We consider the evolution of an interface between an incompressible liquid of viscosity \(\mu _1\) and density \(\rho \), which is laden with surfactant and which is confined below by a wall, and a semi-infinite fluid above of the same density and viscosity \(\mu _2\), as shown in Fig. 1. The bulk surfactant concentration is assumed to not exceed the critical micelle concentration. At equilibrium, the film has a uniform thickness \(h_0\) and a steady shear flow is imposed. The problem is cast in non-dimensional form by scaling lengths with \(h_0\), surface tension with the clean value \(\gamma _0\) that prevails in the absence of surfactant, velocities with \(\gamma _0/\mu _1\), time with \(h_0\mu _1/\gamma _0\), pressures with \(\gamma _0/h_0\), the interface surfactant concentration by the maximum packing \(\varGamma _\infty \), the bulk concentration with \(\varGamma _\infty /h_0\), and the mass flux by \(\varGamma _{\infty }\gamma _0/h_0\mu _1\).
The flow in each fluid region is described by equations for the conservation of mass and momentum. In this study the aim is to focus on the effect of surfactant solubility on the stability of the flow; since the two fluids are assumed to have the same density, the effect of gravity is negligible. The Reynolds number in each layer is defined by \(Re_i=\rho \gamma _0h_0/\mu _i^2\), where \(i=1,2\) is used to label the fluids (see Fig. 1), and is assumed to be small. Consequently the flow is governed by the Stokes momentum equation and the continuity equation,
$$\begin{aligned} 0 = - \nabla p_i + m_i\nabla ^2{\varvec{u}}_i, \qquad \nabla \cdot {\varvec{u}}_i = 0, \end{aligned}$$
(1)
where \(p_i\), \({\varvec{u}}_i=(u_i,v_i)\), \(i=1,2\), are the pressure and velocity fields in the two fluids, the gradient operator is defined in the cartesian coordinate system shown in Fig. 1 by \(\nabla =(\partial _x,\partial _y)\), and \(m_i = 1+(m-1)(i-1)\), with m the viscosity ratio (defined later in (7)). The evolution of the interface at \(y=h(x,t)\) is governed by the kinematic condition
$$\begin{aligned} h_t = v_1 - u_1h_x. \end{aligned}$$
(2)
Subscripts will be used through this paper to either denote variables in the respective fluid (if variable \(i=1,2\) is used) or partial derivatives with respect to the shown variable (where t is time).
The no-slip and no-penetration conditions, respectively, require that \({\varvec{u}}_1=(0,0)\) at the wall, and that velocity in the upper fluid \({\varvec{u}}_2\) is bounded in the far-field as \(y\rightarrow \infty \). Continuity of velocity, requiring that \({\varvec{u}}_1={\varvec{u}}_2\), is imposed at the interface \(y=h(x,t)\) together with the continuity of normal and tangential stresses
$$\begin{aligned}&\left[ -p_i\left( 1+h_x^2\right) + 2m_i\left( h_x^2 u_{ix} + v_{iy} - h_x\left( u_{iy}+v_{ix}\right) \right) \right] _2^1 = \gamma \frac{h_{xx}}{H}, \end{aligned}$$
(3a)
$$\begin{aligned}&\left[ 4m_ih_x u_{ix} + m_j\left( h_x^2-1\right) \left( u_{iy} + v_{jx}\right) \right] _2^1 = -\gamma _xH, \end{aligned}$$
(3b)
where \(H=\sqrt{1+h_x^2}\) and the notation \([F_i]^1_2=F_1-F_2\) is used. The surface tension in conditions (3) is given by the Langmuir equation of state which is \(\gamma = 1 + Ma\ln \left( 1-\varGamma \right) \) [16, 18] and is seen to depend on the interfacial surfactant concentration \(\varGamma \), the evolution of which is described by the convection–diffusion equation [10, 19]
$$\begin{aligned} \frac{1}{H}\Biggl [ \left( H\varGamma \right) _t&+ \left( Hu_I\varGamma \right) _x - \frac{1}{Pe_s}\left( \frac{\varGamma _x}{H} \right) _x \Biggr ] - J_b = 0, \end{aligned}$$
(4)
with \(u_I=u_1(x,y=h(x,t),t)\). Here, the adsorption/desorption flux \(J_b\) is defined by [9]
$$\begin{aligned} J_b = B\Bigl (R_bC(1-\varGamma ) - \varGamma \Bigr ), \end{aligned}$$
(5)
where the bulk concentration C is evaluated immediately below the interface at \(y=h^-\). A positive/negative value of \(J_b\) corresponds to adsorption/desorption of surfactant onto/from the interface. In the film the transport of surfactant molecules is governed by the advection–diffusion equation and associated boundary conditions,
$$\begin{aligned} C_t + {\varvec{u}}_1\cdot \nabla C&= \frac{1}{Pe_b}\nabla ^2C, \quad \; C_y\Big |_{y=0} = 0, \quad \; \frac{h_xC_x-C_y}{H}\Big |_{y=h} = Pe_bJ_b. \end{aligned}$$
(6)
The two boundary conditions ensure that there is no flux of surfactant through the wall and that the flux of surfactant onto the interface matches the adsorption/desorption flux \(J_b\) defined in (5).
The non-dimensional parameters that appear in the equations above are the viscosity ratio, the Marangoni, Biot, and Péclet numbers (surface and bulk), as well as a solubility parameter, respectively, defined by
$$\begin{aligned} m = \frac{\mu _2}{\mu _1},&\quad Ma= \frac{\mathcal {R}\mathcal {T}\varGamma _\infty }{\gamma _0}, \quad B= \frac{k_dh_0\mu _1}{\gamma _0}, \quad Pe_{s,b} = \frac{\gamma _0h_0}{\mu _1{\mathscr {D}}_{s,b}}, \quad R_b = \frac{k_a}{h_0k_d}, \end{aligned}$$
(7)
where \(k_a\), \(k_d\) are the adsorption/desorption kinetic rates, respectively, \({\mathscr {D}}_{s,b}\) are the surface and bulk diffusivities, \(\mathcal {R}\) is the ideal gas constant, and \(\mathcal {T}\) is the absolute temperature. We note that the case of an insoluble surfactant is recovered in one of the limits \(B\rightarrow 0\) or \(R_b\rightarrow \infty \).
Energy budgets
The flow is disturbed by introducing perturbations to the steady state of the form \(f(x,y,t) = {\bar{f}}(y) + {\hat{f}}(x,y,t)\), where the steady state is denoted by the overbar notation and the perturbations are assumed to be small, \({\hat{f}}\ll {\bar{f}}\). Here, f stands for the various variables involved in the problem, i.e. \({\varvec{u}}_i\), \(p_i\), h, \(\varGamma \), C. The steady horizontal velocity is linear in each fluid and given by
$$\begin{aligned} {\bar{u}}_1(y) = sy, \qquad {\bar{u}}_2(y) = \frac{s}{m}(y + m - 1), \end{aligned}$$
(8)
where s is the shear rate at the interface, while the vertical velocities and pressures are constant in both fluids, \({\bar{v}}_{1,2}(y)=0\), \({\bar{p}}_{1,2}(y)=p_0\). The equilibrium state for the surfactant can be found by setting \(J_b=0\) in (5) and is given by uniform concentrations \(0<\bar{\varGamma }<1\) and
$$\begin{aligned} {\bar{C}} = \frac{\bar{\varGamma }}{R_b(1-\bar{\varGamma })}. \end{aligned}$$
(9)
The corresponding equilibrium surface tension is \(\bar{\gamma } = 1 + Ma\ln \left( 1-\bar{\varGamma }\right) \). We note that normally the interfacial concentration \(\bar{\varGamma }\) is prescribed in computations.
To assess the stability properties of the flow and identify the dominant mechanism responsible for interfacial instability, we perform an energy budget analysis. Since the Reynolds number is zero in the present study, the equation for the kinetic energy of the flow does not offer insight into the instability mechanism, but we nevertheless provide it for completeness in Appendix A. Insight can be obtained, however, by examining an equation for the energy of concentration perturbations. To derive this, the linearised convection–diffusion equation for the concentration in the film is multiplied by the perturbation \({\hat{C}}\) and integrated over the film flow region \(y\in [0,1]\). The entire equation is then integrated in one horizontal wavelength \(x\in [0,\Lambda ]\), where \(\Lambda =2\pi /k\) and k is the wavenumber, and spatial periodicity is assumed. Invoking the flux conditions at the wall and interface in (6), the energy budget equation takes the form
$$\begin{aligned} \text {ENC}= \text {DIFC + FLXC} \end{aligned}$$
(10a)
where
$$\begin{aligned} \text {ENC}&= \frac{\mathrm{d}}{\mathrm{d}t} \int _0^\Lambda \int _0^{1} \frac{1}{2}{\hat{C}}^2 \,\mathrm{d} y\,\mathrm{d} x, \nonumber \\ \text {DIFC}&= - \frac{1}{Pe_b}\int _0^\Lambda \int _0^{1} \left( {\hat{C}}_x^2 + {\hat{C}}_y^2 \right) \,\mathrm{d} y\,\mathrm{d} x, \nonumber \\ \text {FLXC}&= - B\int _0^\Lambda \biggl (R_b(1-\bar{\varGamma }){\hat{C}}(1) - \frac{\hat{\varGamma }}{(1-\bar{\varGamma })} \biggr ){\hat{C}}(1) \,\mathrm{d} x. \end{aligned}$$
(10b)
Equation (10b) offers insight into the growth of concentration perturbations and it can be used to identify an instability in Stokes flow [20]. Instability is indicated by a positive value of the ENC term. The diffusion term DIFC is always negative, while the term FLXC is associated with surfactant flux between the bulk and the interface; if the latter effect is sufficiently strong then instability occurs.
Following a similar procedure for the corresponding surfactant transport equation at the interface, but now integrating in the x direction only, the energy equation for the interfacial concentration is found to be
$$\begin{aligned} \text {ENG} = \text {GSH + GU1 + DIFG + FLXG}, \end{aligned}$$
(11a)
where
$$\begin{aligned} \text {ENG}&= \frac{\mathrm{d}}{\mathrm{d}t} \int _0^\Lambda \frac{1}{2}\hat{\varGamma }^2 \,\mathrm{d} x, \nonumber \\ \text {GSH}&= - s\bar{\varGamma }\int _0^\Lambda {\hat{h}}_x\hat{\varGamma } \,\mathrm{d} x, \nonumber \\ \text {GU1}&= - \bar{\varGamma }\int _0^\Lambda {\hat{u}}_{1x}(1)\hat{\varGamma } \,\mathrm{d} x, \nonumber \\ \text {DIFG}&= - \frac{1}{Pe_s}\int _0^\Lambda \hat{\varGamma }_x^2 \,\mathrm{d} x, \nonumber \\ \text {FLXG}&= B\int _0^\Lambda \biggl (R_b(1-\bar{\varGamma }){\hat{C}}(1) - \frac{\hat{\varGamma }}{(1-\bar{\varGamma })}\biggr ) \hat{\varGamma } \,\mathrm{d} x. \end{aligned}$$
(11b)
Instability is present if the term ENG is positive. On the right-hand side in (11b), the term GSH plays a role only in the presence of the background shear, the GU1 term supplies energy due to the perturbed horizontal velocity gradient at the interface, while the term DIFG captures the dampening effect of interfacial diffusion and is always negative. A positive/negative value of FLXG corresponds to a net adsorption/desorption of surfactant onto/from the interface.
The relative sizes of the various terms in (10b) and (11b) can offer insight into the dominant physical mechanisms that provoke instability. Where terms are positive/negative their effect is destabilising/stabilising.
Normal modes
To perform a normal mode analysis it is convenient to introduce the streamfunctions \(\psi _i\), defined so that \(u_i=\partial \psi _i/\partial y\) and \(v_i=-\partial \psi _i/\partial x\). We represent all of the disturbance quantities in the normal mode form \({\hat{f}}(x,y,t) = {\tilde{f}}(y)\mathrm{e}^{ik(x-ct)}\), where k is the real wavenumber to be specified, c is the complex wave speed to be found, and the tilde-decorated variables are eigenfunctions to be determined. The stability of the flow is controlled by the sign of the growth rate \(\lambda \equiv k\mathfrak {I}(c)\); in particular, instability occurs if \(\lambda >0\).
Substituting the normal mode forms into the governing equations (1)–(6) and linearising, we obtain an eigenvalue problem for the complex wave speed c. The streamfunctions satisfy the ordinary differential equation
$$\begin{aligned} {\tilde{\psi }}_{1,2}''''(y) - 2k^2 {\tilde{\psi }}_{1,2}''(y) + k^4{\tilde{\psi }}_{1,2}(y) = 0, \end{aligned}$$
(12a)
with the boundary conditions
$$\begin{aligned}&{\tilde{\psi }}_1(0)={\tilde{\psi }}_1'(0)=0, \qquad {\tilde{\psi }}_2\Big |_{y\rightarrow \infty }={\tilde{\psi }}_2'\Big |_{y\rightarrow \infty }=0, \end{aligned}$$
(12b)
$$\begin{aligned}&{\tilde{\psi }}_1(1) = {\tilde{\psi }}_2(1), \qquad {\tilde{\psi }}_1'(1)-{\tilde{\psi }}_2'(1) = \left( \frac{1}{m}-1\right) \frac{s}{{\tilde{c}}}{\tilde{\psi }}_1(1), \end{aligned}$$
(12c)
where \({\tilde{c}} = c - {\bar{u}}_1(1)\) is the perturbed wave speed. The jump term in condition (12c) arises due to viscosity stratification. The linearised forms of the normal and tangential interfacial stress balances (3) are
$$\begin{aligned}&\left( m{\tilde{\psi }}_2'''(1)-{\tilde{\psi }}_1'''(1)\right) - 3k^2\left( m{\tilde{\psi }}_2'(1)-{\tilde{\psi }}_1'(1)\right) = -\mathrm{i}\bar{\gamma }k^3\frac{{\tilde{\psi }}_1(1)}{{\tilde{c}}}, \end{aligned}$$
(12d)
$$\begin{aligned}&\left( m{\tilde{\psi }}_2''(1)-{\tilde{\psi }}_1''(1)\right) + k^2\left( m{\tilde{\psi }}_2(1)-{\tilde{\psi }}_1(1)\right) = \frac{\mathrm{i}Mak}{(1-\bar{\varGamma })}{\tilde{\varGamma }}. \end{aligned}$$
(12e)
The surfactant concentration perturbation in the bulk satisfies
$$\begin{aligned}&{\tilde{C}}''(y) - k^2{\tilde{C}}(y) - \mathrm{i}kPe_b(sy-c){\tilde{C}}(y) = 0, \end{aligned}$$
(12f)
$$\begin{aligned}&{\tilde{C}}'(0) = 0, \qquad {\tilde{C}}'(1) + Pe_bBR_b(1-\bar{\varGamma }){\tilde{C}}(1) = \frac{Pe_bB}{(1-\bar{\varGamma })}{\tilde{\varGamma }}, \end{aligned}$$
(12g)
and the linearised form of the interfacial surfactant concentration equation (4) is
$$\begin{aligned} \left( -\mathrm{i}k{\tilde{c}} + \frac{k^2}{Pe_s} + \frac{B}{(1-\bar{\varGamma })} \right) {\tilde{\varGamma }} - BR_b(1-\bar{\varGamma }){\tilde{C}}(1) + \mathrm{i}k\bar{\varGamma }\left( \frac{s}{{\tilde{c}}}{\tilde{\psi }}_1(1) + {\tilde{\psi }}_1'(1) \right) = 0. \end{aligned}$$
(12h)
The general solution for the perturbation streamfunctions satisfying Eq. (12a) is
$$\begin{aligned} {\tilde{\psi }}_i(y) = \alpha _{1,i}\,\mathrm{e}^{ky} + \alpha _{2,i}\,y\,\mathrm{e}^{ky} + \alpha _{3,i}\,\mathrm{e}^{-ky} + \alpha _{4,i}\,y\,\mathrm{e}^{-ky}, \end{aligned}$$
(13)
for coefficients \(\alpha _{j,i}\), \(j=1,2,3,4\), \(i=1,2\), to be determined. The far-field conditions in (12b) yield \(\alpha _{1,2} = \alpha _{2,2} = 0\). The general solution for the bulk concentration equation (12f) is
$$\begin{aligned} {\tilde{C}}(y) = b_1\,\mathrm{Ai}(\zeta ) + b_2\,\mathrm{Bi}(\zeta ), \qquad \zeta = (\mathrm{i}ksPe_b)^{1/3}\Bigl (y-\frac{c}{s}-\frac{\mathrm{i}k}{sPe_b}\Bigr ), \end{aligned}$$
(14)
where \({\mathrm{Ai}}\) and \({\mathrm{Bi}}\) are the linearly independent solutions of the Airy equation, and \(b_{1,2}\) are arbitrary constants. Given the exact solutions (13), (14), conditions (12) may be assembled to form the linear system
$$\begin{aligned} {\varvec{M}}\cdot {\varvec{x}} = {\varvec{0}}, \end{aligned}$$
(15)
where the coefficient matrix \({\varvec{M}}\) depends on c and the vector of unknowns is \({\varvec{x}}=(\alpha _{1,1},\alpha _{2,1},\alpha _{3,1},\alpha _{4,1},\alpha _{3,2},\alpha _{4,2},b_1, b_2,{\tilde{\varGamma }})^\mathrm{T}\). Non-trivial solutions are obtained if \(\det ({\varvec{M}})=0\); owing to the presence of the Airy functions in Equation (14), this gives a transcendental equation for the complex wave speed c that in general yields an infinite number of normal modes and which must be solved numerically. In the insoluble limit attained either by taking \(B\rightarrow 0\) or \(R_b\rightarrow \infty \), the equation \(\det ({\varvec{M}})=0\) reduces to a quadratic equation for c corresponding to just two normal modes [5].
Long-wave approximation
Useful insight into the behaviour of the complex wave speed can be gained by considering perturbations of large wavelength. Assuming that \(k \ll 1\), we introduce the expansion for the complex wave speed
$$\begin{aligned} c = c_0 + kc_1 + \cdots , \end{aligned}$$
(16)
substitute it into the transcendental equation \(\det ({\varvec{M}})=0\), and solve at successive orders in k to determine \(c_0\), \(c_1\), etc. In doing so we identify two modes which we term the primary modes, for each of which \(c_0\) is real. The two corresponding values of \(c_1\) are both purely imaginary and yield the leading-order approximation to the growth rate \(\lambda \approx k^2\mathfrak {I}(c_1)\).
Besides the two normal modes that are captured by the expansion (16) there is an infinite number of other modes, which we term secondary modes, whose existence may be attributed to the freedom of the bulk surfactant concentration to disperse in the liquid film. These secondary modes satisfy long-wave expansions different to (16); and, notably, \(\mathfrak {I}(c)<0\) at \(k=0\).
One of the two primary modes is always stable and satisfies
$$\begin{aligned} \mathfrak {I}\big (c_1^{(1)}\big ) = -MaR_b\bar{\varGamma }(1-\bar{\varGamma }) < 0. \end{aligned}$$
(17)
The first-order contribution to the second primary mode has imaginary part
$$\begin{aligned} \mathfrak {I}(c_1^{(2)}) = \frac{A_4R_b^4 + A_3R_b^3 + A_2R_b^2 + A_1R_b+ A_0}{120Pe_sPe_b\left( 1+(1-\bar{\varGamma })^2R_b\right) ^3}, \end{aligned}$$
(18a)
where
$$\begin{aligned}&A_4 = 120(1-\bar{\varGamma })^7\bar{\varGamma }MaPe_sPe_b, \nonumber \\&A_3 = 120(1-\bar{\varGamma })^5\big ( 2\bar{\varGamma }MaPe_s-(1-\bar{\varGamma }) \big )Pe_b, \nonumber \\&A_2 = 8(1-\bar{\varGamma })^3\Bigl ( 15MaPe_sPe_b\bar{\varGamma }- (1-\bar{\varGamma })\big ( 2s^2Pe_sPe_b^2 + 30Pe_b + 15Pe_s \big ) \Bigr ), \nonumber \\&A_1 = -(1-\bar{\varGamma })^2\Bigl ( \big ( 7s^2Pe_sPe_b^2+120Pe_b+240Pe_s \big ) + \frac{30(1-\bar{\varGamma })s^2Pe_sPe_b}{B}\Bigr ), \nonumber \\&A_0 = -(s^2Pe_b^2+120)Pe_s, \end{aligned}$$
(18b)
and it is either stable or unstable depending on the parameters. In particular, noting that the denominator in (18b) is positive, the Descartes’ rule of signs implies that there is exactly one positive value of \(R_b\) at which the numerator, viewed as a polynomial in \(R_b\), changes sign and therefore the flow changes stability. For sufficiently large \(R_b\) we find that \(\mathfrak {I}\big (c_1^{(2)}\big )>0\) so that this mode is unstable in the case of weak solubility, which is qualitatively consistent with established results for insoluble surfactant [3, 5]. Since
$$\begin{aligned} \mathfrak {I}\big (c_1^{(2)}\big ) \rightarrow - \frac{(s^2Pe_b^2+120)}{120Pe_b} < 0 \quad \text {as } R_b\rightarrow 0, \end{aligned}$$
(19)
the second primary mode is evidently stable in the strong solubility limit \(R_b\rightarrow 0\). We conclude that surfactant solubility has a stabilising influence on the flow.
The fact that neither of the two leading-order expressions for the growth rate in (17) and (18b) depend on the viscosity ratio m is striking but it is in line with similar long-wave calculations for insoluble surfactant (e.g. for channel flow [3]). It is intriguing to note that
$$\begin{aligned} \mathfrak {I}\big (c_1^{(2)}\big ) \rightarrow -\infty \quad \hbox { as}\ B\rightarrow 0, \qquad \mathfrak {I}\big (c_1^{(2)}\big ) \rightarrow \infty \quad \hbox { as}\ R_b\rightarrow \infty , \end{aligned}$$
(20)
and hence, curiously, neither of the leading-order growth rates of the two primary modes are consistent with the growth rates presented by Pozrikidis & Hill [5] for insoluble surfactant in the limit \(B\rightarrow 0\) or \(R_b\rightarrow \infty \). This apparent contradiction may be resolved by noting that the expansion (16) breaks down in either of the limits \(B\rightarrow 0\) or \(R_b\rightarrow \infty \); instead the correct expansion should proceed in powers of \(k^{1/2}\).
The situation is reminiscent of the non-uniformity in the long-wave expansion that has been identified in the limits \(s\rightarrow 0\), \(Ma\rightarrow \infty \), \(m\rightarrow 1\), and \(R_b\rightarrow R_b^*\), where \(R_b^*\) is a certain finite value, for the similar flow in a channel (see [4, 9]). We emphasise that the failure to achieve consistency with the results for insoluble surfactant in the limit \(B\rightarrow 0\) or \(R_b\rightarrow \infty \) is a facet of the current long-wave approach; taking either of these limits in the solution to the full transcendental equation \(\det ({\varvec{M}})=0\) stemming from (15) recovers the growth of [5], as is discussed in Appendix B.