COLLOIDS

AND
',""~iioids and Surfaces SURFACES A
ELSEVIER A: Physicochemical and Engineering Aspects 136 ( 1998 ) 81 88

Line tension effect on contact angles:

Axisymmetric and cylindrical systems with
rough or heterogeneous solid surfaces
Abraham Marmur *
Department of Chemical Engineering, Technion - Israel histitute of Technology, 32000 Ha(fa, Israel
Received 9 January 1997; accepted 5 September 1997

Abstract

Equations for the apparent, intrinsic, and actual contact angles are presented, which account for the effect of line
tension in axisymmetric and two-dimensional (cylindrical) systems with rough or chemically heterogeneous solid
surfaces. The central point in the present theory is the realization thai line tension cannot be considered constant.
The dependence of line tension on the geometry of the system may be extremely complicated. Therefore, the simplifying
assumption that line tension is a function only of the position of the contact line is made. The physical meaning of
this assumption is that line tension affects only the contact angle and not the shape of the liquid-fluid interface. In
two-dimensional (cylindrical) systems, this geometrical dependence is responsible for the existence of a line tension
effect, in contrast to the currently held view. The implications of the theory are discussed in terms of the relationships
between the Young's, actual, and intrinsic contact angles. ~! 1998 Elsevier Science B.V.

Kevwords: Line tension: Contact angle: Wetting

I. Introduction the apparent contact angle, and the actual contact

Interfacial phenomena in solid-liquid-fluid sys-
tems are usually described in terms of contact
angles. Depending on the nature of the solid
surface, various definitions of contact angles have
to be considered. The intrinsic contact angle is the
angle between an ideal, i.e. smooth, chemically
homogeneous, rigid, insoluble, and non-reactive
solid surface and the liquid-fluid interface. In
reality, ideal surfaces hardly exist, and most solid
surfaces are rough and heterogeneous to some
extent. Consequently, there is a need to distinguish
between two additional types of contact angles:
* Corresponding author. Fax: + 972-4-8293088:
e-mail: marmurt2i!tx.technion.ac.il
angle. The tbrmer is the angle measured between
the nominal solid surface (which, under low magni-
fication, appears to be smooth) and the liquid-fluid
interface [Fig. l(b)]. The latter is the local angle
between the actual solid surface and the
liquid-fluid interface [Fig. l(c)]. Under some cir-
cumstances, the actual contact angle equals the
intrinsic one; however, this is not always the case.
The first expression proposed for the intrinsic
contact angle is the well-known Young's equation
[1]. Nonetheless, it is well established that this
equation needs to be corrected for the effect of the
three-phase molecular interactions at the contact
line region [2-14]. This is so, since the presence
of a third phase in the close vicinity of each inter-
face may augment the interfacial energies. One

0927-7757/98 S 19.00 ~,c~1998 Elsevier Science B.V. All rights reserved.

PII S0927-7757197 )01)300-2
82 A. Marmur / Colloids Surfaces A: Physicochem. Eng. Aspects 136 (1998) 81-88
Y this idea, the following equation was suggested for
...... I " - l cos Oi =cos Oy - ~
(a)
Co)
(0
Fig. I. The geometry of the system: (a} definition of phases and
coordinates; (b) the apparent contact angle; (c) the actual con-
tact angle.
approach that was studied in order to develop the
necessary correction was to assume the interfacial
tensions to depend on the local thickness of the
liquid layer and on the local slope of the
liquid-fluid (If) interface [ 12, 13]. This approach
led to a very complicated equation for the shape
of the drop, and to an implicit, but relatively
simple, equation for the intrinsic contact angle.
Another approach, which was developed many
years ago [3,4,9,16], followed a suggestion by
Gibbs [2] to introduce the concept of linear (line)
tension. The purpose is to account for the differ-
ence between the internal energy of the actual
system and that of a simplified model of the
system, for which each interfaciai tension is consid-
ered to be unaffected by the presence of the
adjacent third phase. Line tension is then defined
as this difference, per unit length of the three-
phase contact line. In other words, the line tension
concept can be considered as the one-dimensional
analog of the surface tension concept. Based on
the intrinsic contact angle, 0i, of an axisymmetric
drop on an ideal solid surface [3,4,9]:
( 1)
O'lfR
In this equation, 0v is Young's contact angle, ~ is
the line tension, a~r is the If interfacial tension, and
R is the radius of the base of the drop.
Various attempts have been made to either esti-
mate or measure line tension, in order to quantify
the significance of its effect [ 14-24]. Some of these
values differ by as much as about five orders of
magnitude from each other. The main reason for
these huge differences seems to be related to lack
of sufficient theory for proper interpretation of
experimental results. Based on a recent estimate
[ 14], which agrees with some of the measurements,
the line tension effect is important only when the
radii of curvature in the system are of the order
of magnitude of microns or less. In other words,
it seems to be important for micron size (or
smaller) drops as well as for larger drops with
local, micron size radii of curvature due to rough-
ness or heterogeneity of the solid surface. From a
practical point of view then, the effect of line
tension may be mostly important for wetting of
rough or heterogeneous surfaces. However, theory
has so far been concerned only with smooth and
homogeneous surfaces.
Moreover, the line tension in Eq. ( 1) is consid-
ered constant. This assumption is unrealistic [14],
as explained in the following. As mentioned above,
line tension is introduced in order to account for
the effect of the presence of a third phase on each
interfacial tension. This correction may, in prin-
ciple, be calculated from the integral of all the
molecular interactions of all the molecules in the
three phases. It is quite obvious that this integral
must depend on the spatial distribution of the
three phases. Therefore, in general, Sine tension
must depend on the geometries of the solid-liquid,
liquid-fluid and solid-fluid interfaces, as well as
on the contact angle. However, if such a general
dependence of line tension on the geometry of the
system were introduced into the fundamental equi-
librium condition, the result would be an extremely
 A. Marmur / ColloMs Surfatz, s A: Physicochen~. Eng. Aspects 136 (1998) 81--88
complicated integral-differential equation. Such
an equation will not be analytically solvable, and
will most likely be of limited value both in terms
of added insight and from a practical point of view.
Consequently, it makes sense to study the prob-
lem under some simplifying assumptions, though
less extreme than assuming constant line tension.
The fact that the line tension approach enables
various levels of approximation, as discussed in
the following, constitutes a practical advantage
over the variable interfacial tension approach
which was previously mentioned [i 2,13]. Recently,
an approximate theory has been developed for
calculating line tension in the specific case of an
axisymmetric drop on an ideal solid surface, in the
absence of gravity [14]. This theory assumes that
the shape of the drop is not affected by the
existence of line tension, and calculates line tension
directly from the van der Waals interaction
between the solid and the liquid. It leads to the
following approximate equation for the line ten-
sion in a solid-liquid-vapor system (which is valid
for contact angles that are not too low and not
too close to 90 ~):
r = 46V~s~rl cot 0i
In this equation, 6 is a typical distance between
molecules, trt is the surface tension of the liquid,
and trs is the surface tension of the solid. Eq. (2)
demonstrates that line tension is a function of the
intrinsic contact angle, as expected from the gene-
ral considerations mentioned above. In this case,
the intrinsic contact angle is the only geometrical
parameter that matters, since the shape of the drop
is a priori fixed.
When Eq. (2) was introduced into the expression
for the energy of the ~ystem, and the latter was
minimized to get the expression for the intrinsic
contact angle, the following equation resulted [ 14]:
r ~(~2 +3) dr
cos 0i = cos 0v - - - + ---
o'lfR trlfR( 1 + ~2) d:~
where
1- cos 0 i
~_-
sin 0i
Eq. (3) shows that an additional term is needed,
83
in comparison with Eq. (!), to account for the
dependence of line tension on the contact angle.
The combination of Eqs. (2) and (3) leads to an
implicit equation for the intrinsic contact angle
[141.
As mentioned above, corrections to Young's
equation seem to be of practical importance mainly
for systems in which the liquid contacts rough or
heterogeneous surfaces. Therefore, the purpose of
the present paper is to develop an equation that
accounts for the effect of line tension on contact
angles in such systems. Since it is important to
distinguish between the intrinsic, actual, and
apparent contact angles in these systems [25], the
following discussion addresses the relationship
between these angles when line tension effects are
meaningful. Due to mathematical difficulties, the
present treatment refers only to axisymmetric or
two-dimensional (cylindrical) systems.
2. Theory
In general, equilibrium is achieved when the
internal energy of a global isolated system (which
(2) in the present case consists of the solid-liquid-fluid
system together with the environment) reaches its
minimum. From this general requirement, three
equilibrium conditions emerge: (a) uniformity of
temperature throughout the system; (b) uniformity
of the generalized chemical potentials; and (c) the
mechanical equilibrium condition, from which the
equations for the shape of the If interface and for
the contact angle are derived (e.g. Ref. [25]). The
latter takes the following form when line tension
is introduced to account for the three-phase inter-
actions at the contact line:
.'~i ( P f - PI)V~(Y')'dNixk dx
(3)
+d "
I
+~lWl+(Y')i+[as,(x)-Gs~x)]r(x) }
x x k dx+[d(Xkr)].~=x2-[d(Xkz)]x=x=O (5)
(4) In this equation, the subscripts s, 1, f indicate the
solid, liquid, and fluid phase, respectively, P~ ( j =
f,l ) is the pressure in phase j, dNt is the displace-
84 A. Marmur / ColloMs Surfitces A: Physicochem. Eng. A,Tmcts 136 (1998) 81-88
ment of the If interface normal to itself in the
outward direction from phase 1, and aj,, (j,m =
s,l,f) are the interfacial tensions. The local rough-
ness ratio, r(x), is defined as the local ratio of the
actual solid surface area to its projection on the
horizontal plane. For a two-dimensional system
(cylindrical If interface), which is indicated in the
equation by setting k = 0 , x is the horizontal
Cartesian coordinate, Xt and X., (X2 > XI) are the
x values corresponding to the contact lines. For
an axisymmetric system, which is indicated by
setting k = 1, x is the radial horizontal coordinate,
Xt =0, and X, is the x value of the contact line.
In both cases, y is the vertical coordinate of the If
interface, and the prime indicates derivation with
respect to x [the geometry of the system is shown
in Fig. I(a)].
The first integral in Eq. (5) accounts for the
work done by the pressure difference between the
liquid and fluid phases due to the perturbations in
the position of the If interface. It is important to
realize that the values of the pressures which
appear in Eq. (5) alread2y include the effect of
gravity:
P~=Pjo-P~gY ( j = f,l ) (6)
In this equation, Pjo is the pressure that exists or
would have existed in phase j at v=0, g is the
gravitational acceleration, and pj is the density of
phase j.
The second integral in Eq. (5) expresses the
interfacial energies. If the solid surface is chemi-
cally heterogeneous, the interfacial tensions that
involve the solid, i.e. a~ and a,,r, depend on x. The
_+ sign accounts for the fact that, depending on
the inclination of the If interface, an increase in
the If interfacial area may be associated with either
an increase or a decrease in x.
The third and fourth terms in Eq. (5) represent
the line tension correction. They replace the gene-
ral term d ~ ~r [12,13], which is the differential of
the excess internal energy of the system due to the
three-phase molecular interactions. This excess
energy is expressed here, by definition of the line
tension concept, as the product of the line tension
and the length of the co~atact line. These terms
have opposite signs, since the two contact lines (in
the two-dimensional case) move in opposite direc-
tions with respect to the x-axis for the same
variation in the geometry near the contact line. In
the axisymmetric case the fourth term is zero.
As mentioned in the Introduction, these terms
should, in principle, depend on the spatial distribu-
tion of the three phases; however, admitting such
a dependence will lead to severe mathematical
difficulties. Therefore, the central assumption of
the present study is that the geometrical depen-
dence of line tension involves only quantities which
are defined at the contact line, such as the actual
contact angle. Thus, for example, r can be
expressed as r[y'(X)] [for a given geometry of the
solid surface, J's(x), the actual contact angle can
be written in terms ofy'(X)].
However, even this simplified dependence of line
tension leads to mathematical difficulties. This is
so, since the variations considered in order to
search for the minimum in energy include varia-
tions of the shape of the If interface, in addition
to variations in the position of the contact line.
Consequently, the coordinate of the contact line,
X, cannot by itself uniquely determine the slope.
Only after the shape is known will y'(X) be
uniquely defined (for example, if it is known that
the shape is circular and tile volume of the liquid
is given, then the coordinate X uniquely determines
the details of the If interface). Therefore, an addi-
tional simplification is made: line tension is
assumed to be a function of the position of the
contact line only:
r=r(X) (7)
The physical interpretation of this assumption is
that line tension affects only the contact angle and
not the shape of the If interface.
The first two terms of Eq. (5) may be treated as
previously reported [25] to yield:
d {[ ]
A P t , - t~v2Apg + trlrV ! + (.v') 2
+ [rr~l(x)- o',,r(x)lrlx)} v k d.,t-
+ [d(X~r)]., .~x: - [d(Xkr)]., = x, = 0 (8)
where AP-Pr-PI, v-y(x)--ys(x),y,(x)is the
profile of the solid surface [see Fig. l(a)] and
 A. Marmur / Colloids Surfaces A: Physicociwm. Eng. Aspects 136 (1998) 81:88
A p - p , - pf. Eq. (8) is valid for the general case of
a volatile liquid in contact with a rough and/or
chemically heterogeneous solid surface.
The minimization of the integral in Eq. (8),
without considering line tension terms, was pre-
viously performed by standard techniques of calcu-
lus of variations [25,26]. The result was a system
of two independent equations: (a) the Euler equa-
tion, which transforms into the well known
Young-Laplace equation for the shape of the If
interface; and (b) the transversality condition,
which accounts for the fact that the position of a
contact line is a priori unknown, and yields the
equation(s) tbr the contact angle(s).
However, the present discussion focuses on the
line tension effect, therefore the minimization needs
to be extended to include the line tension terms in
Eq. (8). Since these terms depend only on the
position(s) of the contact line(sL as stated in
Eq. (7), they simply need to be added to the
transversality condition, and do not affect the
Euler equation. This is so, because the transversal-
ity condition includes all the terms that deal with
the contact line(s). This conclusion can be formally
proven by repeating the development of the Euler
equation and the transversality condition [25,26],
however, the details are omitted here since it simply
involves adding the line tension terms throughout
all the steps of lhe development. From a physical
point of view this is clearly understandable, since
the basic assumption is that the line tension
depends only on the position of the contact line
and has therefore no effect on the shape of the If
interface.
Thus, the Euler equation remains intact:
d t~F t'.'["
=0 (9)
dx ?y' Pv
and the transversality condition for the present
case is
[F+(.v~-.v')g.v J.~:x, dX, + d[Xkr(X)].,= x,_
-[F+ty;-y') ?vJ,:: X!
dXl - d[Xkr(X)].,: x,(I0)
85
In these equations [25]:
F = {APv--~v2Apg 4._5"
alfV 1 + (),')z
+ --asr(x)]r(x)}x k (11 }
In the absence of constraints on the motion of the
contact lines, dXt is independent of dX2, and so
are the d[(Xkr)].,: x terms. Therefore, each pair of
terms in Eq. (10) that relates to one of the contact
lines independently equals zero. This can be written
in the following form:
F + (y~ - y ' ) d X + d [Xkz(X)]., =x = 0
t'l' dx = x
(12)
This equation yields the expression for the appar-
ent contact angle, 0. As mentioned in the
Introduction, 0 is defined as the angle measured
from the x direction to the tangent to the If
interface which is normal to the contact line [see
Fig. 1(b)]. In the unconstrained case:
cos 0 =
V I + [.),'(x)] 2
k~ d'r,
r(X) cos Or(X)
),~lr alctX
(13)
l + y~(X)y'(X)
Eq. (13) is the most general equation under the
above-stated assumptions. A specific example
which was previously studied [14] is represented
by Eq. (3), which can be directly derived from
Eq. ( 13 ) under the conditions of axisymmetry and
a smooth surface. Eq. (13) is relatively simple in
form, although it should be realized that it is an
implicit equation (on the right-hand side there are
three terms which depend on the contact angle:
the two terms in the nominator that include line
tension, and the term in the denominator that
includes v ' = t a n 0). It should also be mentioned
that Eq. (13) can easily be generalized to include
the effects of constrained contact lines [25], how-
ever this will not be shown here since it is not the
main point of interest in the present discussion. It
86 A. Ahmmw Colh~MsSm:hwes A." Phvsicochcm. Eng. A.wects !36 (1998) 81-88
is also worth mentioning that the definition used
here for the apparent contact angle follows the
mathematical convention for defining angles, and
is somewhat different from the conventional defi-
nition used in the contact angle literature [25].
3. Discussion
As a starting point for the discussion, Eq. (13)
for the apparent contact angle should be compared
with Eq. ( 1 }. The latter has been in use for many
years tbr axisymmetric drops on an ideal solid
surface (for which the intrinsic contact angle is
also the apparent one). Two main differences are
illustrated by this comparison: (a] an additional
term is required to account for the fact that the
line tension is not constant: and (b) correction
factors are required to account for the roughness
of the surface. It is easy to show that Eq. (13)
turns into Eq. 11) if the surface is smooth ( r - I ,
and .v~=0) and the line tension is constant. It is
interesting to notice that chemical heterogeneity
does not explicitly affect the form of the equation.
Its effect is implicit, through the dependence of the
line tension itself on the local chemical nature of
the solid surface. The effect of the geometry of the
contact line itself is explicitly determined by the
value of k and, in addition, implicitly expressed
through the dependence o f d r / d X on this geometry.
The parallel of Eq. (I) for two-dimensional
(cylindrical) systems does not exist in the literature,
since it has been believed that line tension has no
effect on such systems. In contrast, Eq. (13) shows
that line tension may affect two-dimensional (cylin-
drical ) systems. This is so because of the depen-
dence of line tension on the local position of the
contact line [indeed, Eq. ( 13} shows that if the line
tension is assumed constant, i.e. dr/dX=0, there
is no line tension effect in two-dimensional sys-
tems). It is worth noticing that this result holds
whether the solid surface is ideal or not.
Another important outcome of Eq. (13) is
related to the possible difference between the
intrinsic and the actual contact angle. As men-
tioned in the Introduction, the latter is defined as
the angle measured from the tangent to the solid
surface to the tangent to the If interface, both
normal to the contact line [ Fig. I (c)]. The intrinsic
contact angle is the actual contact angle on an
ideal solid surface. It has recently been concluded
[25,27] that if line tension effects are ignored, and
in the absence of constraints, the actual contact
angle equals the intrinsic one. This conclusion
needs to be tested for the effect of line tension.
The actual contact angle is, in fact, the angle
measured from a line of slope ),~ (the local tangent
to the solid) to a line of slope y' (the local tangent
to the if interface). Based on analytical geometry
(regardless of any thermodynamic considerations],
the actual contact angle is given by
I +y'.r~ I +y'y~
COS 0ac = =
+ V[ l + [.v')2 ][ I + (j'~)2] "!-rX/I + (.v') 2
(14)
The second equality in this equation is derived
from the definition of the local roughness ratio:
r - X/! + (y~)2. Eq. (14) is used below to develop
the thermodynamic expression for the actual con-
tact angle, in order to compare this contact angle
with the intrinsic one.
The latter can be derived from Eq. (13) by
substituting r = 1 and v~ = 0 (i.e. a smooth surface):
kr I dr
cos 0 i = cos 0 v ( 15 )
Xo tr d X
When Eq. ( 131is introduced into Eq. ( 15j in order
to eliminate cos 0v, the following equation results
for the intrinsic contact angle:
! +.v'j'~ I(~,
cos 0, . . . . 7 + -
+rV[l+Iy')2] a
(16)
Since the fiist term on the right-hand side of this
equation equals, by Eq. (14), the actual contact
angle, Eq. (16) can be rewritten as
cos 0,.,c = cos 0 i - -- + - 1 ( 171
O" ,
Eq. [17) can now be discussed for a variety of
situations. First, as previously concluded [25,27],
the actual contact angle equals the intrinsic one
when line tensica is ignored (and in the uncon-
 ,4. Marmur ,, (~dh, ids Smfaces A: Physicochem. Eng. Aspects 136 { 1998) 81.-88
strained case, for which these equations apply). In
addition, Eq.(17) show~ that these angles are
always equal when the surface is smooth ( r = 1).
However, the important point to be emphasized is
that the actual contact angle is different from the
intrinsic one for rough surfaces, if the effect of line
tension is meaningful. This conclusion holds for
the axisymmetric case even if the line tension is
constant: it has not been previously noted, since
the effect of roughness has not been hitherto
studied in conjunction with line tension.
It is also useful to directly compare the actual
contact angle with Young's contact angle. For this
purpose, Eq.(15) needs to be introduced into
Eq. (17) to yield
cos (l,,¢ - c o s 0 v - - - + ( 181
OT
This equation shows that the actual contact angle
equals Young's contact angle only if the line
tension can be completely ignored. This conclusion
holds for ideal as well as for rough or hetero-
geneous surfaces.
4. Summary
The following points summarize time results of
the present analysis of line tension effects on
contact angles, which takes into account a simpli-
fied dependence of line tension on the geometry of
the,solid-liquid-fluid system. All conclusions refer
to axisymmetric as well as two-dimensional (cylin-
drical) systems. For axisymmetric systems, these
conclusions also hold under the extreme assump-
tion of constant line tension.
( l ) A new equation for the apparent contact angle
was developed [Eq. ( 13)]. Thi:: equation gener-
alizes previous equations which took into
account either the effects of roughness and
heterogeneity of the solid surface or the effects
of a constant line tension. The new equation
includes all of these effects as well as the
observation that line tension cannot, in gene-
ral, be constant.
(2) The intrinsic contact angle is different l¥om
Young's contact angle whenever line tension
87
is meaningful [Eq. ( 15)]. It should be empha-
sized that this conclusion is true not only for
axisymmetric systems, as previously believed,
but also for two-dimensional (cylindrical)
systems.
(3) The actual contact angle is different from the
Young's contact angle whenever the line ten-
sion is meaningful [Eq. ( 18)].
(4) The actual contact angle is different from the
intrinsic contact angle whenever line tension
is meaningful and the solid surface is rough
[Eq. (17)]. If the solid surface is smooth
(regardless of the line tension), or if line ten-
sion can be ignored (regardless of the rough-
ness) the actual contact angle equals the
intrinsic one.
Acknowledgment
The author thanks Dr. G. Wolansky for a very
useful discussion.
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