Effects of Surface Roughness on Wetting (Theoretical)

C. H U H 1 AND S. G. M A S O N
Department of Chemistry and Pulp and Paper Research Institute of Canada,
McGill University, Montreal, Canada
Received August 31, 1975; accepted July 30, 1976

The effect of roughness of a solid surface on its wettability by a liquid has been studied theoretically
using mechanistic arguments. By calculating the equilibrium shape of a liquid drop resting on a rough
surface, we obtain the relation between the true (or microscopic) equilibrium contact angle at the
three-phase contact line and the apparent contact angle observed macroscopically at the geometrical
contour plane of the solid. By extending a proposal of Shuttleworth and Bailey, we provide a plausible
explanation for hysteresis of the drop shape and contact angle which we evaluate for solid surfaces
with concentric grooves. To calculate the equilibrium drop shape of a liquid on a solid surface whose
roughness is more realistic than concentric grooves, we employ a perturbation method of solving
approximately the Young-Laplace equation for the shape. Although the hysteresis in contact angle
and drop shape cannot be evaluated by the method, the apparent contact angle and the local contact
line positions are approximately predicted when the surface roughness has the form of cross grooves,
hexagonal grooves, and radial grooves. Surfaces having random roughness are also considered and a
modified form of the well-known Wenzel equation is derived which includes a factor for surface
texture in addition to the conventional roughness factor.

I. INTRODUCTION surface. The relation is believed b y m a n y

The equilibrium contact angle which a
liquid surface makes with t h a t of a solid
which it contacts is a conceptually useful
measure of wettability. I t is, however, dif-
ficult to measure reproducibly and to predict
theoretically. An i m p o r t a n t cause of the dif-
ficulties which has received insufficient atten-
tion is the roughness which most solids
inevitably possess. Wenzel (1) and later others
(2-4) derived from thermodynamic considera-
tions a relation between the reproducible con-
tact angle 00 on a molecularly smooth surface
and on the rough surface 0r, in terms of the
roughness ~ (_>1) the ratio of the true to
the geometrical area:
c o s 0r = ~ c o s 00.
The angle Or is the a p p a r e n t contact angle
measured at the geometric level of the rough
1 Present address: Exxon Production Research Co.,
Houston, Texas.
workers to hold for solids whose surface
roughness is random and if the amplitude
and wavelength of roughness are below the
micron range (1, 5), b u t direct experimental
confirmation of the relation has not been
successful; generally the equation fails and Or
tends to fluctuate widely (6). Among efforts
to understand w h a t parameters in addition
to e should be included to explain the anom-
aly, Johnson and D e t t r e (7) adopted the
proposal (2, 4) t h a t a multiplicity of equi-
librium configurations of the liquid surface
(usually a drop) at different locations on the
solid is possible, resulting in widely varying
0r'S even though the local contact angle is
assumed to be uniformly 00; and postulated
[1-I
t h a t a particular configuration is determined
b y the competition between the " v i b r a t i o n a l "
energy of the liquid and an energy barrier
(4, 7-10) due to roughness which impedes the
progress of the spreading liquid. Even though

11
C o p y r i g h t ~ 1977 by A c a d e m i c Press, Inc. Journal of Colloid and Interface Science, Vol. 60, No. 1, J u n e 1, 1977
All rights of reproduction in a n y form reserved. I S S N 0021-9797
 12
a way of calculating the energy barrier was
suggested, the precise nature of the vibra-
tional energy was left unspecified and con-
sequently estimates of its magnitude were
not made.
One prominent aspect common to virtually
all contact angle measurements on solid sur-
faces is hysteresis. The measured 0r depends
on the way with which a liquid drop is formed
on the solid, and in particular the angle
assumed by an advancing liquid drop is
generally larger than when it is receding.
Shuttleworth and Bailey (3) suggested that
when a liquid drop was deposited on the
solid, the local contact angle would slowly
relax to the equilibrium value while the drop
surface would probably maintain the equi-
librium configuration at each instant of time.
The local contact angle would then attain
the equilibrium value when the apparent
contact angle becomes 0r = 00+ q~m, and
similarly for a drop formed by the retraction
of an extended liquid film 0r = 00--q'm t,
where ~m and Sin' are the maximum slope
angles of the respective faces of the solid
surface in the receding and advancing direc-
tions of the contact line. Johnson and Dettre
(7) proposed that because of the vibrational
energy of the drop, the advancing and re-
ceding contact angles would be different from
those of Shuttleworth and Bailey (3).
Because G depends on the way in which
the drop is formed, any study of the roughness
effect requires a rigorous specification of how
the equilibrium of a drop is attained. Instead
of speculating on the nonequilibrium states
leading to the equilibrium state of a constant-
volume drop (3, 7), we have chosen the fol-
lowing way of arriving at the equilibrium
drop, and restrict our consideration to it:
through a hole in the solid the liquid is fed
to the surface (which is horizontal when
gravity effects are appreciable and arbitrarily
oriented in space when they are not) at a
controlled flow rate so that it develops in an
approximately concentric fashion and slowly
enough to exclude viscous effects (11). A liquid
Journal of Colloid and Interface Science, Vol. 60, No. 1, J u n e 1, 1977
HUH AND MASON
drop will then grow and spread outwards on
the solid assuming a sequence of equilibrium
shapes; the feed of the liquid may then be
reversed to create a receding contact line.
While defining precisely the way in which
the drop is formed, this method of forming
the drop and measuring its contact angle is
a fair approximation to common practice,
which is to grow a small liquid drop on solid
by feeding liquid from a syringe above the
surface and to measure the contact angles.
With our convention, which we have found
to be experimentally advantageous (11), the
inevitable dynamic stages of attaining equi-
librium of a constant-volume drop by de-
positing it on the solid may be avoided, while
the equilibrium state is achieved by increasing
the drop volume very slowly under what are
essentially equilibrium conditions.
In Section II, we consider for mathematical
simplicity a liquid drop of radius R on con-
centric grooves as Johnson and Dettre (7)
did, and see how hysteresis occurs. By as-
suming R << (27/pLg) ½where pL is the liquid
density, g is gravity, and 3' is the surface
tension of the liquid, we may neglect the
effect of gravity; however, we later show
that this restriction is not of primary
importance.
Extension of the theory to surface roughness
without axial symmetry is difficult due to
mathematical difficulties in solving the Young-
Laplace equation for equilibrium drop shapes.
In addition to the computational complexity
arising from the nonlinearity of the equation,
a difficulty arises because the exact location
of the liquid boundary is not known a priori,
since only the solid surface configuration and
value of 00 to be observed locally on the solid
are given. However, when the solid surface
is almost flat, but otherwise of arbitrary,
smooth configuration, a perturbation method
can be developed which yields approximate
solutions for the equilibrium drop shape on
the solid. The first-order perturbation solution
was obtained by Huh and Scriven (12) for
axisymmetric meniscus shapes in gravity fields;
 R O U G H N E S S E F F E C T S ON W E T T I N G 13

in Section III we extend the method for multip]icity of the equilibrium shapes and the
higher-order terms of perturbation. The contact angle hysteresis which results from it,
method is valid when E<< 1 and e<<l/R, as we do in Section II with the concentric
where el and l are the characteristic height grooves of finite e. However, it reveals drop
and wavelength of the roughness. Starting behavior which cannot be predicted from the
with a spherical drop for a plane solid sur- concentric-groove models, e.g., a liquid drop
face, we calculate the change in the drop may be in equilibrium only at particular
shape due to the small changes in the surface locations on the surface. We calculate the
configuration, and then obtained Or for the solid approximate shapes of the equilibrium drops
assuming a uniform O0 locally on the solid. on cross grooves, hexagonal grooves, and
Being based on a perturbation scheme which radial grooves.
uses linearized expressions for the Young- In Section IV, we consider random surfaces
Laplace equation and its boundary condi- and develop a modified form of E1-] which
tions, our analysis cannot yet predict the takes account of the surface texture of the

60

50

e..8o, y~
~_ 40 - E • V'E/8 ~ , / z L _ - ~

30

20

I0 -3--T-,I=~,,T , , ITITE,[ i T ~l~l~l

I0 3 I0 4 105 IO s
V/~ ~

120 °

I00 o

~r 80°

60*

40 °

103 104 I06 JO6

b v/~

FIG. 1. Ca) Contact line radius po, and (b) apparent contact angle Or as functions of the drop volume
V for concentric sinusoidal grooves with e = 2~/8 a n d 00 = 80 °. T h e h e a v y center lines are for a geo-
metrically smooth surface. T h e equilibrium p0 vs V and 0r vs V relations are represented by the broken
lines, and the actual relations by the solid lines except that the n u m b e r of grooves traversed in a given
j u m p is indeterminate (see text).
Journal of Colloid and Inter]nce Science, Vol. 60, No. 1, June 1, 1977
 14
solid in addition to the conventional rough-
ness e.
II. CONCENTRIC GROOVES
Hysteresis
We first consider a model solid surface
formed of concentric grooves and an axisym-
metric equilibrium drop which grows slowly
on it (Fig. la, inset). The drop shape is
governed by the Young-Laplace equation
3,[-(1//71) --[- (l/R2)] = m p ,
where R1 and R2 are the two principal radii
of curvature of the drop surface, and Ap is
the pressure difference across the liquid sur-
face. For an equilibrium contact angle 00
uniform along the contact line on the solid,
the drop is a spherical segment of radius R,
provided the effect of gravity is negligible.
For sinusoidal grooves
z = 2~d sin (r/l)p,
the apparent contact angle 0r for a liquid
d~op whose contact line is at p0 is
0r = 00 -- tan-' [-2½~-,cos (Tr/l)oo],
where P and z are radial and vertical coordi-
nates, respectively, and 21 is the wavelength
of the grooves. The volume V of the spherical
drop calculated from simple geometry is
given by
~r (1 -- cos 0r)2(2 + cos Or)
V = -po~
3 sin 3 Or
E (5] /P°
+2½1rd p 0 2 - 2 sin
+ 2(2)½d2p0cos p0 • [-5]
If p0>>l and Or is not close to 0 ° or 180 °,
the first term of [-5] provides a good approxi-
mation for V. We can now calculate the
changes in p0 and Or as V is varied according
to our convention of forming the drop; to
illustrate we have done this (the dotted lines
Journal of Colloid and Interface Science, Vol. 60, No. 1, June 1, 1977
HUH AND MASON
in Figs. la and b) for the case of E = 2~/8
and 00 = 80 °.
For a given V, a multiplicity of equilibrium
drop shapes is possible each providing dif-
ferent 0r'S as previously noted (7, 9). To relate
the multiple equilibrium states with the con-
tact angle hysteresis, we consider a liquid
drop which is growing and is at state O in
Fig. la. As the drop volume is gradually
increased, the change of the equilibrium drop
shape is represented by the solid line between
[-2] O and A, and the contact line radius p0 barely
increases until A is reached. At A, the equi-
librium path is along the line segment be-
tween A and M', corresponding to decreasing
drop volume; since, according to our con-
vention, the drop volume cannot decrease, the
drop shape will go from A to A r, with the
contact line making a nonequilibrium jump?
With further increase of V, the drop will
jump to A". The energy which overcomes
1-33 the energy barrier in this case is therefore
the mechanical energy input during the process
of forming the present equilibrium configura-
tion (e.g., bringing A t to A 't by increasing V).
Similar jumps occur when a liquid meniscus
[-4-]
is displaced through a capillary of variable
cross section, and are known as Haines jumps
(13). When the contact line jumps, it is pos-
sible that inertia will cause it to occur over
more than one equilibrium position, for
example from A t' to A"'. When the process
is reversed by withdrawing liquid, the drop
will follow the path R - R ' - R " . Therefore, the
actual p0 vs V relation (Fig. la) is followed
x By calculating the free energy of each equilibrium
drop configuration as V is varied, we found that the
free energy attains maxima at A and A" and minima
at R and R ' ; the energy at positions of identical V
along AR is greater than those along R ' A and RA";
and the energy at A (or R) is higher than at A' (R'),
as pleviously calculated (7). Thus, energy is available
for a nonequilibrium jump from A and A'. The method
of free energy calculation, described in detail for
drops of fixed V on concentric grooves in (7), can be
readily modified for changing V and is omitted here.
For analogous free energy calculations for menisci at
vertical and inclined plates with horizontal grooves
see (10).
 ROUGHNESS EFFECTS ON WETTING
by the solid rather than dotted line. Figure lb
shows the corresponding apparent contact
angles (the solid line), which reveal that the
equilibrium advancing and receding contact
angles follow the upper and lower envelopes,
respectively, of the curve for 0r. This simple
argument reveals that the nonequilibrium
jump between the equilibrium states is an
essential aspect of the hysteresis, and should
be dealt with as a hydrodynamic problem of
drop instability, as outlined below.
The contact line m o v e m e n t being an ir-
reversible process with nonequilibrium jumps,
the advance and recession of the drop form
a hysteresis loop as we see from Figs. la and b.
The amplitude ( 0 m - 00) of the fluctuation
in 0r (thus, approximately half the contact
angle hysteresis) in Fig. lb is from [4]
0n/- 00 : tan -1 (2½e~-),
which we note is a function of only the ratio
of the roughness amplitude to the wavelength.
The amplitude AV of the volume fluctu-
ations with respect to the solid center line
for the drop growth on a truly flat surface
(see Fig. la) can be calculated from [5-]
and [6-]
AV ~" [-(1 -- cos 0m)2(2 + COS 0m)
003 3 k sin ~ 0m
(1 - cos 00)2(2 + cos 0o)]
sin 30o
\Po/
in which the last term can be safely neglected
because o0>>/- Figure 2 shows AV/oo ~ as a
function of E and 00. The difference AV' of
the drop volumes between the contact line
jumps over single grooves (e.g., A - A " or
R - R " ) can be calculated from the difference
between M and M ' in Fig. la:
(1 -- cos 00)2(2 + cos 0o)
A V ' = 2zclpo2
sin 3 00
which we note is independent of e.
15
50
I¢
~_~v
[ I I TlllE[ [ [ I l[lll
0.01 0.1
[-6] FIG. 2. Calculated amplitude AV of the drop-
volume fluctuations on concentric sinusoidal grooves
as a function of ~ and 0o.
J u m p i n g Mechanism
Whether the jump will be to the next
equilibrium position or over a number of
possible equilibrium positions will be deter-
mined by the dynamics of the contact line.
Immediately after A or R in Fig. la is reached,
the liquid drop becomes unstable and the
contact line will start to move. Because the
/ free energy of A (or R) is higher than that
of A' (or R') as was shown by Johnson and
Dettre (7), the difference, which is of the
order of .fiR, will be converted to the kinetic
energy necessary for jump (""pLu212R), re-
sulting in a velocity u of the contact line
of the order of (7/pLl) I.
The local viscous dissipation will not be
important if the Reynolds number u//p
= (Tl/pLv2) ½>> 1, or equivalently l >> PLVVT
(~,14 nm for water in air), where v is the
kinematic viscosity of the liquid. If the equi-
librium contact angle 00 is more or less in-
, [-8-] stantaneously observed as the contact line
moves, the drop surface will be deformed near
the contact line, as shown schematically in
Journal of Colloid and Interface Science, Vol. 60, No. 1, June 1, 1977
16 HUH AND MASON

contact line than away from it, the resulting

\ deformation of the liquid surface will propa-
\ gate in the folm of a capillary wave toward
x
X the top of the drop, eventually being damped
x\
out by viscous dissipation (14). The contact
\
\ line jump will, therefore, more likely be
\
x\ arrested at the neighboring equilibrium posi-
tion rather than override it, although more
i\ \ rigorous examination is required to establish
L \ \ I the validity of this point. It is pointed out
that the neighboring groove may not neces-
J", ""b, i sarily provide an equilibrium position; when
grooves of different ~'s are present, the
grooves of small ds located in between those
/ k ", X_I/! of larger E's will be skipped over, because
equilibrium on those grooves is not possible
for a given drop volume.
FIG. 3. Schematic diagram of the nonequilibrium
When the groove amplitude and wavelength
j u m p from A to A' (Fig. 1) of the contact line be- are smaller than or of the order of those for
tween the equilibrium configurations of the liquid liquid surface fluctuations due to thermal
drop. For explanation see text. motion, contact line movements due to the
thermal fluctuation and due to the drop in-
Fig. 3, with a resulting local increase of
stability will of course be indistinguishable.
capillary pressure ~ p ..~ "y/l; this is attained
The average wavelength of the liquid surface
at the expense of the liquid inertia OLU~ = 7/1.
As the next equilibrium state is approached, fluctuations due to thermal motion is (15)
therefore, progress of the contact line is more approximately (~re/n')½ = 2.92/(n')~ (~0.9 nm
likely to slow down and no further local for water) where n' is the number of liquid
deformation of the liquid surface is required. molecules per unit area, so that unless the
Because the liquid pressure is higher near the roughness amplitude and wavelength are of

L
6G

L
RI
R"
L
po/~ 4c m
J
L
30

~°TI~,T--~-'I rllllIT I r ilrtlll I I

to 3 io'¢ io 5
V/~ s

FIo. 4. Contact line radius p0 as a function of the drop volume V for concentric sinusoidal grooves
with • = 2~/8 and 00 = 30 °. On retracting the contact line, the drop surface is dissected (at R) as shown
by the inset, a n d a liquid a n n u l u s is left behind to form a composite surface.
Journal of Colloid and Interface Science, Vol. 60, No. 1, June 1, 1977
 ROUGHNESS EFFECTS ON WETTING 17

the order of the dimensions of the liquid (o)

molecules, it would therefore appear that the l
contact line jumps are for the neighboring ~z , , . / / ] ~ /
equilibrium states for concentric grooves; this _L _
//.,¢77~,
question and what happens when the grooves II ~ , ~ Po--~,
are not concentric, however, requires further o

detailed examination.
(b)
Formation of Composite Surfaces
When e is not small, pockets of residual
liquid or air m a y remain at the bottom of
the grooves as the contact line moves, and
a "composite" surface is formed (7, 16, 17).
Figure 4 shows the equilibrium relation be-
V
tween p0 and V for a small contact angle
(00-=30 °) and e = 2 ½ / 8 . We see that the
135"
advancing behavior of the drop is similar to
that of Fig. la, but the receding behavior is STICK JUMP
different; on reducing the drop volume, 0, re- 90"
® (9
duces with the contact line barely retracting, Or
until the drop surface touches the solid sur- 45"
i
Q
face (see inset of Fig. 4 where 0, = 2.06°).
This state is represented by the end point R
O*
of the equilibrium curves of Fig. 4. The drop
surface will be dissected there and the contact
line will retract to the position R ' leaving Fie. 5. (a) A plane solid surface with a model of
behind an annulus of residual liquid settled microscopic edge defect. The groove is circular, has
at the bottom of the grooves. The receding sharp 90° edges, and its width and depth are negligible
compared to the drop size. (b) The contact line radius
behavior of the drop with a large contact
p0, and (c) the apparent contact angle 0r as functions
angle is similar to that of Fig. la, but on of drop volume V for surface shown in (a).

5¢ !--

3c~

IO 3 10 4 I0 a I0 e

V/~ ~

Era. 6. Contact line radius p0 as a function of drop volume V for concentric saw-toothed grooves shown
by the inset (00 = 80°). A typical hysteresis loop is shown by the solid line.

Journal of Colloid and Interface Science, Vol. 60, No. I, June 1, 1977
 18
V -£7-,o.I
5C
4C
po/~
5C
2C
tr11~---~-
10"
FIO. 7. Equilibrium relation between o0 and V for concentric sinusoidal grooves when gravity effects
are appreciable (/(plg/2-v)½= 0.1, 00 = 80°, and , = 2½/8). Comparison with Fig. la shows that the
effect of gravity is small.
increasing V, the drop surface touches the
solid surface (for example, at 0r = 177.94 °
when 00 = 150 °) and annuli of air pockets
are produced to form a composite surface.
Effect of Sharp Edges
The above examples reveal that contact
angle hysteresis is a consequence of the vari-
ation in the slope of the solid, and imply
that the presence of sharp-edged grooves will
play an important role even if their width
and depth are small. To illustrate this point,
we consider a solid surface which is plane
except for an annular groove with sharp edges
which is present as a microscopic defect on
the plane solid. Figures 5b and c show the
effect schematically for 00 = 45 °. On increasing
the drop volume, the contact line sticks to
the inner edge and the apparent contact angle
increases until the critical angle of the edge
07 = 00 + (180 ° - $~) is reached (18) where
q~ ( - 90 ° for the example cited) is the angle
subtended at the sharp edge. Because the
equilibrium drop shapes which have their
contact line inside the groove will have a
smaller volume than that for the critical
angle, the contact line will jump. On reducing
the drop volume, the contact line sticks to
Journal of Colloid and Interface Science, Vol, 60, No. 1, June 1, 1977
HUH AND MASON
i IilI I t I I IITI]
I04 105
v/t ~
the outer edge and the apparent contact angle
decreases until 0r = 0 ° (because the critical
angle of the edge 0r = 00 + (180 ° -- 4~8) < 0 °
cannot be attained). Further consideration of
contact line behavior at sharp edges will be
given elsewhere (I9).
In Fig. 6 we have plotted p0 for concentric
saw-toothed grooves for 00 = 80 °. On in-
creasing the drop volume, the contact line
sticks to the top edge of a groove, moves
along the groove face away from the drop,
jumps as soon as it reaches the bottom edge,
and then sticks to the top edge, and repeats
the process. On decreasing the drop volume,
the process is similar except that the contact
line moves along the groove surface facing
the drop. This kind of contact lille behavior
has been observed and described in detail by
Bartell and Shepard (6).
Gravity Effect
In the foregoing calculations we have as-
sumed for simplicity that gravity is negligible.
To check the validity of this assumption, we
have calculated the variation of p0 with V
for liquid drops subject to gravity; as an
example we show in Fig. 7 the equilibrium
 R O U G H N E S S E F F E C T S ON W E T T I N G 19

relation on sinusoidal grooves when l(pLg/2"r) I was made by employing the approximate
= 0.1 (and taking 00 = 80 ° and e = 21/8 for drop shapes for large sessile drops (20), from
comparison with Fig. la). The calculation which we obtain for V:

V = rapd sin 2
2 3 \ 2 / _ 1 \ po po2 2~po3 /

[
--~-a~po sin Or + 2~Trel po~ - - 2 ('J] (F) sin po + 2(2)le12po cgs (F) po , [-9]

where a -- (23,/PLg)L pressed in terms of the drop volume as

This result is almost identical to the zero
R = [3V/Tr(1 - cos00) 2 ( 2 + cos00)] I. [-10]
gravity case except for high V, since the top
of a large drop under gravity tends to become The plane solid surface configuration m a y be
flat and V does not increase as much as the expressed as z = R cos00 in the cylindrical
spherical drop for a unit increase of p0. The coordinate system (o, z, q~) where p = r sin 0
insensitivity of the roughness effect to gravity andz= rcos0.
is important, because no matter how large When the solid surface configuration is
the drop, roughness is bound to influence changed from a plane to (Fig. 8b)
the wetting equilibrium.
z = R cos 00 + df(p, ok), [11]
where f =---f(p, ¢) is an arbitrary smooth func-
III. NEARLY FLAT SURFACES
tion describing the roughness, we wish to
Perturbation Approximation for Drop Shape
Calculations
A solid surface with concentric grooves is
a highly idealized model and the conclusions
drawn from it m a y not always apply to real ///, //L///// ////7
surfaces, so that a more realistic model is ~ r, O o O I
needed. When the rougness is small but the
surface configuration is arbitrary, we m a y 0
a t t e m p t solutions for the Young-Laplace (o)
equation using perturbation methods. With
this scheme, however, we are unable to
predict the hysteresis because the method
uses linearized equations. Nevertheless, it re-
veals drop behavior which cannot be predicted
from the concentric groove models.
To find the equilibrium shape of a liquid
drop on a given rough surface, we begin by
considering a spherical segment of a drop of
0
radius R on a plane solid surface (Fig. 8a),
(b)
in the spherical coordinate system (r, O, d#) in
the absence of gravity. For a contact angle 00 Fro. 8. Definition sketch of a liquid drop on (a) a
constant along the contact line, R can be ex- plane and (b) a generalized rough solid surface.

Journal of Colloid and Interface Science, Vol. 60, No. 1, June 1, 1977
20 HUH AND MASON

know the new drop shape r = r(O, 4~) which
satisfies the following conditions:
(i) The drop surface satisfies the Young-
Laplace equation [2-];
(ii) the equilibrium contact angle 00 exists
locally along the contact line (the contact
angle condition) ;
(iii) the drop volume is conserved (the
drop volume condition);
(iv) no net horizontal force acts on the
drop to cause translation on the solid (the
horizontal force condition).
We apply these conditions to obtain the
new drop shape.
(i) The Young-Laplace equation. If we ex-
press the curvatures in [2"] in terms of
r = r(O, ~), we get (21) for the Eq. [2-]

W-l I { 10r~2 ! ( ! 02r~ 1 0r)( 1 0r)( 1 02r ~ { (10r~2[

1 + (r-~n 0 0¢//\r 003/ - - 2 ( t O - 0 r sin 0 L r sin0O~¢/-t- I-t-\tO-0//

× , oB ,Or or)' I
(rsin2OO-~rh~/--3W+l+cotO(r--OOo){W+(r~mOOrki,]+c=O, [12a-I

where

W = 1+ + [12b-]
001 r sin 0
and c =- &P/'r is a constant. For the spherical drop on the plane solid, c = 2/R. When the
solid surface is almost flat, e << 1, we attempt solutions of the form
r = R + er (1) + e2r(~) + -.-, [13]

c = (2/R) + ~c(1) + ~2c(2)-t- " " - [14]

Inserting these expressions into [12a-] and collecting the terms of identical powers in ~,
we obtain
02r(1) Or(x) 1 02r(I)
-- + cot 0 + ~- 2# 1) + c(1)R2 = O, [15]
O02 O0 sins 00q~ 2
02#2)
--+cot0
Or(2)
+ - - - -
l O2r(2)
+ 2 r ( : ) + 2 # 1)
(r(l_~ )
+cO)R +c(2)R 2 = 0 , [16-]
002 00 sins 0 04~2

and so on for higher-order terms.

(ii) Contact angle condition. Since the con- and

tact line is where the drop surface intersects
the solid surface, its location may be ex- r(Oc, ¢) cos 0c = R cos 00 + df(po, ¢). [18"]
pressed either by 0 = 0c(¢) on the drop sur- If we assume
face r = r(O, ¢), or by p = pc(q~) on the solid
surface [-11-], and given by 0o = 0o + ~0(')+ e20(2) -[- -.-, [-19-]

r(O~, ¢) sin 0o = po, [-17-] po = R s i n 0 o + ~p(1)_[_ ~2p(2)+ . . . , [20]

Journal of Colloid and Interface Science, Vol. 60, No. 1, June 1, 1977
 ROUGHNESS EFFECTS ON WETTING 21

and insert these expressions into [17] and as the inner product of the unit normals on
[18], and collect terms of identical powers the drop and solid surfaces:
in e, we obtain for location of the line
1 Or 1 Or ]
p(') = (r ~1) - - If cos Oo)/sin 0o, [21] cos Oo = W-~ er - - - - e0 e~
r O0 r sin 0 04)

p(2)--__
R sin s 00
1 I
(r (1) c o s 0 0 - l f ) -
OrO)
00
.[, + + (. ;l-0
\ Op/ \pc 0 4 ) / i

_ _
2 sin 0o
(#1) cos 00 -- If) 2 + Rr (2) sin 00 X e z - - d - Of e o - - - - Of e~ , [233

- - R cos Oo(ru) -- If cos 0o)I O-fl ,
Opl
atp =Rsin0oandz=Rcos00.
Along the line, 00 should be observed at
the microscopic level. We can express cos0o
ap p~ 04) A
at 0 = 0o (or p = po), where (er, e0, %) and
[22]
(eo, e,, %) are sets of unit vectors in the
spherical and cylindrical coordinates, respec-
tively. Equation [23] m a y be expanded as
a Taylor series for 0 = 0 0 (or O = R s i n 0 0 ) ,
from which we obtain

OrO) of
sin O o - - - cos 00# 1) = R I ~ - sin 0o -- l f, [-243
O0 Op

sin O o -
Or(z)
O0
- - cos0or (2) - - - -
,[
R sin s 0o
- - I -Of
- - -Or(1)
-
04) 04)
- cos Oo {(Or(1)) -Jr-( l O f t 2 I
2 \04) 1 \ 04)/ I
02y (1) o2f
+ sin s 0o - - (lf -- cos 00# 1)) + R2l - - - (#1) _ l f c o s 0o) sin 2 0o
005 Op2

+ 1 COS2 00(r(1) COS 00 -- lf)2], [25]

at0=00 (orp=Rsin0o).
Equations [-21] and [22] have been utilized
to get the above expressions. For the differ-
ential equations [15] and [16], [-24] and [-25]
serve respectively as the boundary conditions.
(iii) Drop volume condition. The changed
drop shape should still encompass the speci-
fied drop volume of /-10]. The increase of the
drop volume due to the change of its shape
should therefore be offset by that result-
ing from the surface roughness expressed by
[11]:

f21r fOo
½r3 sin OdOd4) -- ½Ra sin OdOd4)
5? ° dO dO

• 2,, oo 1 sin 0o (pc R sin 0o) COSo] R" sin OdOd4)

-- o -3 L elf(pc) sin 0 -- (pc R sin 0o) cos

= dfodpd4) -- ~i,, Oo(po R sin 0o) df(pc)pdpd4). [-263

Journal of Colloid and Interface Science, Vol. 60, No. 1, June 1, 1977
22 HUH AND MASON

Expanding the above expression in terms
of the powers of ~, we obtain
ff'fo°°r(1)R2sinOdOddp
= lfpdp&b =-- AV". [-27]
dO dO
Because the average of f(p, dp) over a large
area should in general vanish, we may set
A V " - - 0 . The above volume constraint will
determine the value of c tl) in [15].
The drop shape given by [13] now may be
obtained, first by solving the differential
equation [15] for r <° with boundary condi-
tion [24], the unknown constant c m in [15]
being determined from condition A V " = 0.
Knowing r (t), we proceed to solve [16] for
#2) with the boundary condition [-25]. No
attempt is here made to prove the con-
vergence of the perturbation solution thus
obtained. Along the contact line, we can ex-
press the dimensionless configuration function
f(p, ¢) of the solid surface in terms of the
Fourier series
f = a0 o) + DAo) cos
+b,~o) sin g$], [-28-]
whose root-mean-square amplitude we choose
conveniently to be unity. By separating vari-
ables, we get (22) as the solution of [,15-]:

= cot ~(00/2)
r(1) = ~(1) _j_ [-(cos q$ + sin •) sin 0] + l ~] (~ + cos 0)tan ~ ( ~ )
• =2 K2 -- 1

X R sin 0 0 - - -- a, c o s t S + R sin 0 0 - - -- b, sin~q~ , [29a]

do dp
where
--l(R sin 0o (dao/dp) -- ao)(2 cos 0 - 1 -- cos 0o)
~(1) ~__ [,29b]
(1 - cos O0)(2 + cos 00)

and a,, b,, and their derivatives are at
p = R sin 00. The axisymmetric part [,29b] of
[-29a] is obtained by applying the volume
condition [27] with AV" = 0 as noted above.
The solution of [,,16] may likewise be ob-
tained, but is not presented here.
(iv) Horizontal force condition. Equation
[29a] shows that, whenever (R sin Oo(dal/do)
- al) and (R sin Oo(dbl/dp) -- bl) are nonzero
-
shift on the solid until it finds a position
where the two quantities given above become
zero. The horizontal component of the capil-
lary forces along the contact line is, from
the solution of the drop shape,
- ~ cos 0"(¢)
I ( 0r(i)

cos 00 + ~ sin 0 0 - -
at the contact llne, the boundary condition R \ 00
cannot be satisfied. Physically this means
that equilibrium is not possible because the
--r C1) COS 0o)-~ O(e2)l
interracial tension forces acting on the drop
along the contact line are not balanced in
the horizontal direction. Because the solution
for the mode, u = 1, shown in the square = --~ cosOo+-- RsinOo----
R Op
bracket of [-29a] is merely the horizontal
translation of the drop (23), the drop should at p=RsinOo,
Journal of Colloid and Inlerface Science, Vol. 60, No. 1, June 1, 1977
 ROUGHNESS EFFECTS ON WETTING 23

where 0* is the angle between the unit nor- force requirement for the drop shape calcula-
mals to the drop surface at the contact line tion is in addition to the Young-Laplace
and to the horizontal plane. The total force equation and the equilibrium contact angle
F~ acting on the drop in the x-direction is condition, and is not apparent in systems
with axial symmetry because it is then auto-
F , = --'r cos 0* (¢) cos 4,R sin Ood¢ matically satisfied,
~r We may at this point examine the range
= --Tr3'e sin OorRsin Oo(dal/dp) - ax-]l, of validity of our perturbation scheme. Equa-
[30a] tion r29a] shows that the deformation of the
drop surface er (~) is of the order of eR, so that
and similarly the force Fy in the y-direction is
1 Or 1 Or R
Fy = - rr3,~ sin 00
and ,~ ~ - - .
X [R sin Oo(db~/dp) - bill. [30b] r 00 r sin 0 Oq~ l

The drop can locate only at positions on the
solid where it is under no net force. We may
thus assume that al(p) and bx (p) are identically
equal to zero, and the solution for the mode
= 1 does not exist.
Not all locations where these forces vanish
are, however, stable positions for the drop
center. When a small displacement Ax > 0
of the drop from the equilibrium position
tends to impede the displacement because
AF~ _< 0, the drop is in a stable position,
whereas the drop is unstable if 2xF~ > 0.
Using a similar argument for Fy, we can say
that the condition for the stable equilibrium
position is
For the perturbation equations to be valid,
we must have, from [12a] and [23-1,
e(R/l) << 1 or e << l/R. [32-1
Derivation of Apparent Contact Angle
As our main interest is the effect of rough-
ness on the apparent contact angle Or, we
now calculate it from the approximate drop
shape obtained above. For this purpose, we
define 0~ precisely as the angle formed be-
tween the axially symmetric part of the drop
shape ((0) and the plane level of the solid,
where

F, = F ~ = 0 ;
OF~ OF~
< 0 and - - < 0 . [-31-]
'F
~(o) - - - -
27r ~r
r(O, 4~)d4~ = R + ~ ( ' )

Ox Oy
+~2~(2) + 0(~). [33]
Placed at other locations on the solid, the
drop will translate to a stable position. This Thus, we get from [-23-] to [25-1,

O}(~)
cos 0r = cos 00 + sin 0 o - cos 00~(l) +
- - R sin 0 0 - - -- R cos 00~(2)
O0 R2L O0
O}(1)
- sin 0o((1) - - ½ cos 0o - - j ~ -t- cos 00~(') - - -[- cos 00(1 -1- ½ cot 2 0o
00 001 002

--~ cos 0o cot 2 0o)~(~)~] + O(d). [34]

/

From [24-1, [-25-], [29-], and [34-], we can obtain an expression for Or in terms of a,, b. and
their derivatives
el( dao ) ~212.
cos0r = c o s 0 o + - - Rs]n0o---- ao + [-Xo+~'.{X(a. 2)+x(b.2)}-1+O(e3), [35a-1
R do R2 .=2
Journal of Colloid and Interface Science, Vol. 60, No. l, June 1, 1977
 24 HUH AND MASON

where
02~(l) d2ao duo
Xo/-- ao -4- R ~ (~(1) _ aol cos 00) + (1 -- cos O0 cot 20o)ao~(" -- R sin O0- - ~(1)
O02 (tp ~ do

+½ cot 20oao~l -- ½ cos 0o (7)'/ l + ½ cos Oo cot 2 0o~(1)2/I; [35b,]

1 ( -}-COS00 2 ( K(K2 - 1)
x(aa-IFcos00
2sin 20oL Z-- 1 / cosOo)
+ sin 20o + ½ cos 3 0o)

da, a~) ' + + cosoo. /,

X ( R sin 0o - - -- K2 -- sin 2 00 -- cos 3 00 }
do K2 - 1 ][(~+ cosO0)
da. )
X a. R sin Oo-- - a. +½ cos Oo(tc2 -Jy c o s Oo)a 2 .j - R2 sin2 0o (~ + c°s O) d2a.
. . . . .

dp \ K2 - - 1 do2

X ( R s i n 0 o ~da. a. ) - R 2 cos0osin 20oa"d02A'

d2a"1 with K > 2; [-35c-]

and similarly for ),(b,2), and where a,, b,, ((~),
and their derivatives are all at o = R sin 0o.
Thus it follows from [35-] that 0r depends
on the solid surface configuration and the
location of the equilibrium site. These rela-
tions are used in the next subsection for
several models of roughness. It suffices to
calculate 0r with the perturbation term in e
alone, but if there exists no axisymmetric
mode, the term in e vanishes and we must
then seek the term in e2.
The Case ao = 0
When the term in E in [35a'] vanishes, we
m a y derive an alternative expression for [35a-]
in terms of the area ratio of the rough to
the planar surface. Since the drop equilibrium
is influenced by the roughness at the contact
line and is unaffected by the solid surface
inside the drop, we calculate the area ratio
along a thin strip of width 23 near the con-
tact line :

O"~ L 27r
,inoo_, °do'J
E212 27r R,inOo+Sv(O_f~2 =~
=1+
8~'~ sin 0o n sin 00-5 L k O p / R s]-n 0o 00/-lp=R ,i. 0o

X sin OodM4~+ O(e4). [36-]

The area ratio c, thus defined for a particu- drop size, the two values will be substantially
lar drop will be different from e taken over equal. By eliminating d from [35a] without
the entire area of a given solid, but if the the term in e and [-36-], we obtain
roughness is homogeneous and its amplitude
and wavelength are much smaller than the cos 0~ = cos 0o f-~ + ( ~ - 1)q~,], [-37a]
Journal o] Colloid and Interface Science, Vol. 60, No. 1, June 1, 1977
 ROUGHNESS EFFECTS ON WETTING
where
- - 1 + (x0 + ~'. [x(~:) + X(b.~)])/
cos 0012¢~(ao2) + ~ {¢3(afl)+/3(bfl)}] [37b]
K=2
and
fl( afl) -- 4 L k dp / + R ~sin200j ' [37c]
and similarly for t3(b~2). We designate ¢ as
a surface texture factor for reasons dis-
cussed later.
An example of a0 ~ 0 is the surface with
radial grooves discussed in the following sec-
tion. Another important application of [37a]
is made in Section IV to the randomly rough
surface, for which the average d0 -- 0. Using
these two examples, we will show how q,
varies with the nature of the surface roughness.
Applications to Model Surfaces
For a small liquid drop deposited on the
solid surface whose configuration varies regu-
larly, we apply the above derivation to cal-
culate 0r and to determine what parameters
influence it. We also calculate, when the drop
volume is gradually increased (or decreased),
how the contact line progresses (or retreats)
locally on the rough solid surface, and how
0r varies with respect to V.
(i) Concentric grooves. To examine the va-
lidity and limitations of the present perturba-
tion method, we compare its results for the
concentric grooves with the exact solutions
obtained in Section II. For the grooves [-3],
0r can be expressed to the order of e, from [35],
cosOr=cosOo+ L--sinOocos sinO0
. (Fig. 10),
--sin (?)]
sin0o . [.38]
Journal of Colloid and Interface Science, Vol. 60, No. 1, June 1, 1977
25
From [21], p0 to the order ~ is
2M V(1 + cos 01)2
o0 = R sin 00 (2 4- cos 0o) L sin 00
X sin ( ~ sin 0 0 ) - ? cos ( ~ - sin 00)] .
[39]
When we slowly increase the volume of
the drop, 0r shows a nearly sinusoidal fluc-
tuation, and the increase of p0 is also sinus-
oidal. In Figure 9a and b we compare 0r
and p0 from the above approximate solutions
and the exact solutions for e = 2~/40 and
00 = 40 °• We see that Or is approximated
reasonably, but as the drop size is increased,
the perturbation solution cannot predict the
skew of the curve for Or. For small drop
sizes, o0 is reasonably predicted, but again
the multiplicity of the equilibrium drop shapes
(cf. Fig. l) cannot be obtained, because the
method uses linearized equations. Even though
the perturbation method is unable to predict
hysteresis, the fact that the magnitude of
fluctuations in 0r can be reasonably predicted
leads to the possibility that the envelopes of
the fluctuations in 0r may still approximate
the advancing and receding contact angles;
this, however, is a matter which should be
checked experimentally.
(ii) Cross grooves. When the roughness
height varies periodically forming square pat-
terns (as in woven fabrics), the surface con-
figuration can in general be represented by
the Fourier series of the symmetrical form
7r
os(7 Y)
11"
+ 71"
For the simplest case of m = O and n = 1
f= c o s - (x 4- x0) 4- c o s - (y 4- y0) , [40]
l l
]
26 HUH AND MASON

45*
; ' fl
O, 40 o

A,t /
35 °
,/I; , [1/] il4 !t,
•, v
30*

5 IO 50 I00 500 I000

V/23

FIG. 9. Comparison of the exact solution (dashed lines) and the perturbation solution in the order
(solid lines) for concentric sinusoidal grooves for e = 2½/20 and 00 = 40 °. (a) Apparent contact angle Or,
and (b) contact line radius p0 as functions of the drop volume V. The agreement for the amplitude of the
0~-fluctuations is considered to be reasonably good, which suggests the possibility of predicting approxi-
mately the hysteresis in Or (shown by the approximately horizontal lines with arrows).

the Fourier coefficients for [28-] are given by kind, and (xo, yo) is the position of a fixed
reference point on the solid with respect to
o0=[cos( )+cos( )l the origin at the drop center. The coeffi,cients
al and bl can be made equal to zero when
the drop center stays at the peaks (e.g.,
x0 = y0 = 0), pits (x0 = y0 = l), or the saddle
points (x0 = l and y0 = 0). We can further
show from [31] that among these equilibrium
positions, only the pit positions are stable.
l/ Any drop deposited with its center within
a square block bounded by four peaks (Fig. 10)
would slide to the stable equilibrium position
at the center of the square. Following the
and terminology of Johnson and Dettre (7), we
can state that each stable location is sepa-
rated from the neighboring ones by "energy
\ l / "\l/' barriers": to move a drop with its center at
where J is the Bessel function of the first the stable position 1 to another stable posi-
Journal of Colloid and Interface Science, Vol. 60, No. l, June 1, 1977
 ROUGHNESS EFFECTS ON WETTING 27

tion 2 in Fig. 10, we must bring the drop Figures 13a and b show (for 00 = 40”, E = 0.05,
center first to the position 3. The work re- 0.10) the detailed location of the contact line
quired W’ is, from [30b] and [41c], on the cross grooves calculated from [Zl].
We note that for a small drop, the contact
W’ = -~yt sin e. cZyO line assumes an almost square shape which
reflects the geometry of the surface: as the
drop size increases, the contact line becomes
more circular. We also note that since, in
the example chosen 00 < 90”, the contact line
is reluctant to go over the ridges and the
-2-71 r"; "")1. [42] peaks, but surges past the valleys and pits
easily revealing the phenomenon of capillary
This energy barrier is in addition to any channelling. Unlike the concentric grooves,
resulting from the multiplicity of the equi- the contact line thus seeks out those parts
librium drop shapes for the drop center re- of the surface where it can progress more
maining at one position on the solid (7). easily.
From [35a] and [41a], we obtain for 0, to (iii) Hexagonal grooves. Surface configura-
the order E, tions with hexagonal symmetry can in general
be represented by the Fourier series of the
form (24)

j=g-gd ,,[,,, (Fmx) COS gny,

-i-Jo ("""f" "")I, [43] m=l n=l

for a given I/ (by way of R through [lo]). + cos i Cm + 3n)x 1 cos {g Cm - n)y }
1
The average of pc taken along the drop
circumference, PO’,is
+ cos ; (m - 3n)x)
262 i
po’ = R sin B. +
(2 + cos e,) sin e. 3&r

x f-
TR sin e.
x cos -g (m + n>y
i II .

1
For the simplest case of m = n = 1,

xJl(,Rqneo)]. L-441
j= (5J[2cos ($(x+x,,)

Figures lla and 12a show, for 00 = 40” and

Gr
140” and 6 = 0.05 and 0.1, how b’= varies x cos (“-G (Y + Yo)
with respect to V. Figures lib and 12b show
the corresponding changes in PO’.The ampli-
tude of the fluctuations in 8, decreases as the
fcos {;cx+x,,)], c451
drop size increases for the cross grooves ;
while for the concentric grooves (Fig. la) the
amplitude remains approximately constant. the Fourier coefficients al and 61 can be cal-
Jourd oj Colloid ad Interface Science, Vol. 60, No. 1. June 1. 1977
28 HUH AND MASON

FIG. 10. Perspective view of a model surface with sinusoidal right-angled cross grooves. Stable equi-
librium positions of the drop center are denoted by + at the groove pits. A denotes peaks and the solid
lines ridges a n d valleys. Positions 1 and 2 (over pits) are stable. All other positions, e.g., 3, are unstable.

- eo : 4 o " / ~ : 0.40
,,50° -

8,

40'

30'

5x I0 5x I00 5x I000
v/2' 3

Oo: 4 0 °

IC

p,;,,.l
E .

5x I0 5x I00 5x I000
b V/,Z a

FIG. 1 l. Perturbation solutions to the order e for drops on sinusoidal cross grooves (see Fig. 10) with
= 0.1 and 0.05, a n d e0 = 40 ° for both. (a) Apparent contact angle Or, and (b) average radius of contact
line p0' as functions of V.

Journal of Colloid and Interface Science, Vol. 60, No. 1, June 1, 1977
 ROUGHNESS EFFECTS ON WETTING 29

culated as at the peaks (x0=y0=0), pits (x0=2l/3

a n d y0 = 0) a n d the saddle p o i n t s (x0 = 1
a n d y0 = 0) of the solid, a n d of these, o n l y
at = - - 2 sin cos
\3/ the pits provide stable e q u i l i b r i u m positions.

+
(21rxo~ T h e coefficient a0 can be o b t a i n e d a n a l y t i -
cally as
ao --- - - 2 (])½Jo (2~-p//), [-46c-]

from which we see t h a t values of 0r are almost

bl = --2(2)5 cos sin X - - T - / identical to those for the cross grooves.
Figure 14 shows as a n example for
= 0.02(a2) ~ a n d 00 = 40 ° a n d different V's,
the detailed location of half the c o n t a c t line
on the model calculated from [-21]. W e ob-
These become zero w h e n the drop center is tained the first 50 F o u r i e r coefficients n u -

- Oo = 140 o
150 o • = 030

140 °

130 °
l i I II~1,1 t f I I,I~,I i I T I
I02 5x [03 5x I04 5x
v/~ 3

15
0o= 140 °

I0

e: - 0 . 0 5 - - - - - ~
T

102 5x I0 3 5x 104 5x
V/~. 3

FIo. 12. Perturbation solutions to the order e for drops on sinusoidal cross grooves (see Fig. 10) with
e = 0.1 and 0.05, and 00 = 140 ° for both. (a) Apparent contact angle 0r, and (b) average radius of
contact line p0' as functions of V.
Journal of Colloid and Interface Science, Vol. 60, No. 1, J u n e 1, 1977
30 HUH AND MASON

~o =40°
E = 0.1 V / ~ 3 = 16.11 =1289 : 455.2

,. . . .
.°07 .,.
7o

FIG. 13. Detailed location of half the contact line for sinusoidal cross grooves for different drop volumes:
(a) When ~ = 0.1 and 00 = 40 °. As in Fig. 10, h denotes a peak, + a pit, and the solid lines denote ridges
and valleys; Each semicircle represents the average radius p0'. (b) When , = 0.05 and 8o = 40 °. The
grid lines are ridges, and the nearly circular lines are contours of constant z on the drop surface. For the
first configuration at the top left, p(°)/l = 3.0, and the successive ones (downward and from left to right)
have p(°)/l increasing with equal increments of 0.3. These shapes were computer drawn.

merically employing the standard subroutine
p r o g r a m m e d in an I B M S-360 computer and
using a recursive technique.
(iv) Radial grooves. We next consider a drop
whose center coincides with the origin of the
radial grooves on a solid (Fig. 15, inset). F o r
a radial groove, f is a function of only one
variable, ¢ + dp where d is a constant, and
we can expand f in terms of the Fourier series
f = ~ [{d, cos (dKp) + e, sin (dKp)} cos K¢
g~2
+ { - - d , sin (dKp) + e, cos (dKp)} sin K¢-],
where d, and e, are constants, and a 0 - 0.
To maintain the drop center at the origin,
we also assume al = bl = 0. Because a0 = 0,
0, is given b y [37a-].
Figures 15a and b show 0r in terms of a
when
f = 21 sin K¢. [47"]
W e note t h a t the area ratio ~ of [36-] is con-
s t a n t whereas e is a function of p. We also
note t h a t q5 (defined in r37b]) depends only
on the surface shape, i.e., the choice of the
Fourier mode K, b u t not on the groove am-
plitude which is reflected in g. As K increases
Journal of Colloid and Interface Science, Vol. 60, No. I, June 1, 1977
and the wavelength of the roughness becomes
much smaller than the drop size, E37a-]
r a p i d l y approaches the Wenzel equation [-17.
Table I shows for the surface of [47"] (I) as
a function of 00 and K, and we see t h a t at
K = 10, ]~[ < 0.04 for most values of 00.
W i t h radial grooves, whose p r o m i n e n t char-
acteristic is the absence of the axisymmetric
mode a0, we m a y therefore say t h a t [-1-] is
valid provided the amplitude and wavelength
of roughness are smaller than the drop size.
IV. RANDOMLY ROUGH SURFACES
As real surfaces generally do n o t show
periodic variations in contour, the roughness
is usually characterized n o t b y a concrete,
definitive surface configuration b u t b y an
averaged, statistical description. E m p l o y i n g
the p e r t u r b a t i o n solution of Section I I I , we
now a t t e m p t to predict 0r for solid surfaces
with random roughness. W e define the average
of a q u a n t i t y F for a given solid surface,
e.g., the height or slope of the roughness, as
one averaged after m a n y measurements at
different positions xn on the surface:
N
P~ = / ; ( x . ) -- lira (l/N) Z F(x.). [48-]
 ROUGHNESS EFFECTS ON WETTING 31

lllllll'n ,I I ,I I ,I I ,I , , ,

111e--,
L(
I
m
I

I[ Ill ,,,,,,,
I IIIllll IllllI

Ilillll] ] IIIII1[ IIIIllll[lll

IIIlllJ ] Illlll[ IIlIIII

IIIllll IIIIIII IIIIIII

LIllllllllll

,,,,,,, Iltt iiii

b
FIG. 13--Continued

We also define the correlation between two assume )~(0) = 1. Rice (25) has shown that
quantities F and G as the slope autocorrelation and the slope-height
correlation can be obtained from the height
FG(xr) = F ( x . ) a ( x . + x~) ---= lim ( l / N ) autocorrelation as

N 62 _ _
X Y'. F(x.)C(x. + xr). [49] __ - - :,<,>
n=l \ as/ d~~ [51 a]
If the solid surface roughness is isotropic, and
the correlation is a function only of the dis-
tance n ~ lXrl between two points. Of d ~
f_0f (7) = f(n) = - - ff(~). [51b-1
Randomness implies that the averages of as 0s d~/
the variations in height, slope, and curvature
of the roughness vanish : We also note that the average of the area
ratio ~ will become e.
f = o f / o s = o V / o s ' = o, [503 We now calculate the averages of the Fourier
coefficients a, and b, and their p-derivatives
where s is either the x- or y-coordinate.
of [28-] :
However, in general, their correlations do not
vanish, and they can be obtained experi- ~r

mentally by tracing the solid surface profile

in many different directions on the solid with
a,(#) = ( l / r )
f --f
f(x,,+pcosck, y , , + p s i n ~ ')

two profilometers separated by a correlation × cos K4,d4,, [-52-1

distance 7. We will then obtain, for example,
the height autocorrelation )~2(n), for which we and similar expressions for b,(o) and their
Journal of Colloid and Interface Science, V o l . 6 0 , N o . 1, J u n e 1, 1977
32 HUH AND MASON

8o = 4 0 "
E = 0.02 2"V'~'3 V/,~ 3= 16.11 = 128.9 = 435,2
~l-( p('~l= 3.0/ Z =9.0 7
+ ' +

t.

Fro. 14. Detailed half of the contact line for sinusoldal hexagonal grooves for different drop volumes
(e = 0.02(])] and 00 = 40°); -[- denotes a peak, and the solid lines valleys.

p-derivatives, where (xn, y~) are the coordi- locations on the solid where the h o r i z o n t a l
n a t e s of t h e c e n t e r of a g i v e n drop. T h e force c o n d i t i o n is observed. B e c a u s e t h e
positions (Xn, y,) for the d r o p centers are a v e r a g i n g process requires r a n d o m selection

(a) 8o = 120"

f =V'2sink~

WENZEL

Or

T 1 f I I l 1 t

60* (b) eo- GO*

EQUATION

k= 2 %. 4 5

0ol I rL ~r I I
1.0 1.2 1.4 1.6 =.e 2.0
O"

FIG. 15. Apparent contact angle 0, on radial sinusoidal grooves shown by the inset (the dotted lines
represent the ridges and the solid lines the valleys) when (a) 00 = 120 ° and (b) 60 = 60 °.
Journal of Colloid and Interface Science, V o l . 60, N o . 1, J u n e 1, 1977
 ROUGHNESS EFFECTS ON WETTING 33

of the measuring locations, d, then is not the see that d, = 0, and similarly for/), and their
average of a, according to the precise defini- p-derivatives.
tion of [48-1. We nevertheless assume that it The correlations for a~ and b~ can be calcu-
is a close approximation, and from [50-] we lated as

~,~(o) + b,~(p) = (1/Tr2) f ( x . 4- o cos t, y,, 4- p sin O / ( x . 4- o cos t', y,~ 4- p sin t')
~r 7r

X [-cos K: cos Kt' 4- sin Kt sin J ] d l d l '

= (i/~ ~ /~12~p[-i - cos (t - t ' ) 3 q cos K(t - t')dtdl'

and similarly,
= (2/~-)
/0 f2[-2 O sin (}/2)] cos K(d~, [53a3

~-p/ 4- \ ~ - p / ; --~ ff 2p sin 2 cos ~ cos ~ t ~

d~7

1[ d2a~_l d2b._l d2a.+l d2b~+l7

+ -- ,, E53b3
L dp ~ do 2 do2 dp 2 I

a~ - - 4- b,, - - - ff 2p sin cos K}.'/}. [-53c]

do 2 do 2 d~l~

a, - - - 4- b~ - ff 20 sin sin cos K}:t}, [-53d]

do dp x d71 2 2

da* d2a* db" dZb~ 2 f o" d 3 ~) ~

__ __ .~_ -- ] __ f2 2p sin sin - cos ~ cos K}d(. [-53e-]
do do 2 do do 2 7r d~ ~ 2

In deriving these equations, use is made of obtain the average Or in terms of 3, 00, and
[-51a and b-]. the roughness correlations [-53a-]-[-53e-] of a
Because do ~ 0, we can utilize [-37a-] to given surface :

cos Or = COS 00[; + ( ; -- 1)~'3, E54a]

where
= --1 + (X0 4- ~ [-X(a,
-5) + X ( ~ ) - ] ) / c o s 00[-2fl(~002)-b ~ [fl(~-fi2)+ ~3(bfi)}-], [-54b-]

and the correlations U53a] and [53e] are tities are used instead of the values evaluated
obtained at p = R sin 0o. Equation [54a] is at a particular position on the solid. Corn-
identical to [37a] except that averaged quan- paring [37b] and [54b], we note that while
Journal o f Colloid and Interface Science, V o l . 60, N o . 1, J u n e 1, 1977
34 HUH AND MASON

TABLE I
Calculated Surface Texture Factor cI, for Single-Mode Radial Groovesa
Oo ( ° ) ,:
2 3 4 5 10 100

20 1.99 0.50 0.22 0.12 0.024 2.0 X 10 -4

40 2.01 0.50 0.22 0.12 0.023 1.8 X 10 -4
60 2.33 0.58 0.25 0.13 0.023 1.6 X 10-4
80 4.72 1.17 0.48 0.25 0.035 1.4 X 10-4
100 -3.05 --0.77 -0.30 -0.15 -0.014 6 X 10-s
120 -0.60 -0.16 -0.059 --0.027 -0.0011 4 )< 10-5
140 --0.18 --0.046 --0.017 --0.0074 7 X 10-~ 2 X 10-5
160 --0.036 --0.0094 --0.0035 --0.0015 7 X 10-n 5 X 10-~

a Oovalues of ~I, calculated by numerical solutions of [-37b].

of [37b-] is a function of 00 and R , and is formed; but it is not possible to account

also differs from location to location for a for this, since we have employed the per-
given surface, ~b of [-54b-] is a function of turbation solutions of Section I I I .
only 00 and R for the given solid. Keeping these shortcomings in mind, we
We have derived ['54a-] in a form closely now apply [54-] to a surface whose height
resembling the Wenzel equation CI'] with an autocorrelation follows a Gaussian distribution
added contribution ~ which accounts for the
correlation characteristics of roughness of the if(n) = e-~(./.) ~. Ess3
solid surface under study. I t is emphasized
that while the derivation of [-1-] is thermo- From [53a-], we can calculate
dynamic, that of [54a] is mechanistic. As
indicated earlier we have called 7~ a surface a, ~ q- b, ~ = 2e-(,/,o2I.(p2/a2),
texture factor, because it reveals the difference
where I , is a modified Bessel function; simi-
in the surface textures for two surfaces of
larly the terms [-53b]-[53e] can be calculated.
identical e, which the Wenzel equation cannot
Figure 16 shows ~ as a function of the ratio
differentiate. Because e > 1, the Wenzel equa-
of the drop radius to the characteristic cor-
tion predicts 0r _< 00 for 00 _< 90 ° and 0r > 00
relation distance, R / a . We see that as
for 00 > 90°; this m a y not always hold with
R / a - - * oo, 7~--~0: When the drop size is
[-54a'] because ¢p m a y be negative (Table I
large compared to the characteristic roughness
and below).
correlation distance, we recover on the average
I n practical application of the above formal
the Wenzel equation [-1]. I t is not known at
derivation we encounter two difficulties. The
present whether this convergence to the
first is the fact, mentioned above, that the
Wenzel equation holds for the particular cor-
position (xn, y,) for the drop centers are not
relation function of E55] or it generally holds
truly random ones. When we determine the
for others; this observation warrants further
correlations for a given solid surface, the investigation.
profile measurements are made without refer-
ence to the probable drop position; a possible
V. SUMMARY AND DISCUSSION
compromise is that the equilibrium drop posi-
tions are sufficiently random that [-53a]- How surface roughness causes wetting hys-
[-53e] are the averages in the sense of [49] teresis has been studied b y considering a liquid
for practical purposes. The second difficulty drop growing or retracting concentrically on
is that 0r depends on the way the liquid drop a solid surface with axisymmetric grooves.
Journal of Colloid and Interface Science, Vol. 60, No. 1, June 1, 1977
 R O U G H N E S S E F F E C T S ON W E T T I N G
0.'
~ 0 o- 140"
¥ o
-0.5 - o-40-
T T F T
0 5
FIG. 16. Surface texture factor V~as a function of R/o~ on a random surface with Gaussian roughness.
When R/cx ~ ~ , the Wenzel equation El-[ applies.
Contact line movement in the form of sudden
jumps between equilibrium configurations was
emphasized, which appears visually as the
well-known stick-slip phenomenon (11). Un-
less the roughness amplitude and wavelength
are of the same order of magnitude or smaller
than those for the thermal fluctuations of
the liquid surface, each jump for concentric
grooves is likely to occur to the adjacent
equilibrium position rather than over several
intermediate positions. It may, nevertheless,
be possible to jump over a number of equi-
librium positions as a result of mechanical
vibrations transmitted to the system.
Extension of these ideas for surface geome-
tries other than the concentric grooves re-
quires solution of [-2] for nonaxisymmetric
drop shapes, and the approximate scheme
given in Section III is a start toward the goal.
A new class of equilibrium drop configurations
and the roughness energy barriers, demon-
strated in Section III, add to the information
on the multiplicity of drop configurations,
and thus improves our understanding of the
hysteresis. When the surface roughness is
nonconcentric, progress of the contact line
may exhibit the capillary channeling, prefer-
ring either the valleys (when 00 < 90 °) or
Journal of Colloid and Interface Science, Vol. 60, No. 1, June 1, 1977
35
;¢1÷1'
l !
I l 1 T T / ,
I0
R
ridges (when 00 > 90 °) on the solid, as shown
in Fig. 13. Nonequilibrium jumps will prob-
ably also be limited to the portions of the
contact line length.
There exists a possibility that the envelopes
of the fluctuations in the Or calculated by
the perturbation method may approximate
the advancing and reducing contact angles,
as is the case with concentric grooves; if so
our perturbation method permits a rough
estimate of the contact angle hysteresis for
solid surfaces with regular roughness. This
possibility should, of course, be confirmed
experimentally. Fstimates of the magnitude
of the contact angle hysteresis for randomly
rough surfaces of solid can be of value in
the practical assessment of the solid surface
roughness via measurements of wetting hys-
teresis and should be the main thrust of any
extension of the present study. In studies on
the roughness effect on wettability, little use
has been made of the roughness correlations
determined experimentally by profilometry
(11), an aspect which warrants further
consideration.
The thermodynamic considerations in de-
riving [-1-] have received extensive theoretical
attention (4, 7, 10). Since wetting is not gen-
36 HUH AND MASON

erally reversible and nonequilibrium jumps included in any comprehensive analysis of

between equilibrium states occur, we believe wetting and spreading.
that our mechanistic analysis leading to the We have assumed thus far that the equi-
apparent contact angle expression [35a] should librium contact angle 00 on a molecularly
be extended to include these aspects. Having smooth and homogeneous solid is constant
found (Fig. 15) that [-35a] reduces to [-1] regardless of the way with which the liquid
for radial grooves when the roughness wave- drop is formed on the solid, and the contact
length is much smaller than the drop size, angle hysteresis when the surface is molecu-
in which case a drop can advance and retract larly smooth is absent. Even though repro-
reversibly, we can say that here wetting ducible contact angles on smooth surfaces
occurs free of energy barriers (7). It is noted have been reported, contact angle hysteresis
in this regard that on the idealized roughness of 00 may still exist due to the plastic or
models (7, 10), 0r calculated from [-1] was viscoelastic behavior of liquid near the contact
shown to be the contact angle which provided line as the drop is formed. Whether or not
the minimum free energy among all of the the local contact angle on the rough solid
possible equilibrium 0r's; further thermo- surface is truly 00 is another question which
dynamic examination of [-1] on rough surface should be confirmed experimentally.
may be expected to provide valuable insights. In view of the earlier and present studies
If we treat the contact angle measurements on the heterogeneity and roughness effects,
in the statistical sense, we obtain [-54a], the general practice of assuming the advancing
which takes into account the nature of the contact angle as the equilibrium contact angle
surface roughness. Gaussian roughness [-55] and using it for thermodynamic derivations
indicates that when the drop is large com- of solid interfacial free energies etc., should
pared to the characteristic correlation distance be reexamined.
of roughness, i.e., 7~--~ 0, 1-54] reduces to [-1].
Whether or not this convergence holds for LIST OF SYMBOLS
other types of roughness should be further
examined, as we have already noted. Efforts a = (23,/PEg)½
a~, b, = Fourier coefficients for solid
should also be directed to resolve the dif-
surface configuration [-28]
ficulties discussed regarding the derivation
c; c (~) = A p / 7 ; perturbation terms
of [-54a], particularly in relation to the con- dm,~, d,, e, = constants
tact angle hysteresis. ei = unit vectors in spherical
An important aspect of roughness which (i = r, 0, and q~) and in cy-
we have only briefly touched upon is the lindrical (i = p, z, and q~)
presence of the sharp edges. When the contact coordinates
line Comes across a sharp edge of solid and f = solid surface configuration
sticks to it, the equilibrium contact angle will F~, Fu = surface tension force acting
no longer be observed (18). Since many real on the drop in the x- and
"flat" solid surfaces contain microscopic edges, y-directions
F, G = configuration variables for
consideration of the edge effect should be
a given solid surface, [-48]
included. Also, we have restricted our atten-
and [49]
tion to the roughness (or geometric) effects
g = gravity
on the contact angle, and have ignored the l = half-wavelength of rough-
obviously important, but much more com- ness mode
plex, effects of surface-chenfical heterogeneity Ap = pressure difference across
(7, 26, 27). Both aspects should therefore be drop surface
Journal of Colloid and Interface Science. Vol. 60. No. l, June 1, 1977
 ROUGHNESS EFFECTS ON WETTING 37

r, O, rk = spherical coordinates ~; ~(~) = axisymmetric component or

r j r (i) = r-coordinate of drop surface ; r; perturbation terms
perturbation terms o, z, ¢ = cylindrical coordinates
R drop radius pc; 0(¢); p (~) = o-coordinate of contact line
R1, R~ = principal radii of curvature position ; perturbation
of drop surface terms; R sin 0o
S x- or y-coordinate PL = liquid density
U contact line velocity 00; p0' = Do for concentric grooves;
V = drop volume average of oc
A V , A V ' , A V " = volume changes defined by e; ~ = area ratio ; area ratio defined
1-73, E83, 1-273 by [-36-]
function defined by [-12b-] ¢~ = solid angle of edge
W' = work required to cross an era, ¢~' = maximum slope angles of
energy barrier, [-42-] solid surface
~; 7I, = surface texture factor de-
x, y, z = Cartesian coordinates
fined in [,37b]; value in
xn, y~ = coordinates of a drop center,
[54b~
Xn --= (X,, y,)
xo, yo = position of the reference
Note: An upper bar designates a quantity
point on surface
averaged by [-48] and [-493.
Xr correlation distance
g = z-coordinate of surface con-
tour ACKNOWLEDGMENTS

The authors are grateful to Professor R. G. Cox

Greek and Mr. J. F. Oliver for many helpful suggestions.
characteristic correlation This research is supported by the Defense Research
Board of Canada (DRB) Grant 9530-47).
distance in [-553
term defined in [-37c-]
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=
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3. SHUTTLEWORTH,R., AND BAILEY, G. L. J., Discuss.
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,/ =
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12. HuH, C., AND SCRIVErr, L. E., Symposium on
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