Confinement Effects in Dip Coating
Confinement Effects in Dip Coating
Confinement Effects in Dip Coating
When a flat plate is withdrawn from a liquid pool, a liquid film is deposited on
the plate. This simple process is called dip coating. In the case of vertically upward
withdrawal, gravity competes with the surface tension and viscous drag, and the
balance between those determine the meniscus shape and hence the film thickness.
Most of the previous studies on dip coating assumed that the pool is sufficiently large
so that the stationary container wall does not affect the film thickness. However, the
cases where the stationary wall affects the entrained film have not been examined
thoroughly so far. In this confined dip coating, the film thickness deviates from that
of unconfined dip coating under the same conditions such as the withdrawal speed
and the physical properties of the liquid. The meniscus in a confined pool is more
curved than that in an unconfined pool owing to wetting on the stationary wall,
which is parallel to the plate. Besides, a channel between the moving plate and the
stationary wall appears; therefore, the flow inside the channel should be included in
an analysis of confined dip coating. In the present study, we analyse the mechanism
that determines the film thickness, both theoretically and numerically.
Key words: capillary flows, coating, thin films
1. Introduction
Perhaps the simplest way to produce a thin liquid film is to deposit a layer
of liquid onto a substrate via withdrawal from a liquid pool. The physics of the
process is known as the drag-out problem or the Landau–Levich problem, after
pioneering studies by Landau & Levich (1942). The corresponding prototypical dip
coating flow is popular not only in laboratory experiments (Scriven 1988) but also
in industry (Schunk, Hurd & Brinker 1997) because of its simplicity. Dip coating
and related methods are sufficiently flexible to produce films on different geometries
(Bretherton 1961; Wilson 1982; Park & Homsy 1984; de Ryck & Quéré 1996) and
can be applied to fluids with various properties (Krechetnikov & Homsy 2005, 2006;
Afanasiev, Münch & Wagner 2007; Dixit & Homsy 2013a,b; Javidi, Pope & Hrymak
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2016; Maillard et al. 2016). The study of Landau & Levich (1942) can be also
extended to related systems such as the formation of Marangoni-driven films on a
heated substrate partially immersed in a liquid pool (Münch 2002; Münch & Evans
2005, 2006).
(1942) determined h∗∞ for low Ca at which gravitational drainage can be negligible.
A number of authors extended the study of Landau & Levich (1942) by including
gravitational drainage (White & Tallmadge 1965; Spiers, Subbaraman & Wilkinson
1974; Wilson 1982), inertia (Kheshgi, Kistler & Scriven 1992; de Ryck & Quéré 1998)
or the normal viscous stress at the meniscus (Spiers et al. 1974; Esmail & Hummel
1975b) in their studies.
Numerical analyses (e.g. finite element (FE) or finite volume computations) have
also been commonly used to determine h∗∞ because no simple film-thickness-predicting
equation covers low to high Ca and to extend the study to complex fluids (Réglat,
Labrie & Tanguy 1993; Jin, Acrivos & Münch 2005; Jenny & Souhar 2009; Campana
et al. 2010; Abedijaberi et al. 2011; Filali, Khezzar & Mitsoulis 2013).
Most of the previous studies on dip coating, including those referred to earlier,
have considered withdrawal of a substrate in the direction opposite to gravity from
an sufficiently large pool. In this unconfined dip coating system, most of the pool
remains virtually static, except in the small region near the moving substrate, where
the flow can be recognised inside the extremely curved meniscus viewed in the far
field (Krechetnikov & Homsy 2006). However, the results of those studies cannot be
directly applied to many practical situations in which the pool is confined, such as a
coating on fibre (Quéré 1999) or laboratory experiments (Ahn et al. 2015). Although
Kheshgi et al. (1992) considered a confined pool in the dip coating problem, his study
considered a meniscus distortion due to an obstacle near the static meniscus.
In the present study, we define the confined pool as a pool where the stationary
container wall parallel to the substrate has an effect on the film thickness and forms
a channel with the substrate. There are, however, no limitations along the withdrawal
direction, as in the usual unconfined dip coating. In a confined dip coating system,
two clearly distinct flow regimes appear depending on the capillary number Ca: the
meniscus-controlled regime for low Ca and the channel-controlled regime for high Ca.
Typical dip coating flows under these regimes are shown schematically in figure 1.
The film thickness is dominantly controlled by the meniscus shape in the meniscus-
controlled regime and by the channel width, which is defined as the distance between
the substrate and the stationary wall, in the channel-controlled regime. Both regimes
exhibit distinct scaling behaviours. We analysed these behaviours theoretically and
numerically. The results of the present study can be used to predict the film thickness
entrained from a confined pool that can be encountered in thin-film productions in
industry or laboratory experiments.
2. Formulation of problem
In dip coating problems, the flow can be divided into three regions: the film
entrainment region (region I), the dynamic meniscus region (region II) and the static
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meniscus region (region III), as shown in figure 1. In the film entrainment region, the
deposited liquid film translates along the moving plate. The characteristic length lf for
this region can be easily determined by considering the balance between the viscous
and gravitational forces. In the static meniscus region, the meniscus shape in that
region is determined by the balance between the capillary and gravitational forces.
A simple force balance analysis also yields the characteristic length lc , known as
Confinement effects in dip coating 3
Meniscus shape
at high-Ca limit
I
II
Container wall
II
III IV
IV
l
F IGURE 1. Schematic of confined dip coating system for (a) meniscus-controlled regime
and (b) channel-controlled regime. (a) For the flow in the meniscus-controlled regime, i.e.
the region excluding the regions close to the moving plate (I and II), the liquid is virtually
stationary (III and IV). (b) For the channel-controlled regime, the static pool disappears,
and the dynamic meniscus region (II) fills the channel. The dotted line represents the
meniscus shape at the high-Ca limit. See appendix A for a discussion of region IV.
the capillary length. The aforementioned two regions are connected by the dynamic
meniscus region where the dynamic effects due to liquid in motion should be
considered. In this region, the meniscus shape is set by the balance between the
viscous drag, surface tension and gravity, provided inertia is absent. The meniscus
profile along the moving plate determines the constant film thickness h∗∞ . In addition
to the aforementioned three regions, when a pool is confined, the channel region
(region IV) appears far below the meniscus, and the characteristic length of this
region is the channel width l. The flow in this region is fully developed as described
in appendix A.
For unconfined dip coating, Landau & Levich (1942) determined h∗∞ at a low
capillary number Ca, under which gravitational drainage is negligible, as
the physical properties of the fluid (ρ, µ and σ ). In the present study, it is assumed
that a substrate is a flat plate and the coating liquid is a pure Newtonian fluid (i.e.
there are no surfactants or particles) that wets the plate completely. For the flow
where the foregoing assumptions are valid, the Buckingham π theorem yields four
dimensionless numbers describing the flow system uniquely. The numbers are the
dimensionless thickness T, the dimensionless channel width L, the capillary number
Ca and the material number m:
s
h∗∞ l µus ρσ 3
T≡ , L≡ √ , Ca ≡ , m≡ . (2.2a−d)
l σ /ρg σ gµ4
Note that three dimensionless numbers are required to define an unconfined dip
coating flow uniquely (Tallmadge & Soroka 1969); however, the newly introduced
parameter, the channel width l, generates the additional dimensionless number
L. Another important number, the Reynolds number Re, can be obtained by the
combination of the other numbers (2.2):
Here, we limit our study to a Stokes flow (Re 1); T is solely determined by Ca
and L. Accordingly, we set the value of m to 10−5 in FE computations. Under this
condition, we can assume a confined dip coating flow to be a Stokes flow because
we explore the range in Ca up to 102 such that Re ' mCa.
∇ ∗ · v ∗ = 0, (2.4)
∇ ∗ · T ∗ + ρ g = 0, (2.5)
where v ∗ is the velocity, T ∗ is the total stress tensor and g is the gravitational field.
The no-slip conditions at the moving plate and stationary wall are
v ∗ = v ∗s at y∗ = 0, (2.6)
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v ∗ = 0 at y∗ = l. (2.7)
The stress balance and the kinematic condition at the meniscus are
nm · T ∗ = σ κ ∗ nm at y∗ = h∗ (x∗ ), (2.8)
nm · v ∗ = 0 at y∗ = h∗ (x∗ ), (2.9)
Confinement effects in dip coating 5
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A
x
S
x
I II III IV
F IGURE 2. Formulation of the problem. All variables are scaled for the static meniscus
region. A meniscus profile h is represented as a function of the x coordinate. The dotted
curve represents an imaginary static meniscus with a contact angle θc in the absence of
flow. The solid line represents the meniscus shape due to the flow. The meniscus shape
deviates from the shape of the static meniscus in the dynamic meniscus region (region II).
In the inset, κ0 is the curvature at the centre of the imaginary static meniscus and is
discussed in § 3.
where i, j are the unit vectors in the positive directions of the axes; and κ ∗ is the
curvature of meniscus:
κ ∗ = −∇ ∗ · nm . (2.11)
Here, we set the pressure on the gas side to zero. Finally, the stress tensor T ∗ of a
pure Newtonian fluid is given by
(2.13a−d)
The variables in these scales are denoted by overbars, and the equations and conditions
in the component form become
∂u ∂v
+ = 0, (2.14)
∂x ∂y
2/3 ∂ u ∂ 2 u ∂p
2
1/3 2
Ca + 2− − Ca L = 0,
∂x 2
∂y ∂x
(2.15)
4/3 ∂ v 2/3 ∂ v ∂p
2 2
Ca + Ca − = 0,
∂x2 ∂y2 ∂y
u = 1, v = 0 at y = 0, (2.16a,b)
" 2 #
∂u ∂v ∂u 2/3 ∂v
2/3 dh 2/3 dh
2Ca − + Ca −1 + Ca = 0,
dx ∂x ∂y dx ∂y ∂x
" 2 #−3/2
2/3 ∂u 4/3 ∂v 2/3 ∂v d2 h
dh 2/3 dh
p+ Ca + Ca − 2Ca = − 2 1 + Ca
∂y ∂x ∂y
dx dx dx
at y = h(x), (2.17)
dh
u =v at y = h(x). (2.18)
dx
The importance of gravity in the dynamic meniscus region is represented by
Gd ≡ Ca1/3 L2 , (2.19)
which appears in the first equation of (2.15).
+ = 0, (2.21)
∂x ∂y
∂ u ∂ 2u ∂p
2
2
Ca + 2 − − L = 0,
∂x ∂y ∂x
2
(2.22)
∂ v ∂ 2v ∂p
2
Ca + 2 − = 0,
∂x 2 ∂y ∂y
Confinement effects in dip coating 7
u = 1, v=0 at y = 0, (2.23a,b)
" #
∂u ∂v ∂u ∂v
2
dh dh
2 +− −1 + = 0,
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dx ∂x ∂y ∂y ∂x
dx
" 2 −3/2
# at y = h(x),
dh ∂u ∂v ∂v d2 h
dh
p + Ca + − 2Ca = − 2 1 +
dx ∂y ∂x ∂y
dx dx
(2.24)
dh
u =v at y = h(x). (2.25)
dx
∂u ∂v
+ = 0, (2.27)
∂x ∂y
∂ u ∂ 2u ∂pc
2
L2
+ − − = 0,
∂x2 ∂y2 ∂x
Ca
(2.28)
∂ v ∂ 2v ∂pc
2
+ 2 − = 0,
∂x 2 ∂y ∂y
u = 1, v=0 at y = 0, (2.29a,b)
u = 0, v=0 at y = 1. (2.30a,b)
The subscript c is added to p to distinguish it from that for the static meniscus region.
Similar to the dynamic meniscus region, the term associated with gravity appears in
the momentum balance equation (2.28):
L2
Gc ≡ . (2.31)
Ca
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3. Meniscus-controlled regime
For a low capillary number Ca, the dynamic meniscus region connects the film
entrainment and the static meniscus regions. In this low-Ca regime, the flow rate
through the film entrainment region is determined by the force balance in the
dynamic meniscus region. The meniscus in a confined pool is more curved than
that in an unconfined pool, and the increase in curvature changes the capillarity and
8 O. Kim and J. Nam
hence affects the force balance in the dynamic meniscus region. Therefore, the film
thickness h∗∞ deviates from that of the unconfined dip coating case.
The radius of curvature of the meniscus is comparable to half the channel width l in
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the static meniscus region. Following Krechetnikov & Homsy (2006), a simple scaling
analysis can be performed with l instead of the capillary length lc in the dynamic
meniscus region:
us σ /(l/2) h∗∞
µ ∗2 ∼ , ∼ l−1 , (3.1a,b)
h∞ ld ld2
where ld is the extent of the dynamic meniscus region. Rearranging these expressions
yields
T ∼ Ca2/3 . (3.2)
In what follows, the prefactor of Ca can be determined.
The term inside the parentheses of the preceding equation is the flow rate through
the dynamic meniscus region. This flow rate is constant with respect to x and should
be equal to that through the film entrainment region h∞ . This flow-rate-matching
condition yields a third-order ordinary differential equation of the meniscus profile in
the dynamic meniscus region:
d3 h h∞ − h
3
=3 3
. (3.5)
dx h
In addition, h in the limit to the film entrainment region is the film thickness h∞ :
h → h∞ as x → ∞. (3.6)
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It becomes the boundary condition for (3.5), and the equation can be transformed into
the universal form (Bretherton 1961). The second derivative of the meniscus profile h
in the limit to the static pool region can be obtained via numerical integration of the
transformed equation:
d2 h
→ 1.3376h∞ as x → −∞. (3.7)
dx2
Confinement effects in dip coating 9
Under the same condition (Ca1/3 1), the viscous force is negligible in the
static meniscus region. Therefore, the Stokes equations and boundary conditions
(2.22)–(2.25) for that region can be greatly simplified as
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" 2 #−3/2
d d2 h dh
2
1+ = L2 , (3.8)
dx dx dx
where C is an integration constant. Again, we consider only the part of the meniscus
along which d2 h/dx2 > 0. For an unconfined pool, C vanishes in our coordinate system.
However, for a confined pool, C has a finite value because the dimensionless curvature
of a static meniscus does not vanish except for θc = π/2, as shown in figure 2. C is
determined by the pressure profile along the meniscus. The liquid-side pressure p0 at
the centre point Oe of the static meniscus is selected as the pressure datum and is
equivalent to −κ0 , where κ0 is the curvature at point O.
e The liquid-side pressure at
any point A on the meniscus in the inset of figure 2 can be obtained by considering
either the hydrostatic pressure at A or the capillary pressure jump across the curved
meniscus at that point. Both should be identical, and hence C = κ0 . Equation (3.9)
then becomes " 2 #−3/2
d2 h dh
2
1+ = L2 x + κ0 . (3.10)
dx dx
Following the idea of Landau & Levich (1942), we also use the classical curvature-
matching condition to determine the dimensionless film thickness T, i.e. the curvature
of the static meniscus at the ‘upper’ boundary is matched to that of the dynamic
meniscus at the ‘lower’ boundary. For the static meniscus, the slope of the meniscus
vanishes at the matching point:
dh
→0 as h → h∞ . (3.11)
dx
This gives the curvature at that point:
static
d2 h p
2
= L 2 + (κ0 /L)2 . (3.12)
dx h→h∞
For the dynamic meniscus, equation (3.7) can be rewritten using the variables for the
static meniscus region:
dynamic
d2 h Ca2/3
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= 1.3376 . (3.13)
dx2 h→∞ T
Finally, from the matching between the curvatures (3.12) and (3.13), T is given by
1 0.9458 2/3
T=p Ca . (3.14)
1 + (κ0 /L)2 /2 L
10 O. Kim and J. Nam
We define the term involving the curvature κ0 in the preceding equation as
1
Cc ≡ p . (3.15)
1 + (κ0 /L)2 /2
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The expressions inside the parentheses are identical to (2.1) with the corresponding
characteristic lengths. This identity implies that the previous result of Landau &
Levich (1942) can be corrected by introducing Cc for confined dip coating. Therefore,
we call Cc the confinement-correction factor for the meniscus-controlled regime.
The value of κ0 is required to determine Cc and the complete equation (3.14).
Equation (3.10) can be integrated and rearranged as
dh L2 x2 /2 + κ0 x − 1
=p . (3.17)
dx 1 − (L2 x2 /2 + κ0 x − 1)2
2 − k2 h π i 2 h π i L
F , k − F(φ, k) − E , k − E(φ, k) − = 0, (3.18)
k 2 k 2 2
where
2L π + 2θc
k= p (elliptic modulus), φ= , (3.19a,b)
κ02 + 4L2 4
and F and E are the elliptic integrals of the first and second kind, respectively. For a
given L, k can be evaluated from (3.18), and then we can obtain Cc directly instead
of κ0 .
Figure 3 shows the confinement-correction factor Cc as a function of the
dimensionless channel width L for different contact angles θc , and Cc exhibits small-
and large-L limiting behaviours clearly. In the small-L limit, a more confined pool
(smaller L) yields a meniscus with a smaller Cc at a given θc . In the large-L limit, Cc
approaches unity, which implies that confinement effects disappear, i.e. equation (2.1)
is recovered from (3.16). A detailed examination of these two limits can be found in
appendix C.
Interestingly, the power-law dependence of Cc on L is independent of θc at small
L, and hence κ0 depends only on θc . It is related to the influence of gravity on the
meniscus shape and is discussed in § 6.
It
√is particularly interesting to analyse (3.14) in the small-L limit. In this limit, Cc →
L/ 2 cos θc , as explained in § C.1. The resulting equation becomes independent of L
and exhibits the power-law behaviour O(Ca2/3 ):
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0.9458
T=√ Ca2/3 . (3.20)
2 cos θc
Therefore, the prefactor of (3.2) depends only on θc in the small-L limit. When the
coating liquid wets the wall almost completely (small θc ), the meniscus is distorted
Confinement effects in dip coating 11
101
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100
10–1
10–2
further, and a thinner film is entrained. Similar results can be found in the inclined
unconfined dip coating problem (Wilson 1982); the thinner film is located on the side
where the meniscus shape is concave.
The matching condition of Landau & Levich (1942) that yields (3.14) appears to
be irrational. However, matched asymptotic expansions show that this condition is
valid for Ca1/3 1 (Wilson 1982; Park & Homsy 1984; Münch 2002). Equation
(3.14) is equivalent to the leading-order approximation of the asymptotic expansion in
Ca1/3 . Hence, the error behaviour of the equation can be predicted by investigating the
previous study of Wilson (1982), in which unconfined dip coating is discussed. In his
study, when the inclination angle α = 0 (vertical withdrawal), C2 in (30) corresponds
to our C in (3.9) and (3.14) becomes the leading-order term of his equation (39).
In terms of our characteristic length, the first correction is O(Ca) (note that the first
correction is O(Ca1/2 ) in his study because of the different characteristic length from
the present study). Therefore, one might expect the error behaviour of (3.14) to be
O(Ca) for low Ca. However, Wilson (1982) also discussed the non-uniformity in his
asymptotic series that arises from α. We, therefore, can predict the non-uniformity
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arising from the contact angle θc , which changes the meniscus profile at the given Ca
and L, in confined dip coating. The error behaviour is briefly discussed in § 5.3.
The approach that leads to (3.14) can also be easily extended to other film-thickness-
predicting equations on the basis of the curvature matching for unconfined dip coating
such as that of White & Tallmadge (1965) and Spiers et al. (1974). See appendix B
for details.
12 O. Kim and J. Nam
4. Channel-controlled regime
At high Ca, it is expected that the viscous force transferred from the moving plate
is sufficiently large to set the contact line on the stationary wall in motion (i.e. the
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contact line may move upwards along the wall) as with the forced wetting (Blake
& Ruschak 1979); there is no steady-state flow as long as the contact line moves.
However, the contact line would eventually cease to move and be pinned on a wall
that has received special treatments such as an application of surface roughening or at
the sharp corner of a wall that the moving contact line reaches (Oliver, Huh & Mason
1977), as shown in figure 1(b). In what follows, we consider a steady-state flow with
the pinned contact line.
1
T→ 2
as Ca → ∞. (4.5)
This result appears to be similar to that of unconfined dip coating: h∗∞ /lf becomes
independent of Ca in the high-Ca limit in the absence of inertia and surfactants
(Esmail & Hummel 1975b; Weinstein & Ruschak 2001; Jin et al. 2005). However,
the film thickness h∗∞ itself increases without bound with Ca in unconfined dip
coating, whereas h∗∞ is bounded in confined dip coating.
Confinement effects in dip coating 13
5. Numerical computations
5.1. Finite element model
To solve the Stokes equations with the Galerkin finite element method (G/FEM), we
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nm · nw = − cos θ, (5.1)
where nm and nw are the outward normal unit vectors on the meniscus and the wall,
respectively. The definitions of the normal and tangent vectors and a contact angle in
our FE model are shown in figure 4. When the coating liquid near the stationary wall
remains in static equilibrium, the static contact angle θc is used instead of θ.
Dip coating is a self-metered method in that the flow rate is determined by the force
balance inside the coating flow (Weinstein & Ruschak 2001). Therefore, a velocity
profile should not be prescribed at the inflow or outflow boundary a priori; such a
prescribed velocity profile presets the film thickness h∗∞ .
In this regard, the FEM has an advantage over other methods, because of the
free boundary condition (Papanastasiou, Malamataris & Ellwood 1992). The FEM
can extend the validity of the weak form of the governing equations to synthetic
boundaries (inflow and outflow boundaries), instead of replacing them with unknown
essential or natural boundary conditions, such that
where nb is the outward unit normal vector at either the inflow or outflow boundary.
The free boundary condition (5.2), which is typically used for an outflow boundary,
appears not to impose any boundary condition at all; however, it provides an effective
boundary condition (Renardy 1997).
We apply the free boundary condition (5.2) not only to the outflow boundary but
also to the inflow boundary. To the best of the authors’ knowledge, this has never
been attempted before. In our FE model, both the inflow and outflow boundaries are
located sufficiently far from each other so that the velocity fields and the gradient
of the pressure fields are expected to approach asymptotic limits at both ends. This
asymptotic state includes ‘fully developed’ flows (Renardy 1997). Applying the free
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boundary condition to the inflow boundary allows the pressure to take any value
at the boundary. It yields the undetermined position of the contact line with the
contact angle prescribed by (5.1). However, at a given Ca and L, both the position
of the contact line and the contact angle should be fixed to have a unique solution
in the frame of reference for our model, but it is impossible to impose them as
boundary conditions in our FE framework simultaneously. Therefore, an additional
14 O. Kim and J. Nam
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F IGURE 4. Numerical flow domain and corresponding boundary conditions. All boundary
conditions, unit vectors and a contact angle are represented. The free boundary condition
is applied to both the inflow (bottom) and outflow (top) boundaries. The velocity profile
is not prescribed.
condition or constraint is required to find the unique solution. It would seem that
the mesh configuration of the physical domain of interest provides the additional
condition required to determine the position of the contact line implicitly. When the
mesh generation equation (explained in the following) is solved with (2.4) and (2.5)
simultaneously, we can find the unique (steady-state) solution. However, the detailed
mechanism of how the mesh configuration fixes the position of the contact line is
not clear.
As discussed earlier, the physical domain of interest of the confined dip coating flow
should be surrounded by three physical boundaries (the meniscus, the stationary wall
and the moving plate) and two synthetic boundaries (the inflow and outflow planes).
All the boundary conditions are summarised in figure 4.
To find the meniscus shape via standard techniques for boundary value problems,
the set of differential equations and boundary conditions on the unknown, deformable
‘physical’ region R in the x∗ y∗ -plane should be transformed one to one into an
equivalent set on the known, fixed ‘computational’ region G in the ξ η-plane. Here
R and the set on it are transformed by an equation of the form x∗ = M(ξ ), where
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where n is the number of nodes used for the nodal position and velocity and m is the
number of nodes used for the pressure, and the coefficients x∗i , v ∗i and p∗i are unknown
values to be determined at each node.
The weak forms of (2.4), (2.5) and (5.3) are obtained by multiplying them by the
weighting functions and then integrating over the ‘physical’ region R. The essential
boundary conditions are implemented by replacing the corresponding weighted
residual equation with the desired velocity or node specification. The natural boundary
conditions are implemented through the boundary integrals, which follow from the
divergence theorem. Note that the free boundary condition (5.2) is treated as the
natural boundary condition.
The G/FEM reduces the Stokes and mesh generation equations (2.4), (2.5) and (5.3)
to a set of nonlinear algebraic equations with respect to the basis function coefficients,
R(z, λ) = 0, (5.5)
where z is the solution vector consisting of the FE coefficients of x∗i , v ∗i and p∗i ; and
λ is the parameter vector containing the parameters for the dip coating flow, such as
l, us , θc , ρ and σ . The system of nonlinear equations (5.5) is solved using Newton’s
method:
J R (zi |λ)δzi = −R(zi , λ),
(5.6)
zi+1 = zi + δzi ,
where J R (z) is the Jacobian matrix of R. The solution vector z is accepted as the
solution to the problem when kR(zi )k2 < 5 × 10−9 . The typical value of the solution
https://doi.org/10.1017/jfm.2017.421
The initial guess was obtained by replacing the unknown meniscus shape with a
known arc of a circle and substituting the stress balance condition (2.8) with the
kinematic condition (2.9) and Navier’s slip condition with a large slip coefficient β =
108 along the meniscus, β(tm nm : T ∗ ) = tm · v ∗ . Nodal positions were not included in
the unknowns because the normal and tangential unit vectors at the meniscus were
known at this stage; Navier’s slip condition and the kinematic condition (2.9) were
applied to the x∗ - and y∗ -components of the momentum equation (2.5), respectively.
The base solution at Ca = 0.01, L = 5 and θc = 30◦ was computed using the initial
guess. Figure 5 illustrates the mesh configuration of the base solution. Along the
meniscus, a total of 125 elements and 251 nodes were used to resolve the meniscus
shape.
The solutions for different values of the capillary number Ca and the dimensionless
channel width L were computed by using the pseudo-arc-length continuation (Bolstad
& Keller 1986), starting from the base solution. us and l were chosen as the
continuation parameters to adjust Ca and L, respectively. During the continuation
in l, the distance d between the inflow and outflow boundaries should be adjusted
simultaneously to ensure a fully developed flow at the inflow and outflow boundaries.
When the inflow is not fully developed, the accuracy of the flow rate through the
https://doi.org/10.1017/jfm.2017.421
flow domain could be compromised, and hence the film thickness h∗∞ . Unlike other
numerical models (Jin et al. 2005; Campana et al. 2013), we did not restrict the
shape of the free surface at the corner of the element where the outflow boundary
and the free surface are placed. Hence, the free surface slope with respect to the
moving plate is a major indicator of fully developed flow. When the outflow is not
fully developed, the thickness being measured from the moving plate to the free
Confinement effects in dip coating 17
100
Equation (4.5)
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Equation (3.14)
10–1
10–2
10–3
10–2 10–1 100 101 102
Ca
surface along the outflow boundary is larger than the film thickness h∗∞ . According
to our numerical tests, it turns out that d/l = 6 ensures a virtually parabolic velocity
profile and a zero slope of the free surface at the corner at the outflow boundary. We
therefore maintained d/l = 6 during the continuation.
Steady-state solutions are obtained within 3–5 iterations except for the base solution
obtained using the initial guess. To guarantee a high accuracy for h∗∞ , we verified that
the mesh configuration near the highly curved meniscus is properly resolved for every
solution.
10–1
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10–2
10–3 –2
10 10–1
Ca
F IGURE 7. (Colour online) Error behaviour. The error is defined as the difference
between the analytical and numerical results. The dimensionless film thickness T is
predicted by (3.14) and (3.20) for L = 1 and L = 0.1, respectively. The plot shows the
errors of O(Ca) at θc = 30◦ and O(Ca4/3 ) at θc = 0◦ , as indicated by Wilson (1982)
and Park & Homsy (1984), respectively.
vanish eventually in the high-Ca limit, and the flow will become a Couette flow (see
appendix A for details). The numerical results are consistent with the discussion in
§ 4.1. Interestingly, dpc /dx is independent of L at small L (<0.5) for high Ca, as
shown in figure 9(b), and hence T is also independent of L. This independence is
identical to that found in the low-Ca regime with small L. Finally, all the numerical
results show that l is the critical parameter for both regimes.
Confinement effects in dip coating 19
(a) 1.0
0.8
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0.6
0.4
0.2
0 30 60 90
(b) 2 (c) 2
1 1
0 0
–1 –1
0 0.5 1.0 0 0.5 1.0
y y
F IGURE 8. (Colour online) Influence of container wall wetting on film thickness and
meniscus shape for L = 0.1 and various Ca. (a) Plot of RT ≡ (T − T0 )/T0 , where T0 is
the value at θc = 0. The effect of the wall wetting on the film thickness diminishes as
Ca increases. (b,c) The coordinates are scaled with l. The arrows denote the direction of
increasing θc . The meniscus shape changes significantly for Ca = 0.01, whereas it changes
slightly for Ca = 5.
Gd ≡ Ca1/3 L2 . (6.1)
20 O. Kim and J. Nam
(a) 10 3
10 2
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101
100
10–1
10–2
10–3
100 101 102
(b) 101
100
10–1
10–2
10–3 0
10 101 102
Ca
F IGURE 9. (Colour online) (a) The ratio of gravitational force Gc to pressure force dpc /dx
and (b) dpc /dx as a function of capillary number Ca for different L at θc = 30◦ . (a) Gc
decays faster than dpc /dx as Ca increases. (b) When the pool is sufficiently confined (L <
0.5), dpc /dx becomes independent of L. Although dpc /dx does not vanish completely, even
at an extremely high Ca of up to 102 , it clearly decreases monotonically.
Note that Gd is an upper bound of ρgh∗ /(σ /l). Gd vanishes when the channel is
confined further (L < 0.5), which reinforces the capillary force due to the highly
https://doi.org/10.1017/jfm.2017.421
curved meniscus. For small L, gravity is negligible in the Stokes equations (2.15)
and (2.22), and T becomes independent of L as shown in (3.20). This means that
the effect of gravity diminishes not only in the dynamic meniscus region but also in
the static meniscus region. It is already signalled in κ0 . For low L, κ0 depends only
on θc as mentioned in § 3.1 and becomes κ0 = 2 cos θc ; therefore, the meniscus shape
becomes an arc of a circle in the low-Ca limit.
Confinement effects in dip coating 21
The resulting Stokes equations (without gravity) can also be found in the Bretherton
problem in Hele-Shaw cells, where gravity is also insignificant (Park & Homsy 1984).
Furthermore, equation (3.20) with a zero contact angle becomes the leading-order
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approximation for the problem. Note that this contact angle stands for a two-sided
coating on the walls of the cells. The Bretherton problem in Hele-Shaw cells,
therefore, can be regarded as the limiting case of the confined dip coating problem,
and the error behaviour is consistent with O(Ca4/3 ) as indicated by Park & Homsy
(1984), as shown in figure 7. See appendix E for a comparison between confined dip
coating and the Bretherton problems.
In the channel-controlled regime, similar to the meniscus-controlled regime, the
competition between the gravitational and viscous forces can be measured by
L2 ρgl
Gc ≡ = . (6.2)
Ca µus /l
Gc vanishes when the plate withdraws rapidly or when the channel is highly confined
(Ca L2 ), which enhances the viscous force inside the channel. In the high-Ca limit,
T becomes independent of L. This corresponds to the vanishing of the gravitational
effect.
The independence of T from L for both low- and high-Ca regimes reveals a change
in the number of dimensionless numbers required to describe the confined dip coating
flow uniquely. As discussed in § 2.1, for withdrawal of a flat substrate from a pool
of a pure Newtonian fluid, unconfined dip coating flows require three dimensionless
numbers (or two for inertialess flows: h∗∞ /lc and Ca). Adding the channel width l
to the dimensional analysis increases the number of dimensionless numbers to four
(or three for inertialess flows: T, Ca and L). However, when the gravitational effect
vanishes, the number becomes three again (or two for inertialess flows: T and Ca).
Note that the definitions of T and Ca are independent of g. According to the FE
computations, these vanishing gravitational effects occur over the entire range of Ca
when L is sufficiently small; e.g. L < 0.5 according to our numerical results, as shown
in figure 6.
The change in the number of dimensionless numbers for the system implies a
transition of the system’s characteristic length. The length of the unconfined pool is
the capillary length lc . When the pool is confined, the newly introduced l competes
with lc , and this competition is parameterised by L = l/lc . When the gravitational
effect vanishes, lc is no longer effective, and l becomes the only characteristic length
for confined dip coating flows.
7. Concluding remarks
The unconfined pool assumption is valid only in the absence of a stationary wall
influencing the film thickness h∗∞ . In such a pool, h∗∞ should be independent of the
channel width l; i.e. T is inversely proportional to L, regardless of Ca. This criterion
for an unconfined pool can be expressed as
https://doi.org/10.1017/jfm.2017.421
∂(LT)
= 0. (7.1)
∂L
Otherwise, a pool is confined. It should be emphasised that the pool can be confined
either via small L or via high Ca, and hence it is possible for an unconfined pool
to become confined as Ca increases. In a confined pool, l becomes the appropriate
22 O. Kim and J. Nam
characteristic length of the system, and two major changes occur: an increase in
the curvature of the meniscus and an intensification in the viscous stress inside
the channel. The increased curvature enhances the capillarity and affects the force
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balance in the dynamic meniscus region. The intensified viscous stress dominates the
(dimensional) pressure gradient in the channel region. These changes affect the flow
rate and hence the film thickness h∗∞ , and we call them the confinement effects in
dip coating.
In confined dip coating, the role of gravity in the force balance diminishes when
Ca1/3 1 and L < 0.5; or Ca L2 . Consequently, the characteristic length is no longer
determined by the material properties but by the channel width l. The confinement
effects for a dip coating flow are strongly associated with the vanishing gravitational
effect and the increasing importance of the newly introduced characteristic length l.
The dynamic and channel regions are important as they determine the flow rate and
hence the film thickness at low and high Ca, respectively. The thickness-determining
mechanisms in each region correspond to the two regimes of confined dip coating
flows, i.e. the meniscus- and channel-controlled regimes. The criteria for both regimes
cannot be explicitly determined because the threshold Ca of both regimes depends
on the dimensionless channel width L, as shown in figure 6. However, when the
gravitational effect vanishes (L < 0.5), the ranges of Ca . 0.1 and Ca & 10 can be
established for the meniscus- and channel-controlled regimes, respectively.
Between the two regimes, there is a regime where the normal viscous stress
becomes comparable with the capillary pressure in the dynamic meniscus region.
This regime was also observed in unconfined dip coating (Esmail & Hummel 1975a;
Jin et al. 2005). The meniscus shape changes abruptly in the dynamic meniscus
region for low Ca, but the magnitude of the change diminishes as Ca increases, as
shown in figure 10(a). For high Ca > 1, the shape does not change significantly, and
hence the capillary pressure jump. In contrast, the normal viscous stress increases
monotonically and dominates the capillary pressure, as shown in figure 10(b). In this
regime, the flow is no longer unidirectional, and the strong acceleration along the
meniscus generates a non-negligible normal viscous stress in the dynamic meniscus
region. Under these conditions, lubrication-type simple models cannot be used, and
a nonlinear two-dimensional model must be employed to determine the meniscus
shape (Esmail & Hummel 1975b). Analysis of this regime is beyond the scope of
the present study but merits further discussion.
Inertia was not considered in the present study. The importance of inertia depends
on the material number m. The inertia begins to surpass the surface tension at a Weber
number (We = ReCa) close to unity and becomes comparable to the viscous drag
(Campana et al. 2013). For unconfined dip coating, thickening or thinning of the film
occurs above a threshold value of Ca at large Re and low Ca (Tallmadge & Stella
1968; de Ryck & Quéré 1998) or at large Re and high Ca (Esmail & Hummel 1975b),
respectively. In both cases, the maximum thickness scaled with lf exists. Besides, the
meniscus shape in the dynamic meniscus region becomes wavy, and the coating flow
becomes unstable (Esmail & Hummel 1975b; Kamotani, Ostrach & Kizito 1999; Jin
et al. 2005). On the basis of these results, it is expected that thickening or thinning
of the film can also occur in confined dip coating with inertia, depending on Re
https://doi.org/10.1017/jfm.2017.421
(or m) and Ca. However, the maximum thickness occurs at a lower Ca than that in
unconfined dip coating, because the narrow channel causes further acceleration of the
flow near the meniscus at the same Ca. Furthermore, the waviness of the meniscus
shape and hence the instability of the meniscus are also expected to be suppressed,
because of the presence of the stationary container wall. This regime remains to be
analysed.
Confinement effects in dip coating 23
(a) 5
4
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x 2
–1
0 0.2 0.4 0.6 0.8 1.0
y
(b) 5
0
10–2 10–1 100 101
Ca
F IGURE 10. (Colour online) Meniscus shape change and maximum normal viscous stress
for L = 1 and θc = 30◦ . (a) The coordinates are in units of l. The arrow denotes the
direction of increasing Ca. The meniscus shape changes abruptly in the dynamic meniscus
region for low Ca, but this change diminishes with increasing Ca. (b) τnn m
is the maximum
magnitude of the normal viscous stress on the meniscus. τnn is expressed in units of
m
capillary pressure based on the meniscus shape, which is an arc of a circle with a contact
angle of 30◦ at the wall. τnnm
increases monotonically with Ca. It should be mentioned
that the numerical results obtained with quadratic basis functions for the velocity and
position variables yield wiggles in the profile of the normal viscous stress on the meniscus.
Therefore, the result for the magnitude of τnn m
may be less accurate than those for other
primitive variables, such as the position and velocity.
value. Hocking (2001) explained that this non-uniqueness arises, at a low capillary
number Ca, from the presence of the three-phase contact line. Münch & Evans
(2005) and Jin et al. (2005) investigated the non-uniqueness of the film thickness
and the meniscus shape systematically by studying the phase space of an ordinary
differential equation for the shape. Furthermore, Münch & Evans (2006) examined
the interaction between the meniscus and the advancing front in the context of
24 O. Kim and J. Nam
Marangoni-driven films. In the dip coating problem, multiple solutions were observed
experimentally (Snoeijer et al. 2006, 2008), calculated asymptotically (Benilov et al.
2010) and computed numerically (Gao et al. 2016).
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The present study is limited to complete wetting of the moving plate by the
coating liquid, so that the three-phase contact line at the front of the entrained film is
meaningless from the standpoint of thickness determination. In confined dip coating,
the film thickness h∗∞ for complete wetting is uniquely determined and is thinner
than that in unconfined dip coating. However, for partial wetting, the deposited film
exhibits complex behaviour; a thick film in comparison with the film for complete
wetting can appear at the front of the entrained film in unconfined dip coating.
Snoeijer et al. (2006) and Gao et al. (2016) showed experimental evidence and
numerical predictions regarding the appearance of the thick film, respectively. They
also reported that the thickness of the thick film is determined solely by the physics
of the three-phase contact line; therefore, we speculate that the thick film would not
be significantly affected in confined dip coating.
In the present study, there is no restriction on the liquid supply to the channel.
Therefore, the meniscus reaches a steady state and fixes to the wall. Note that, if the
liquid supply is limited or is unable to keep pace with the removal by the entrained
film, the meniscus cannot be fixed to the wall. In the meniscus-controlled regime,
the meniscus recedes with constant velocity, which is a function of the size of the
container and the flow rate. In the channel-controlled regime, the solution cannot reach
a steady state; the pinned meniscus eventually invades the channel along the wall. It
is very similar to the low-flow limit phenomena induced by a limited supply of liquid
in slot coating flows (Carvalho & Kheshgi 2006). They are signalled by an invasion
of the channel between the coating die and the moving plate by the downstream
meniscus.
Acknowledgements
This research was supported by the Basic Science Research Program (NRF-
2016R1D1A1B03931632) and by the Global Frontier R&D Program of the Center for
Multiscale Energy Systems (2012M3A6A7054861) funded by the National Research
Foundation of Korea (NRF) under the Ministry of Science, ICT and Future Planning,
Korea.
by de Ryck & Quéré (1996). When D is sufficiently long, the flow becomes fully
developed under the meniscus. This means that δ approaches and even surpasses l;
i.e. the viscous stress from the moving plate reaches the container wall. Therefore,
for confined dip coating, a small channel width is sufficient to ensure a fully
developed flow. Within this flow, the viscous force is balanced by the pressure
and the gravitational force.
Confinement effects in dip coating 25
1.0
0.9
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0.8
0.7
0.6
0.5
0.4
0.3
0.2
FEM results
0.1 Jin et al. (2005)
Lee & Tallmadge (1974)
0
10–4 10–3 10–2 10–1 100 101 102
Ca
The value of dpc /dx at the inflow boundary can be evaluated from the velocity
profile at that boundary. When the flow is fully developed, the velocity profile is given
by (4.1):
1 L2
dpc
u=1+ + (y2 − y) − y. (A 2)
2 Ca dx
Note that the velocity profiles at the inflow boundary from the FE computations are
virtually parabolic and are almost perfectly fitted to (4.1), as shown in figure 12.
This strongly suggests that all the computed flows at the inflow boundary are fully
developed. The pressure gradient is directly obtained from the fitted equation.
controlled regime
Following White & Tallmadge (1965), equation (3.7) can be augmented by the
gravitational drainage:
dynamic
d2 h (Ca − T 2 L2 )2/3
= 1.3376 . (B 1)
dx2 h→∞ T
26 O. Kim and J. Nam
1.0
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0.8
Couette flow
0.6
0.4
u
0.2
–0.2
–0.4
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y
F IGURE 12. (Colour online) Velocity profiles at inflow boundary for different Ca under
L = 1 and θc = 30◦ . The solid lines (excluding the line indicated by the arrow) are quadratic
functions following equation (4.1), which are fitted to the FE computation results (filled
symbols). The line indicated by the arrow represents the velocity profile of a pure Couette
flow. As Ca increases, the profile approaches that of a pure Couette flow.
The modified White–Tallmadge model for confined dip coating flow can be obtained
in a manner similar to that described in § 3.1:
0.9458
T = Cc (Ca − T 2 L2 )2/3 . (B 2)
L
As shown in figure 13, the corrected equation (B 2) satisfactorily predicts T in the
low-Ca regime. In the thin-film limit, i.e. an extremely low-Ca flow, equation (B 2)
reduces to (3.14) because the gravitational effect vanishes.
L = k cos θc + O(k3 )
https://doi.org/10.1017/jfm.2017.421
as k → 0, (C 1)
and with the relation (κ0 /L)2 = 4/k2 − 4, the expansion for the confinement-correction
factor about the point k = 0 of order one in k is
k
Cc = √ + O(k3 ) as k → 0. (C 2)
2
Confinement effects in dip coating 27
100
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10–1
10–2
10–3
10–2 10–1 100 101 102
Ca
κ0 = 8β(φ) exp(−L/2), (C 5)
where β(φ) = exp[2(sin φ − 1)] cos φ/(1 + sin φ). The confinement-correction factor
can then be approximated as
1
p . (C 6)
1 + 32β 2 exp(−L)
28 O. Kim and J. Nam
Equation (C 6) becomes unity for large L, because of the vanishing confinement
effects.
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h∗∞
= 1.3376Ca2/3 . (E 1)
l/2
Note that the gap size is the same as l. In contrast to the confined dip coating problem,
the static meniscus shape in the cells is approximated as an arc of a circle with a
constant curvature of 2/l to leading order O(1) (see Park & Homsy 1984, equations
(4.6) and (4.25a)). Furthermore, the flow in the Hele-Shaw cell has plane symmetry,
but the flow in confined dip coating does not. These discrepancies produce differences
in the prefactors between equations (3.20) and (E 1), except for low L and a zero
contact angle. This exceptional case is discussed in the main text.
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