux. This boundary condition is derived based on a linear interpolation of the individual velocity of the components by mass fraction. However, it should be noted from the aspect of thermodynamics that the velocity is not an extensive variable. A linear interpolation/average of the individual velocity $\boldsymbol u_i$ engenders an additional contribution to the kinetic energy, which is proportional to the product of the individual velocities of the components, $\boldsymbol u_i\boldsymbol {\cdot } \boldsymbol u_j$, $i\neq j$. We refer to Abels et al. (Reference Abels, Garcke and Grün2012) for more discussions when diffusion is considered for two immiscible fluids with a large density ratio. In the present section and in the following analysis, the fluid velocity is assumed to be continuous in the normal direction; no evaporation takes place.

11.2. Comparison with wedge flow

In this section, we compare the flow field with the theory of Huh & Scriven (Reference Huh and Scriven1971). In Huh & Scriven (Reference Huh and Scriven1971), a planar $\alpha$–$\delta$ interface at the triple junction is considered; the fluid contacts a solid wall with a contact angle of $\theta$. The wall moves with a constant velocity $\boldsymbol {U}= (U, 0, 0)$. By defining the stream function $\psi (r,\varphi )$ in the polar coordinates $(r,\varphi )$ with the origin at the triple junction,

(11.1a,b)\begin{equation} u_{r}={-}\frac{1}{r}\frac{\partial \psi}{\partial \varphi},\quad u_{\varphi}=\frac{\partial \psi}{\partial r}, \end{equation}

we have the bi-harmonic equation for a 2-D steady-state flow:

(11.2)\begin{equation} \frac{1}{r}\frac{\partial}{\partial r}\left\{r \frac{\partial}{\partial r} \left[\frac{1}{r} \frac{\partial }{\partial r} \left(r \frac{\partial \psi_{i}}{\partial r}\right)\right]\right\}+ \frac{2}{r^{2}}\frac{\partial^{4}\psi_{i}}{\partial\varphi^{2}\partial r^{2}} +\frac{1}{r^{4}}\frac{\partial^{4}\psi_{i}}{\partial \varphi^{4}} -\frac{2}{r^{3}}\frac{\partial^{3}\psi_{i}}{\partial^{2}\varphi\partial r} + \frac{4}{r^{4}}\frac{\partial^{2} \psi_{i}}{\partial\varphi^{2}}=0. \end{equation}

In the individual fluids, we have the respective stream functions, $\psi _{\alpha }$ and $\psi _{\delta }$. The general solution of the bi-harmonic equation for a bounded velocity in the polar coordinate reads (Huh & Scriven Reference Huh and Scriven1971)

(11.3)\begin{equation} \psi_{i}(r,\varphi)=r(a_{i}\sin \varphi +b_{i}\cos\varphi+ c_{i}\varphi\sin \varphi+d_{i}\varphi\cos\varphi),\quad r\geq0,\enspace \varphi\in[0, 180^\circ]. \end{equation}

The eight coefficients $a_{i}$, $b_{i}$, $c_{i}$, $d_{i}$, $i=\alpha,\ \delta$, are determined by the corresponding boundary conditions (see details in the supplementary material). We highlight two boundary conditions which are modified in the current work. In Huh & Scriven (Reference Huh and Scriven1971), the normal velocities of the fluid–fluid interface are assumed to be zero:

(11.4)\begin{equation} \left.\frac{\partial \psi_{i}}{\partial r}\right|_{\varphi=\theta}=0,\quad i=\alpha,\ \delta. \end{equation}

This boundary is used to keep the interface planar. ‘Because the interface is idealized as being perfectly flat, no condition can be imposed on the normal stress acting at it’. In lieu of the assumption for the zero normal velocity at the fluid–fluid interface, we modify this boundary condition as

(11.5)\begin{equation} \left.\frac{\partial \psi_{\alpha}}{\partial r}\right|_{\varphi=\theta}= \left.\frac{\partial \psi_{\delta}}{\partial r}\right|_{\varphi=\theta}. \end{equation}

The modified condition ensures the continuity of the velocity in the normal direction of the fluid–fluid interface, which is known as the impenetrability constraint. In this way, the normal velocities at the interface in both fluids are not necessarily zero. This is the key way to achieve a Marangoni vortex across the liquid–liquid interface (Golovin, Nir & Pismen Reference Golovin, Nir and Pismen1995; Wang, Selzer & Nestler Reference Wang, Selzer and Nestler2015).

Another boundary condition in Huh & Scriven (Reference Huh and Scriven1971) is the stress balance in the tangential direction of the fluid–fluid interface:

(11.6)\begin{equation} \eta_{\alpha} \frac{\partial^{2}\psi_{\alpha}}{\partial\varphi^{2}}= \eta_{\delta}\frac{\partial^{2}\psi_{\delta}}{\partial\varphi^{2}}. \end{equation}

Notably, when applying the modified boundary condition for the normal velocity at the fluid–fluid interface, the stress balance condition has to be adjusted as well. The tangential viscous stress in polar coordinates is expressed as

(11.7)\begin{equation} \tau_{r\varphi}=\eta \left[r\frac{\partial }{\partial r}\left(\frac{u_{\varphi}}{r} \right) +\frac{1}{r}\frac{\partial u_{r}}{\partial \varphi}\right]. \end{equation}

Because of the zero normal velocity, the first term in the viscous stress of (11.7) vanishes and only the second term is considered in (11.7). By considering non-zero normal velocity, we modify the stress balance equation at the fluid–fluid interface as

(11.8)\begin{equation} \eta_{\alpha}\left[r\frac{\partial}{\partial r}\left(\frac{1}{r} \frac{\partial \psi_{\alpha}}{\partial r}\right)-\frac{1}{r^{2}} \frac{\partial^{2}\psi_{\alpha}}{\partial \varphi^{2}}\right]= \eta_{\delta} \left[r\frac{\partial}{\partial r}\left(\frac{1}{r}\frac{\partial \psi_{\delta}}{\partial r}\right) -\frac{1}{r^{2}}\frac{\partial^{2}\psi_{\delta}}{\partial \varphi^{2}}\right]. \end{equation}

Moreover, in the condition of (11.6), only the viscous stress is considered. The surface-tension-related curvature effect in the tangential dimension is overlooked. In this way, the Marangoni flow cannot come into play. We modify this boundary in the next section to account for the Marangoni effect. Other boundary conditions are the same as in Huh & Scriven (Reference Huh and Scriven1971) and listed in the supplementary material.

With the theory of Huh & Scriven (Reference Huh and Scriven1971), an exemplary streamline for a contact angle of $\theta =90^\circ$ and a viscosity ratio of $\eta _{\alpha }/\eta _{\delta }=0.01$ is illustrated in figure 10(I-c) (see Appendix B for other contact angles). Two flow vortices appear in the low-viscosity fluid (left) and one flow vortex is observed in the high-viscosity liquid (right). We consider the same scenario in the simulation, as demonstrated figures 10(I-a) and 10(I-b). Some important set-ups are adopted in the simulation. (i) The wall velocity $U$ is used to calculate the viscous shear force on the first layer on top of the substrate (Jacqmin Reference Jacqmin2000). (ii) The variation of the viscosity in space is achieved by expressing its dependence on the composition as

(11.9)\begin{equation} \eta(\boldsymbol \phi)=\exp[-\varsigma(\phi_{3}-\phi_{3}^{\delta})]. \end{equation}

The viscosity ratio is controlled by the factor $\varsigma$; a value of $\varsigma =-7$ leads to a viscosity ratio of $\eta _{\alpha }/\eta _{\delta }=0.01$. In comparison with the linear interpolation, the exponential function avoids non-physical values of negative viscosity and is more numerically stable. Note that the exponential relation does not mean that the viscosity varies exponentially across the interface. The composition is symmetric in space for a flat interface. For a curved interface, the composition profile is slightly curved according to the Gibbs–Thomson relation. In this way, the viscosity is almost symmetric across the interface but affected by the curvature. (iii) Inflow and outflow boundary conditions are applied on the left, right and top boundaries. (iv) The reciprocal of the Weber number is set to be 0, e.g. $\varepsilon \equiv {1}/{{We}}=0$, so that the surface tension (${\propto }{1}/{{We}}$) has no effect on the flow evolution. The streamlines from the simulation are demonstrated in figure 10(I-a). A noticeable difference from Huh & Scriven (Reference Huh and Scriven1971) is the non-zero normal velocity at the fluid–fluid interface. To compare the simulation with the theory of Huh & Scriven (Reference Huh and Scriven1971), we subtract all the velocity by a reference value to have an almost zero normal velocity at the fluid–fluid interface. The resulting streamlines in the reference frame are depicted in figure 10(I-b). This strategy has been used in Jacqmin (Reference Jacqmin1996) as well. As in the theory of Huh & Scriven (Reference Huh and Scriven1971), two flow vortices are observed in the low-viscosity liquid and one flow vortex is achieved in the high-viscosity liquid. A noticeable difference of figure 10(I-b) from figure 10(I-c) is that the streamlines close to the substrate pass through the interface near the triple junction. This characteristic is also observed in the simulation results of Jacqmin (Reference Jacqmin2000) and is further discussed in figure 11(V).

Figure 10.

Comparison with wedge flow for a contact angle of 90$^\circ$. The simulations are based on composition $P_{3}$ of the symmetric phase diagram. The Reynolds number is 1. The reciprocal of the Weber number is zero ($\varepsilon \equiv {1}/{{We}}=0$) to exclude the surface tension effect. (I) The streamlines from the simulation with $g_{ij}=0$ corresponding to a contact angle of 90$^\circ$ and a viscosity ratio of 0.01 (a), and from the theory of Huh & Scriven (Reference Huh and Scriven1971) (c). For comparison, a reference velocity of order $U/1000$ is subtracted in (a) to account for the reference frame; the resulting streamlines are shown in (b). In the theory, by applying the boundary conditions, we obtain the following coefficients for the streamlines: $a_{\alpha }=2.35$, $b_{\alpha }=-4.24$, $c_{\alpha }=-1.5$, $d_{\alpha }=1.35$, $a_{\delta }=-1.01$, $b_{\delta }=0$, $c_{\delta }=6.45$, $d_{\delta }=0.014$. (II) The streamlines for a viscosity ratio of 1 from simulation (a) and the theory of Huh & Scriven (Reference Huh and Scriven1971) (b). (III) A quantitative comparison for the velocity $u_{r}/U$ in the vertical direction along the interface as a function of the viscosity ratio between simulation and the theory of Huh & Scriven (Reference Huh and Scriven1971).

Figure 11.

Flow pattern with Marangoni effect for a flat liquid–liquid interface and a contact angle of 90$^\circ$. (I) In the simulation, composition $P_{3}$ of the symmetric phase diagram is considered. The Reynolds number and Weber number are 1 and 10, respectively. The viscosity ratio is 1 by assigning $\varsigma =0$. For the theoretical streamlines, the coefficients are $a_{\alpha }=6.87$, $b_{\alpha }=-6.28$, $c_{\alpha }=-{\rm \pi}$, $d_{\alpha }=2$, $a_{\delta }=-3$, $b_{\delta }=0$, $c_{\delta }={\rm \pi}$, $d_{\delta }=2$. The pulling velocity of the substrate is $U=1$. (II) The simulation set-up is the same as (I) except for a different viscosity ratio of 0.01. For the theoretical streamlines, the coefficients are $a_{\alpha }=3.71$, $b_{\alpha }=-6.28$, $c_{\alpha }=-2.13$, $d_{\alpha }=2$, $a_{\delta }=-0.85$, $b_{\delta }=0$, $c_{\delta }=0.76$, $d_{\delta }=-0.16$. (III) The simulation set-up is identical to (II) except that the composition is $P_{1}$. The Marangoni vortex vanishes for composition $P_{1}$. (IV) A decrease of the Weber number to 1 (increasing the Marangoni effect by a factor of 10), we again obtain a similar flow pattern with three vortices. (V) Comparison with the flow patterns in Jacqmin (Reference Jacqmin2000) for $\theta =90^\circ$ and $\eta _{\alpha }/\eta _{\delta }=1$. (a) Reproduced with permission, Copyright Cambridge University Press 2000. (b) Theoretical flow patterns with $a_{\alpha }=2.26$, $b_{\alpha }=-1.89$, $c_{\alpha }=-9.43$, $d_{\alpha }=6$, $a_{\delta }=-7$, $b_{\delta }=0$, $c_{\delta }=9.43$, $d_{\delta }=6$. (c) Theoretical flow patterns with $a_{\alpha }=1.75$, $b_{\alpha }=-2.20$, $c_{\alpha }=-1.1$, $d_{\alpha }=0.7$, $a_{\delta }=-1.7$, $b_{\delta }=0$, $c_{\delta }=1.1$, $d_{\delta }=0.7$.

We reconsider the reasonableness of the condition (11.4). In the simulation, we set a viscosity ratio of 1 by setting $\varsigma =0$ and the substrate is pulling to the right with a velocity of $U=1$. The streamlines from the simulation are presented in figure 10(II-a). The resulting parallel streamlines demonstrate a linear velocity in the vertical dimension, which is obviously the solution of the Laplace equation for the fluid velocity. However, according to the theory of Huh & Scriven (Reference Huh and Scriven1971), we obtain two flow vortices, as shown in figure 10(II-b). These theoretical streamlines significantly differ from our simulation results with continuous non-zero normal velocity at the fluid–fluid interface. The reason for these differences is as follows. The theory of Huh & Scriven (Reference Huh and Scriven1971) considers a sharp interface model, where the triple junction is a singularity point. By using the resulting coefficients $a_{i}$, $b_{i}$, $c_{i}$ and $d_{i}$, it can be readily shown that the velocities $u_{r}$ and $u_{\varphi }$ at the triple junction $r=0$, $\varphi =90^\circ$ are different in the $\alpha$ and $\delta$ phases. This indicates a discontinuity in the fluid velocity at the triple junction, giving rise to a breakup of the velocity at the fluid–fluid interface. This result is non-physical on the continuum scale since there is no reason for the discontinuity in the fluid velocity when the two fluids have the same viscosity (equal viscosity and no surface tension means one-phase flow). In contrast to the sharp interface model, the diffuse interface model in the current work avoids the singularity problem in the continuum scale and the fluid velocity is continuous everywhere. In the diffuse interface, the triple junction is resolved by a triple region. The movement of the triple region is governed by the natural boundary condition, resulting from the minimization of the free energy functional $\mathcal {F}(\boldsymbol \phi, \boldsymbol {\nabla }\boldsymbol \phi )$ in accordance with the energy law. The question of whether the diffuse interface model resolves the singularity problem has been discussed by Cox (Reference Cox1986) and Jacqmin (Reference Jacqmin2000). The answer is yes. Detailed discussions about the contact line in the diffuse interface model are provided in Jacqmin (Reference Jacqmin2000).

Despite the difference in the normal velocity $u_{\varphi }$, the tangential velocities $u_{r}$ at the fluid–fluid interface from the theory of Huh & Scriven (Reference Huh and Scriven1971) and the simulation are comparable, as demonstrated in figure 10(III). In the simulation, we vary the viscosity ratio $\eta _{\alpha }/\eta _{\delta }$ from 0.1 to 10 by changing the parameter $\varsigma$. When $\eta _{\alpha }/\eta _{\delta }=1$, we have the velocity parallel to the substrate and thus $u_r=0$ at the interface. When $\eta _{\alpha }/\eta _{\delta }<1$, the velocity $u_{r}$ is negative and downward (see figure 10I-c); when $\eta _\alpha /\eta _{\delta }>1$, the velocity $u_{r}$ becomes positive. The velocity $u_{r}$ as a function of the viscosity ratio is centrosymmetric with respect to the point $(\eta _{\alpha }/\eta _{\delta }, u_{r})=(1,0)$ in the logarithm scale. The reason is that the case $\eta _{\alpha }/\eta _{\delta }>1$ with a positive pulling velocity $U$ is identical to the scenario $\eta _{\delta }/\eta _{\alpha }<1$ with a negative pulling velocity $-U$. As shown in figure 10(III), the simulation results for $u_r$ coincide well with the analysis of Huh & Scriven (Reference Huh and Scriven1971).

Next, by using the modified boundary condition (11.5), we obtain distinct flow patterns according to the theory of Huh & Scriven (Reference Huh and Scriven1971). The theoretical flow patterns for a viscosity ratio of 1 and 0.01 are shown in figures 11(I-b) and 11(II-b), respectively. In the former case, we observe three flow vortices, one on the left, one on the right and one across the interface; the flow pattern is symmetric to the interface. With an increase in the viscosity of the right-hand fluid by a factor of 100, the symmetric flow pattern breaks down; all the flow vortices tilt to the less viscous fluid. In the simulations, we obtain similar flow patterns by varying the viscosity ratio (figures 11I-a and 11II-a). A difference of the simulation from figure 10 is that the Weber number is set to $10$ in figures 11(I) and 11(II). A Weber number of 10 and a Reynolds number of 1 indicate a comparable effect between surface tension and the viscous forces. The left and right flow vortices result from the viscous effect. The flow ray passing through the interface is attributed to the Marangoni force, as is demonstrated in the next section; this flow ray is what is observed in figure 9 at $t=150$ and $t=400$. In both theory and simulations, we see that the streamlines pass through the interface, demonstrating non-zero normal velocity at the fluid–fluid interface.

According to (11.3), the normal velocity at the fluid–fluid interface for $\theta =90^\circ$ is proportional to the coefficient $d_{\alpha }$. By using the modified boundary condition (11.5), a constraint has been removed. In order to have a well-defined system of equations for the coefficients of the stream function, we assign a value for $d_{\alpha }$ to account for the effect of the normal velocity; in this way, a constant velocity $u_{\varphi }$ is assigned to the interface. This is of course not a rigorous mathematical derivation, but rather an empirical model with idealization. The empirical model indeed provides a way to explain the Marangoni effect, where the normal velocity is non-zero. The validity of the empirical model is further demonstrated in figure 11(V) by comparing with the numerical results of Jacqmin (Jacqmin Reference Jacqmin2000). Based on the theoretical flow pattern in figure 11(I-b), we decrease $d_{\alpha }$ to 0.7 and obtain narrow and compressed flow ray across the interface, as shown in figure 11(V-b). In contrast, an increase in the value of $d_{\alpha }$ results in broad flow rays across the interface, as depicted in figure 11(V-c). The flow pattern in figure 11(V-b) is comparable with the numerical results obtained in Jacqmin (Reference Jacqmin2000), where the Laplace equation for the chemical potential and the bi-harmonic equation for the stream function are solved numerically. A difference is that the flow near the substrate at the triple junction passes through the interface in figure 11(V-a), while the flow cannot pass the triple junction in figure 11(V-b). Note that the streamline in figure 11(V-b) at the substrate is parallel to the substrate away from the triple junction and suddenly becomes upward/downward at the triple junction. This characteristic obtained by Jacqmin is also observed in our simulation results (figures 11(I,II) and 10(I)).

Next, we analyse the Marangoni effect by considering the balance between the gradient of the chemical potential and the viscous stress. In the diffuse interface model, the Marangoni force is computed by the gradient of the chemical potential $-\sum _{j=1}^{K-1} \phi _{j} \boldsymbol {\nabla } (\mu _{j} -\mu _{K})$ subjected to the Gibbs–Duhem relation. Its balance with the viscous stress in the tangential direction $\boldsymbol {t}$ is expressed as

(11.10)\begin{equation} -\sum_{j=1}^{K-1} \phi_{j}\boldsymbol{\nabla} (\mu_{j}-\mu_{K}) \boldsymbol{\cdot} \boldsymbol t =\boldsymbol n \boldsymbol{\cdot} \eta_{\alpha} (\boldsymbol{\nabla} \boldsymbol u_{\alpha}+ \boldsymbol{\nabla} \boldsymbol u_{\alpha}^{{\rm T}}) \boldsymbol{\cdot} \boldsymbol t - \boldsymbol n \boldsymbol{\cdot}\eta_{\delta} (\boldsymbol{\nabla} \boldsymbol u_{\delta} + \boldsymbol{\nabla} \boldsymbol u_{\delta}^{{\rm T}})\boldsymbol{\cdot} \boldsymbol t. \end{equation}

For an incompressible fluid, this balance equation is rewritten as

(11.11)\begin{equation} \sum_{j=1}^{K-1} (\mu_{j}-\mu_{K})\boldsymbol{\nabla} \phi_{j} \boldsymbol{\cdot} \boldsymbol t =\boldsymbol n \boldsymbol{\cdot} \eta_{\alpha} (\boldsymbol{\nabla} \boldsymbol u_{\alpha}+ \boldsymbol{\nabla} \boldsymbol u_{\alpha}^{{\rm T}}) \boldsymbol{\cdot} \boldsymbol t - \boldsymbol n \boldsymbol{\cdot}\eta_{\delta} (\boldsymbol{\nabla} \boldsymbol u_{\delta} + \boldsymbol{\nabla} \boldsymbol u_{\delta}^{{\rm T}})\boldsymbol{\cdot} \boldsymbol t. \end{equation}

These two equations indicate that either the chemical potential or the composition gradient induces Marangoni flow. A difference of the wetting effect of the present ternary fluid from the binary liquid is demonstrated in figures 11(III) and 11(IV). By changing the composition from $P_{3}$ to $P_{1}$ and keeping all other conditions the same, we see that the Marangoni vortex vanishes (figure 11(III)). However, with a decrease in the Weber number to 1 and fixing all other conditions, the Marangoni vortex appears again (figure 11(IV)), resulting from the competing effect with the viscous force. This demonstrates that the Marangoni flow in the ternary system is strongly dependent on composition and phase diagram. The absolute value of the chemical potential at composition $P_{1}$ is less than that at $P_{3}$ (see figure 4), so that the Marangoni effect at $P_{1}$ is less pronounced than at $P_{3}$.

11.3. Comparison with theory coupling with fluid flow and chemical potential

The wetting effect of a two-component and two-phase system is in fact a mathematical problem of the coupled Laplace and bi-harmonic equations (Jacqmin Reference Jacqmin2000). The former and the latter are responsible for the chemical potential and the stream function, respectively. By considering the coupling between the chemical potential and the stream function, a leading-order analysis has been carried out by Jacqmin (Reference Jacqmin2000). This analysis for the stream function and chemical potential is valid for $\theta =90^\circ$ and a viscosity ratio of 1. As in the work of Huh & Scriven (Reference Huh and Scriven1971), the leading-order analysis of Jacqmin (Reference Jacqmin2000) is for a planar interface, where the curvature effect is not considered. Because of the singularity at the triple junction, it is a knotty issue to address the analytical solution of the coupled Laplace and bi-harmonic equations. In addition, for multicomponent liquids, one should envisage a system of coupled Laplace equations for the chemical potential of different components. This makes the analysis even more complex. In the diffuse interface approach, the singularity problem is avoided and the coupled Laplace equation can be solved numerically. In this section, we present a simple analysis for the wetting effect by considering the coupling between the chemical potential and the stream function. This analysis is an example for $\theta =90^\circ$ based on Wang et al. (Reference Wang, Selzer and Nestler2015).

The Marangoni effect in Jacqmin (Reference Jacqmin2000) is induced by pulling the wall with a velocity $U$, which breaks down the symmetry of the composition across the interface. In contrast to this method, we place two nearby droplets to break down the symmetry of the composition. By this consideration, the analysis is carried out in bipolar coordinates ($\varrho$, $\varphi$). The Laplace equation and the biharmonic equations read

(11.12)\begin{equation} \left.\begin{gathered} \nabla^{2} \mu_{i}=0,\\ \nabla^{2} \nabla^{2} \psi=0, \end{gathered}\right\} \end{equation}

and have the general solution

(11.13)\begin{equation} \left.\begin{gathered} \mu_{i}(\varrho,\varphi)=(\cos \varrho-\cos \varphi)^{1/2}\sum_{n=1}^{\infty} G_{n}\cosh(n+1/2)\varrho P_{n}(\cos\varphi),\\ \psi(\varrho,\varphi)=(\cos \varrho-\cos \varphi)^{{-}3/2}\sum_{n=1}^{\infty} X_{n}(\varrho) C_{n+1}^{{-}1/2}(\cos\varphi), \end{gathered}\right\} \end{equation}

where $G_{n}$ and $X_{n}$ are coefficients to be determined by the boundary condition at the droplet–surrounding interface. The terms $P_{n}$ and $C_{n+1}^{-1/2}$ represent the Legendre and Gegenbauer polynomials, respectively. We refer to Wang et al. (Reference Wang, Selzer and Nestler2015) for a comprehensive analysis. In contrast to a planar interface, we apply the stress balance between the viscous stress and the chemical potential gradient in the tangential direction on the surface of the droplet:

(11.14)\begin{equation} \eta_{\alpha}\tau^{\alpha}_{\varrho\varphi} - \eta_{\delta}\tau^{\beta}_{\varrho\varphi} = \frac{Re}{We}\sum_{j=1}^{K}\left(\frac{\cosh \varrho-\cos\varphi}{q}\right) \frac{\partial \mu_{j}}{\partial \varphi}. \end{equation}

The factor $q$ relates to the radius of the droplet in bipolar coordinates. For $\theta =90^\circ$, the analysis for the wetting effect is obtained by considering the mirror symmetry with the following boundary conditions at the substrate:

(11.15)\begin{equation} \frac{\partial \mu_{i}}{\partial y}=\frac{\partial \psi}{\partial y}= \frac{\partial^{3} \psi}{\partial y^{3}}=0. \end{equation}

The isolines of the chemical potential and the streamlines from the analysis are shown in figure 12(II) for a viscosity ratio of 1 and a contact angle of $90^\circ$. The isolines of the chemical potential near the substrate are perpendicular to the substrate, demonstrating a contact angle of $90^\circ$ in the analysis. The non-uniform chemical potential along the droplet interface is balanced with the viscous stress, inducing the Marangoni flow. The streamlines near the substrate are parallel to the substrate, resulting from the no-slip constraint for the fluid velocity on the substrate. As shown in the analysis, we observe the formation of two Marangoni vortices within the gap of the two droplets. The streamline passes through the droplet interface, resulting from the boundary condition for the continuity of the velocity in the normal direction of the droplet. The Marangoni vortex is also observed in the numerical simulation, as depicted in figure 12(I). Composition $P_4$ for the symmetric phase diagram is used for the simulation. The droplet has a radius of 40 and a distance apart of 10. The Weber and Reynolds numbers both are set to be 1. Inflow and outflow boundary conditions are used on the left, right and top boundaries. Because of the geometrical asymmetry, the chemical potential within the gap of the droplet differs from that outside the droplet, as depicted by the isolines. This chemical potential gradient results in the Marangoni vortex. Both simulation and theory demonstrate the formation of two Marangoni vortices within the gap of the droplets.

Figure 12.

Formation of Marangoni vortex from simulation and analysis for a contact angle of $\theta =90^\circ$ and a viscosity ratio of 1. (I) Simulation results. Two droplets with a radius of 40 and an initial distance apart of 10 for composition $P_{3}$ of the symmetric phase diagram. The Weber and Reynolds numbers both are unity. (a) Streamlines and (b) isolines of the chemical potential $\mu _{3}$. (II) Analysis. (a) Streamlines and (b) isolines of the chemical potential. The analysis is based on solving the coupled Laplace and bi-harmonic equations in bipolar coordinates. In both simulation and theory, we observe the formation of the Marangoni vortex at the liquid–liquid interface.

12. Three immiscible fluids

In this section, we consider a three-phase three-component system. Not only are the $\alpha$ phase and the $\beta$ phase immiscible with each other, but both phases are also immiscible with the $\delta$ matrix. Under such circumstance, the free energy landscape has three local minima, as demonstrated in figure 1(III).

Similar to the previous discussion, we validate our phase-field model for the three-phase configuration. The following simulation parameters are adopted: $(\chi _{12},\chi _{13}, \chi _{23},\chi _{123})=(2.5,2.5,2.5,4.0)$. And $\kappa _{i}=1$, $D_{i}=1$, $\tau _{i}=1$ are chosen for all components, $i=1,2,3$. At the beginning, we place two circular (2-D) or spherical (3-D) droplets with a radius $R=40$ and a centre distance of $25$ on the substrate. The simulation domain size is $400\times 140$ for 2-D simulation and $200\times 74\times 200$ for 3-D simulation. To reduce the computational time, fluid dynamics is not considered during the time evolution.

The simulated equilibrium wetting morphologies in two and three dimensions are displayed in figures 13(I) and 13(II), respectively. Here, three different scenarios are investigated. (a) Left panel: both the $\alpha$ phase (blue) and $\beta$ phase (red) are hydrophilic, which corresponds to the following wall free energy parameters: $g_{13}=-0.2$ and $g_{23}=-0.1$. (b) Middle panel: the $\beta$ phase is hydrophilic, while the $\alpha$ phase is hydrophobic. The wall free energy coefficients are selected as $g_{13}=-0.2$ and $g_{23}=0.2$. (c) Right panel: both the $\alpha$ and $\beta$ phases are hydrophobic with $g_{13}=0.3$ and $g_{23}=0.2$.

Figure 13.

Wetting morphologies of three immiscible phases. (I) The 2-D simulation: blue, $\alpha$ phase; red, $\beta$ phase; violet, $\delta$ phase. (II) The 3-D simulation. Top and bottom panels are top and side views, respectively. Blue, isosurface of $\alpha$ phase; red, isosurface of $\beta$ phase. The surrounding of the $\delta$ phase is transparent. In each case, three different scenarios are presented. Left panel: $\alpha$ and $\beta$ phases both are hydrophilic. Middle panel: $\alpha$ is hydrophobic and $\beta$ is hydrophilic. Right panel: $\alpha$ and $\beta$ both are hydrophobic.

The simulated contact angles on the substrate $\theta _{ij}$ for all phases are tabulated in table 1 and prove to be directly comparable with the theoretical values via Young's law. The Young's contact angle is calculated by using the three interfacial tensions $\gamma _{\alpha \delta }$, $\gamma _{\alpha S}$ and $\gamma _{\delta S}$ which are estimated by the path integrals according to (5.2) and (5.3). The integral paths for cases (a)–(c) in two dimensions are shown in figures 14(I), 14(II) and 14(III), respectively.

Table 1.

The contact angles from simulations in figure 13 compared with the theoretical values. The definition of contact angle corresponds to the notations in figure 2.

Figure 14.

The composition integral routines on the three-phase diagram for the calculation of the interfacial tensions. The solid lines connect the black dotted equilibrium bulk compositions which vary from one to another across the interfaces. Red: phase $\phi _{1}$ to $\phi _{3}$; blue: $\phi _{2}$ to $\phi _{3}$; grey: $\phi _{1}$ to $\phi _{2}$. The coloured dashed line traces the continuous changes from the bulk composition to its corresponding surface composition marked with an open circle.

For both 2-D and 3-D simulations, the equilibrium contact angles have very small deviations from the theory. Besides, we also compare the contact angles at the three-phase triple junction, namely $\theta ^{\prime }_{12}$, $\theta ^{\prime }_{13}$ and $\theta ^{\prime }_{23}$, with the theoretical calculation according to Neumann's triangle rule. The precise naming method of all contact angles can be found in figure 2. The results are demonstrated in table 1 and excellent agreements between simulation and theory are observed. The contact angle in three dimensions differs slightly from that in two dimensions, which might be attributed to the different curvature constitution in two and three dimensions, as well as the measurement precision discussed in the supplementary material.