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 Interfacial Phenomena and Heat Transfer, 2 (1): xxx–xxx (2014)

APPLICATION OF THE NONLINEAR

POISSON-BOLTZMANN MODEL TO THE STABILITY
OF AN ELECTROLYTE FILM

Christiaan Ketelaar & Vladimir S. Ajaev∗

f
Department of Mathematics, Southern Methodist University, Dallas, TX 75275

oo
∗
Address all correspondence to Vladimir S. Ajaev, E-mail: ajaev@smu.edu

The stability of a thin liquid film of an electrolyte on a solid substrate is investigated. The effects of surface tension,
viscous flow, and electric field described by the nonlinear Poisson-Boltzmann equation are considered in the framework
of a lubrication-type model. Conditions for film breakup due to electrostatic interaction of interfacial charges are investi-
gated. Linear stability criteria are formulated using elliptic integrals. Nonlinear evolution of the film is then investigated
using numerical finite-difference-based methods. Comparison to the predictions of the approximate Debye-Hückel model
is discussed.

Pr
KEY WORDS: thin films, rupture, stability analysis, electrostatic forces, disjoining pressure

1. INTRODUCTION
or
Investigations of stability of thin liquid films have a number of applications, such as flotation and foam dynamics,
[discussed, e.g., in the well-known books by Edwards et al. (1991) and Israelachvili (2011)]. Kabov (2000) and
Kabov et al. (2011) show that thin liquid films are also important for the development of microscale heat transfer
systems, whereas Braun (2012) discusses liquid-film stability in the context of the dynamics of the tear film in the
eye. A comprehensive review article by Oron et al. (1997) provides an overview of studies of thin-film flows driven
by gravity, capillarity, thermocapillarity, solutocapillarity, and disjoining pressure. Craster and Matar (2009) discuss
th

further developments in the field, with detailed description of recent results on surfactant-driven films, evaporating
films, and fingering instabilities. Ajaev (2013) reviews the theoretical work on film rupture by thermocapillarity and
the main instability mechanisms for isothermal films, as well as recent experimental studies of films of polymers,
molten metals, and aqueous solutions.
The most thoroughly investigated driving mechanism of film rupture is due to London-van der Waals dispersion
Au

forces. Ruckenstein and Jain (1974) conducted theoretical studies on the spontaneous rupture of thin liquid films on
a solid substrate by these forces, whereas Scheludko (1962) studied the phenomenon experimentally. Williams and
and Davis (1982) and Burelbach et al. (1988) made further refinements to the models of van der Waals rupture by
analyzing the nonlinear evolution of an unstable thin film on a solid substrate using a lubrication-type approach.
An alternative mechanism of film rupture is due to electrostatic effects. In order to understand this mechanism,
most relevant for film of electrolytes, it is important to review the basic physics of the interaction of two charged
surfaces separated by an electrolyte film. Studies of electric fields in thin layers of liquid electrolytes have been im-
portant to colloid and interface science. The classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloid
stability, developed by Derjaguin and Landau (1941) and Verwey and Overbeek (1948), takes into account the elec-
trostatic interaction between charged spherical particles separated by a liquid layer. Because of the screening effects
of ions in the liquid, each particle is surrounded by an electrical double layer. The electrostatic interaction between
identical spherical particles can then be described as an interaction between the double layers, with the electric field
in the region between the particles described by the nonlinear Poisson-Boltzmann equation. In addition, the authors

2152–5080/14/$35.00 °
c 2014 by Begell House, Inc. 1
2 Ketelaar & Ajaev

NOMENCLATURE

c arbitrary constant of integration z ion valency

Ca Capillary number
d film thickness Greek Symbols
e elementary charge γ growth rate
F incomplete elliptic integral ² electric permittivity of the liquid
G instability measure term ζ perturbation to the base state
h η

f
interface height derivative of the potential with
k wave number respect to y

oo
kB Boltzmann constant θ angle transformation
K complete elliptic integral κ film thickness scaled to Debye length
no bulk ionic concentration λ wave length
p pressure λD Debye length
po atmospheric pressure µ kinematic viscosity
P characteristic pressure σ surface tension of the liquid
q surface charge density φ angle of the elliptic integral
t
T
u
v
x
y
time
temperature
horizontal velocity
vertical velocity
horizontal axis
vertical axis
Pr ψ
Ψ
electrostatic potential
characteristic electrostatic potential

Subscripts
1
2
solid substrate
liquid-gas interface
or
of the DLVO theory took into account the effect of the London-van der Waals dispersion forces. The predictions of
the theory are in good agreement with many experimental observations of colloidal systems. In the limit of the liquid
layer thickness being much smaller than the radius of the curvature of the spherical particle, the problem reduces to the
interaction of electrically charged flat surfaces, a configuration that is often used to provide many important insights
into the physics of interaction of colloidal particles.
th

The study of electrostatic interaction between dissimilar particles is also important for applications (e.g., for
describing colloidal systems that contain several different types of particles). Hogg et al. (1966) developed a model of
double-layer interaction between dissimilar spherical colloidal particles using the linearized version of the Poisson-
Boltzmann model, often referred to as the Debye-Hückel (DH) approximation. The interaction energy was expressed
in terms of given (fixed) potentials of the particle surfaces. Parsegian and Gingell (1972) used the DH approximation
Au

to study the interaction between flat dissimilar surfaces of both constant potential and constant charge density and
identified the conditions for the interaction to be repulsive or attractive. An application of the same approach to the
case of spheres of fixed unequal charges can be found in Usui (1973). However, it is important to note that all studies
based on the DH approximation are limited to the case of low potentials of the interacting solid surfaces.
One of the earliest analytical solutions of the full nonlinear Poisson-Boltzmann equation was formulated by Gouy
(1910) and Chapman (1913) for a surface in contact with an infinite region filled by a liquid electrolyte containing
two types of ions. Grahame (1947) used the same approach to formulate a relationship between the surface charge
density and the potential of the solid for this configuration. Applications of the nonlinear Poisson-Boltzmann equation
to the electrostatic interaction of identical charged surfaces were developed in the framework of the DLVO theory and
discussed in Verwey and Overbeek (1948) and Honig and Mui (1971). Electrostatic interaction of dissimilar surfaces
was investigated based on the Poisson-Bolztmann equation by Derjaguin (1954) and Devereux and de Bruyn (1963).
Further improvements of the model for this configuration were proposed by several authors (Bell and Peterson, 1972;
Gregory, 1975; McCormack et al., 1995; Ohshima, 1974).

Interfacial Phenomena and Heat Transfer

Application of the Nonlinear Poisson-Boltzmann Model 3

An important special case of a nonsymmetrical layer of liquid electrolyte is a film bounded by two different bulk
phases, a solid substrate and a gas phase; note that one of the bounding surfaces is deformable. Mazzoco and Wayner
(1999) studied the electrostatic effects for a wetting film on a solid substrate, whereas Pushkarova and Horn (2008)
determined the electrostatic component of disjoining pressure for bubble-solid interactions in electrolyte solutions.
These studies showed that the liquid-solid and liquid-gas electrical potential may differ in value and in sign; thus,
attractive interfaces can become repulsive. Experimental studies by Schulze et al. (2001) showed that aqueous films
can be destabilized by the presence of electrostatic charges at both interfaces.
By understanding the basic physics of the interaction of two charged surfaces separated by a film of electrolyte,
we can develop the stability criteria for an electrolyte film on a charged substrate. The objective of the present study
is to incorporate the nonlinear Poisson-Boltzmann model equation into the stability analysis of a thin electrolyte film

f
on a substrate. We investigate both the linear stability and the nonlinear evolution of the fluid interface. Of particular

oo
interest are the conditions of film rupture due to the effect of charges at the solid-liquid and liquid-gas interfaces. The
results are compared to our previous study, (Ketelaar and Ajaev, 2014), which is based on the DH approximation of
the Poisson-Boltzmann equation.

2. FORMULATION
We consider a thin liquid film of viscosity µ and dimensional thickness d on a flat solid surface, as shown in Fig. 1. The
Cartesian coordinates along the solid and normal to it are denoted by x and y, respectively. The liquid is a symmetric

Pr
electrolyte with ions of valencies z and bulk concentrations no . The Debye length is defined as

λD =
r
²kB T
2e2 n0 z 2
where ² is the electric permittivity of the liquid, kB is the Boltzmann constant, and T is the temperature. We note that
the Debye length determines the characteristic thickness of the screening layer formed in the liquid near a charged
surface, [discussed in more detail, e.g., in Probstein (1994) and Kirby (2010)].
(1)

The solid substrate is electrically charged and has a constant electric charge density q1∗ . At the liquid-air interface,
or
we consider a constant electric charge density q2∗ . The dimensional film thickness is denoted by h∗ . When the interface
deforms as a result of the instability, the film thickness is a function of both the horizontal coordinate x∗ and time
t∗ . By using the film thickness d as the vertical length scale and Ψ = kB T /(ze) as the scale for the electrostatic
potentials, the Poisson-Boltzmann equation for a symmetric electrolyte is written as follows:
th

ψyy = κ2 sinh(ψ) (2)

where κ = d/λD . We assume that the horizontal length scale is much larger than d, as specified below; thus, the
derivatives of the potential with respect to the horizontal coordinate are neglected. The boundary conditions are for-
mulated in terms of nondimensional charge densities q1 = q1∗ λD /(εΨ) and q2 = q2∗ λD /(εΨ) as follows:
Au

ψy |y=0 = −κq1 (3)

gas
y* q*
2
liquid electrolyte
h*
q*
1
x*
solid
FIG. 1: Sketch of a thin film of liquid electrolyte on a flat solid substrate.

Volume 2, Number 1, 2014

4 Ketelaar & Ajaev

ψy |y=h = κq2 (4)

To analyze how the electrostatic effects affect the evolution of the thin film, we can simplify the Navier-Stokes equa-
tions to a system of lubrication-type equations, [discussed, e.g., in Ajaev (2012) and Ajaev et al. (2010)]. We introduce
the capillary number Ca = µU/σ, where σ is the surface tension the air-liquid interface, and define the horizontal
length scale as Ca−1/3 d. In order to balance the electrostatic, capillary, and viscous contributions to the stresses in the
film as it deforms, we define the velocity and pressure scales as follows,
3/2
(2n0 kB T d)
U= (5)
µσ1/2

f
P = 2n0 kB T (6)

oo
The dimensionless horizontal and vertical velocity components, u and v, the pressure p, and time t, can now be defined
in terms of our velocity and pressure scales in the following manner:
u∗ v∗ p∗ U t∗
u= , v= , p= , t= (7)
U Ca1/3 U P 3dCa−1/3
The use of these scalings allows us to write the nondimensional Stokes flow equations in the following form:

Pr
px = Ca2/3 uxx + uyy + sinh(ψ)ψx

py = Ca4/3 vxx + Ca2/3 vyy + sinh(ψ)ψy

ux + vy = 0
The momentum equations simplify further with the assumption of small capillary number, leading to

px = uyy + sinh(ψ)ψx
(8)

(9)
(10)

(11)
or
py = sinh(ψ)ψy (12)
Note that, in this model, the effects of gravity are neglected and the liquid flow description includes an electrostatic
body force term in the momentum balance. The scaled components of this force, sinh(ψ)ψx and sinh(ψ)ψy , appear
on the right-hand sides of Eqs. (11) and (12), respectively.
At the solid wall (y = 0), the viscous flow satisfies the usual boundary conditions of zero slip and zero normal
th

velocity. At the interface (y = h), the conditions of tangential stress and capillary pressure jump are written in the
following form:
κuy + q2 (ψx + κq2 hx ) = 0 (13)
1
p − p0 = −hxx + q22 (14)
2
Au

where p0 is the scaled atmospheric pressure. The kinematic boundary condition at the liquid-air interface is
1
ht + uhx = v (15)
3

3. EVOLUTION EQUATION
The advantage of the lubrication-type formulation is that it allows one to reduce the viscous flow problem to a single
partial differential equation for film thickness using the following steps. Direct integration of Eq. (12) leads to the
conclusion that p − cosh(ψ) is independent of y. To obtain the horizontal velocity profile, we integrate Eq. (11) in y
with the boundary condition (13) and the no-slip condition at the substrate, resulting in
µ ¶
1 ψ
u = (p − cosh ψ)x (y 2 − 2yh) − hx q2 q2 h + y (16)
2 κ x

Interfacial Phenomena and Heat Transfer

Application of the Nonlinear Poisson-Boltzmann Model 5

This velocity profile together with the continuity equation (10), the kinematic boundary condition (15), and the pres-
sure jump condition (14) leads to an evolution equation for the film thickness in the following form:
· µ ¶ ¸
3 3 2 ψ2
ht + h (hxx + cosh ψ2 )x − q2 h q2 h + =0 (17)
2 κ x x
where ψ2 is the potential at the liquid-air interface, found from the Poisson-Boltzmann model as discussed next.
Because we are interested in situations when the film dynamics is dominated by electrostatic effects, we do not
consider other possible contributions to disjoining pressure, such as London-van der Waals dispersion forces.
To determine the potential ψ2 at the solid-liquid interface, we analyze the nonlinear Poisson-Boltzmann equation

f
[Eq. (2)]. It is a second-order differential equation that can be rewritten as a first-order differential equation if we
introduce η(ψ) = ψy , then use

oo
dη 1 dη2
ψyy = (ψy )y = η= (18)
dψ 2 dψ
The resulting differential equation
dη2
= 2κ2 sinh ψ (19)
dψ
is integrated once, leading to
2
(ψy ) = 2κ2 (cosh ψ + c)

Pr c= q − cosh(ψ2 )
2 2
(20)
The integration constant c is related to the value of the potential ψ2 at the air-liquid interface (y = h) through the
constant surface charge boundary condition [Eq. (4)], which together with Eq. (20) gives the following expression:
1 2
(21)

This integrated form of the Poisson-Boltzmann equation [Eq. (20)], does not, in general, lead to explicit solutions for
potential but will be used later to find film stability criteria expressed in terms of elliptic integrals.
or
4. LINEAR STABILITY ANALYSIS
To study linear and nonlinear stability of the electrolyte film, we consider perturbations of the base state corresponding
to a film of uniform thickness, equal to 1 in our nondimensional units. The behavior of a small perturbation ζ(x, t) to
the base state is described by the linearized version of (17)
th

ζt + ζxxxx + Gζxx = 0 (22)

where ·µ ¶ ¸
3 dψ2 3
G= sinh ψ2 − q2 − q22 (23)
2κ dh 2 h=1
Au

On the basis of Eq. (22), the growth rate γ of a small sinusoidal perturbation of a wave number k is given by
¡ ¢
γ(k) = k 2 G − k 2 (24)
Perturbations of all wave numbers decay for G < 0, indicating stability. We note that the spatial domain is assumed
to be infinite; thus, all wave numbers are present. Therefore, there will always be wave numbers corresponding to
instability for G > 0 or, equivalently,
dψ2 3 dψ2 3
sinh ψ2 − q2 − q22 > 0 (25)
dh 2κ dh 2
The growth rate of the fastest instability mode then corresponds to the maximum value of the function γ(k), equal to
G2
γmax = (26)
4

Volume 2, Number 1, 2014

6 Ketelaar & Ajaev

and reached at the wavelength

√
2 2π
λ= √ (27)
G
Note that G depends on the solution of the Poisson-Boltzmann equation, which in turn is a function of three inde-
pendent nondimensional parameters, q1 , q2 , and κ. The charge density of the solid substrate is typically negative in
applications; thus, we assume q1 < 0 for the rest of the present work. However, we note that once a solution ψ(y) is
found for q1 < 0, one can easily obtain a solution for q1 > 0 by a transformation q1 → −q1 , q2 → −q2 , ψ → −ψ.
The transition from a stable to unstable film can only take place under the condition of G = 0. On the basis of
Eq. (23), this condition can only be satisfied if

f
µ ¶
dψ2 3q2 3

oo
sinh ψ2 − − q22 = 0 (28)
dh 2κ 2

where the left-hand side is evaluated at h = 1.

Let us first consider the case of q2 < 0. Together with the condition of negative q1 and Eqs. (3) and (4), this
implies that ψy changes sign at some point (ym , ψm ). Note that this is a point of maximum because ψyy < 0,
assuming negative ψ, according to Eq. (2). Integrating Eq. (20) with the appropriate choice of sign for ψy (positive
for y < ym , negative for y > ym ), we obtain

2
Z

ψm
ψ1
√
Pr
dψ
cosh ψ + c
+
Z

ψ1
ψ2
√
dψ
cosh ψ + c
√
= − 2κh

Let us now introduce a new variable φ such that cosh ψ = (1 − c)csc2 φ − 1 and denote the values of the p new variable
corresponding to ψ1 , ψ2 , and ψm by φ1 , φ2 , and φm , respectively. It is also convenient to define k̃ ≡ 2/(1 − c).
Equation (29) is then written in the following form:
(29)
or
F (φ1 , k̃) − 2F (φm , k̃) + F (φ2 , k̃) = −k̃ −1 κh (30)

where we used the canonical definition of the incomplete elliptic integral of the first kind,
Z φ
dφ̃
F (φ, k̃) = q (31)
th

0 1 − k̃ 2 sin2 φ̃

Note that because c = − cosh(ψm ), the quantity k̃ is always real and less or equal to unity, as required by the
definition of the elliptic integral.
For the case of q2 < 0, Eq. (20) can be transformed by introducing a new variable θ such that cot θ = sinh ψ/2,
Au

leading to the following expression:

F (θ1 , k̄) − F (θ2 , k̄) = κh (32)
p
where k̄ = (1 − c)/2 and we use θ1 and θ2 to denote the values of the new variable corresponding to ψ1 and ψ2 ,
respectively.
Equations (30) and (32) give implicit but analytic representations of ψ2 as a function of κ for h = 1 and also
allow us to obtain formulas for dψ2 /dh at the gas-liquid interface. Substituting these results into the condition (28)
and using the standard Matlab function fzero, we obtain the critical value of κ for the instability as a function of the
charge densities q1 and q2 . In order to represent the stability results in the form of two-dimensional stability diagrams,
it is convenient to introduce a new variable q̂ = q2 /q1 . A typical stability diagram in q̂ – κ variables for q1 = −0.01
is shown in Fig. 2. The stability diagram remains qualitatively the same when q1 is varied over a wide range.
A well-known approximate solution of Eq. (2) can be obtained by considering the linearized version of this equa-
tion, valid in the limit of small ψ and known as the DH approximation. The condition of G = 0 in the framework of

Interfacial Phenomena and Heat Transfer

Application of the Nonlinear Poisson-Boltzmann Model 7

10

6 unstable

f
stable
0

oo
−2
unstable
−4
0 0.1 0.2 0.3 0.4 0.5
κ
FIG. 2: Stability diagram for q1 = –0.01.

with the coefficients defined by

Pr
this approximation leads to the analytical formulas derived by Ketelaar and Ajaev (2014). Using the formulation and
notation of the present paper, the stability branches then satisfy the following quadratic equation:

q̂(κ) =
√
−B ± B 2 − 4AC
2A
(33)
or
A = −2κ cosh κ + 3 sinh κ − 3 sinh3 κ (34)
B = −2κ(cosh2 κ + 1) + 3 sinh κ cosh κ (35)
C = −2κ cosh κ (36)
We verified that in the limit of q1 → 0, the predictions of our nonlinear model match the results based on the DH
th

approximation. However, as q1 is increased, the difference can be significant. This is illustrated for the upper stability
branch in Fig. 3. Stability boundaries are shown for two values of q1 and for the DH approximation. The stability
boundary shifts to the left as we increase the magnitude of the charge density, leading to expansion of the stability
domain of the diagram. Thus, it is important to take into account the nonlinear effects in the description of the electric
field in the film unless the magnitude of q1 is very small. We focus on the upper stability branch here because it is
Au

more relevant for practical applications, but similar conclusions can be made for the changes in the lower branch.

5. NONLINEAR EVOLUTION OF THE INTERFACE

The linear stability analysis provides stability criteria for an infinitesimal perturbation of the interface shape, but to
track the evolution of the interface in the regime when significant film thinning and possibly film rupture are observed,
the full nonlinear evolution equation (17) must be solved numerically. We carried out such solution using the finite-
difference discretization in both space and time, starting with a small initial sinusoidal perturbation. The nonlinear
Poisson-Boltzmann equation is solved numerically at each time step using the bvp4c subroutine in Matlab. The key
measure of interface evolution important for practical applications is the scaled minimum film thickness, which we
denote by a. It is shown as a function of time by a solid line in Fig. 4. The result based on the DH approximation
for the electrostatic potential is also shown in the graph by a dashed line for comparison. Clearly, both curves show
that significant film thinning is taking place. Because the dimensional values of the minimum film thickness can be

Volume 2, Number 1, 2014

8 Ketelaar & Ajaev

10

f
5

oo
4

2
0 0.1 0.2 0.3 0.4 0.5
κ
FIG. 3: Upper stability branch for different values of the substrate surface charge: q1 = –0.01 (solid line), q1 = –0.02

0.9
Pr
(dashed line) and for the Debye-Hückel model (dotted-dashed line).
or
0.8
a
th

0.7

0.6
PB
DH
Au

0.5
0 2 4 6 8 10 12 14
t
FIG. 4: Minimum film thickness versus time for q1 = 0.2, q̂ = −2, κ = 0.2.

very small for later times, film rupture in this regime can be expected, as a result of London-van der Waals forces or
fluctuations of the interface shape. We note that although both DH and PB models predict the same general behavior,
there is a difference between the rates of film thinning; the difference becomes more pronounced for higher values of
the substrate charge density.
To illustrate the limitations of the DH approximation, we note that there is a region in parameter space in which
its predictions are different from the full Poisson-Boltzmann model not only quantitatively but also qualitatively. The
plot in Fig. 5 shows a simulation in which film thinnning is predicted by the DH model, but the solution based on the

Interfacial Phenomena and Heat Transfer

Application of the Nonlinear Poisson-Boltzmann Model 9

0.9

a
0.8

f
oo
0.7

PB
DH
0.6
0 50 100 150 200
t

Pr
FIG. 5: Minimum film thickness for q1 = 0.2, q̂ = 2.4, κ = 0.2.

PB equation indicates that a small initial perturbation of the interface shape decays and thus the film is stable. Thus,
the DH approximation can lead to predictions of film rupture in the regime when the film is in fact stable.

6. CONCLUSIONS
or
We consider the effects of electrostatic forces on the stability of thin electrolyte films. A model is developed based on
the classical lubrication-type approach for the viscous flow in the film and the nonlinear Poisson-Boltzmann equation
for the electrostatic potential. The conditions of constant charge densities at the solid substrate and liquid-gas interface
are imposed. The instability arises as a result of electrostatic interaction of the charges at the substrate and the liquid-
gas interface.
th

The linear stability analysis leads to analytical expressions for the scaled film thickness at which transition occurs
between the stable and unstable films. Parametric studies of the stability criteria are presented in terms of the scaled
values of the substrate surface charge density and the surface charge density at the interface. The results are compared
to the predictions of the DH approximation. The agreement between the two models is found only for very small values
of the substrate surface charge density, leading to the conclusion that the full nonlinear Poisson-Boltzmann equation
must be used to accurately determine film stability in practical applications not involving very small electrostatic
Au

potentials. The full nonlinear model is formulated and solved numerically, leading to solutions for minimum film
thickness as a function of time.

7. ACKNOWLEDGMENTS

This work was supported by the National Science Foundation under Grant No. CBET-0854318.

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Interfacial Phenomena and Heat Transfer