Collo~ds and Surfaces, 43 (1990) 195-206 195

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

Determination of Line Tension from the Drop Size

Dependence of Contact Angles

D. LI and A.W. NEUMANN

Department o~~ec~an~cal Engineering, U~~vers~ts of Toronto, Toronto, Ontario _&l&SlA4
(Canada)

(Received 28 December 1988; accepted 27 April 1989)

ABSTRACT

The drop size dependence of the advancing contact angle of dodecane and ethylene glycol on
carefully prepared FC-721, Zonyl FSC and DDOA surfaces has been studied by means of axisym-
metric drop shape analysis. The contact angles were measured in air and were found to decrease
by 3 to 5 degrees as the radius of the three-phase contact line increased from approximately 1 to
5 mm. This phenomenon is interpreted in terms of line tension by the modified Young equation.
Our experimental results show that the line tensions are positive and of the order of 1 /tJ m-r for
all the three solid-liquid systems in our study; these results are consistent with previous work in
our laboratory. The occasionally observed phenomenon that contact angles increase as the radius
of the three-phase contact line increased on less carefully prepared surfaces is ascribed to the
corrugation of the three phase contact, line.

INTRODUCTION

The realization of the theoretical and experimental significance of line ten-

sion in three-phase equilibrium systems seems to be increasing rapidly. For
example, knowledge of line tension may lead us to estimate the linear excess
functions, such as linear adsorption, at the three-phase transition zone, to un-
derstand heterogeneous nucleation and such processes as the initial formation
of the three-phase line in the immersion of a solid or the attachment of a bub-
ble. The line tension concept was first suggested by Gibbs [1 ] and later devel-
oped in the generalized theory of capillarity [ 2 f by Boruvka and Neumann. In
analogy to the surface tension defined for a two-dimensional surface, line ten-
sion is defined as the force operating in the one-dimensional three-phase line,
or alternatively, as the free energy per unit length of the three-phase contact
line [l,Z].As one of the thermodynamic equilibrium conditions for a three-
phase (solid-liquid-vapour ) system containing curved surfaces and a curved
three-phase contact line, the mechanical equilibrium condition for any point
at the three-phase contact line has been derived [ 21 as

0166-6622/90/$03.50 0 1990 Elsevier Science Publishers B.V.

196

Yl”COS o=YS”- Ysl - flxgs (1)

where yly, ySVand yS1are the surface tensions of the liquid-vapour interface, the
solid-vapour interface and solid-liquid interface, respectively; 0 is the contact
angle; o is the line tension and ~~~is the local curvature of the three-phase line
in the plane of solid phase. Equation (1) is called the modified Young equation,
which considers the contribution of line tension to the equilibrium of the three-
phase line. Let us consider a sessile drop, as shown in Fig. 1. Only if the drop
is truly axisymmetric, the curvature of the three-phase line, ]cps,in Eqn (1)
will be:
1
Qs =-
R

where R is the radius of the three-phase contact circle. Axisymmetry of the

drop requires that the solid surface is horizontal, planar, smooth and homo-
geneous. Under these conditions Eqn (1) reduces to

Yl”~OS @=Ysv-ys, -; (3)

When R-+cq Eqn (3) will be replaced by the classical Young equation:

Yl”COS RQ = Ys” - Ygl (4)

Combining Eqn (3 ) with Eqn (4 ) yields

Equation (5 ) shows that the contact angle will vary with drop size, or more
explicitly, with the radius of the three-phase contact circle, and that line ten-
sion can be related to the measurable quantities, contact angle, liquid surface
tension and radius of the three-phase contact circle. Therefore, it should be

Vapour Axisymmetric Sessile Drop

Circular Three Phase Line

Fig. 1. Schematic of an axisymmetric sessile drop on a planar solid surface.

 197

possible to determine the line tension by measuring the dependence of contact

angle on the radius of the three-phase contact circle.
There have been a number of experimental studies of line tension consid-
ering the dependence of contact angle on the radius of the three-phase contact
line. Unfortunately, there is no consensus on both the sign and the order of
magnitude of line tension. Recently a review of the subject has been given by
Toshev et al. [ 31. For the systems containing an oil lens on the surface of water,
positive line tensions were reported from approximately 60 $ m-l by Lang-
muir [4 J to 5.0*10-3iuJ m-l by Gershfeld and Good [5] and 2.0-10-5$ m-*
by Harkins 161. For a sessile drop on a fluid-~uid interface, Wallace and
Schiirch [ 71 reported a decrease of contact angle with an increase in the radius
of contact line, the corresponding line tension was found to be positive and to
vary from 1.0*10m2 to 2.4*10p2 iuJ m-l. For liquid drops on solid surfaces,
Ponter and Boyes [8,9] and Ponter and Yekta-Fard [lO,ll] showed that, in
different environments, there are opposite trends of the dependence of contact
angle on drop size: in the pure vapour atmosphere, the contact angles decrease
with the increase in the drop size, which will correspond to positive line ten-
sions; in air or nitrogen saturated water vapour, the contact angles increase
with the increase in drop size, which would correspond to negative line ten-
sions. The line tension values calculated from their data range from 1 to 10 iuJ
m -I. Also, for liquid drops on solid surfaces, Good and Koo [ 121 found that
the contact angle decreased as the drop size decreased; their results would yield
negative line tensions in the range of -6 to - 17 ,EJm-l. However, they be-
lieved that the observed effects were due to the heterogeneity of the solid sur-
face, and not necessarily to line tension. On the one hand, there is no a priori
reason to doubt any of these reports; on the other hand, it seems unlikely that
line tensions could be negative as well as positive, and that they could range
over several orders of magnitude for chemically and energetically similar sys-
tems. We suspect that at least some of the existing problems have to do with
the influence of different environments, as suggested by Yekta-Fard and Pon-
ter [ 111, and with dif~~ulties of interpretation and measurement of contact
angles on surfaces which are rough and heterogeneous.
Our previous report [l3] of contact angles as a function of drop size has
shown that, for five n-alkanes on a Teflon surface, the line tension is positive
and approximately equal to ‘2ruJm-‘; correspondingly, the contact angles de-
crease by approximately 5 o when the drop size is increased from approximately
1 mm to 5 mm in contact radius. The technique used to measure contact angles
of sessile drops was axisymmetri~ drop shape analysis (ADSA) [ 141. However,
at that time, the ADSA technique still required image acquisition by photo-
graphing sessile drops and by digitizing these photographs manually, by means
of a digitizing tablet. While this strategy certainly avoided operator subjectiv-
ity of the type ordinarily connected with goniometer contact angle measure-
198

ments, its accuracy was still somewhat limited. Furthermore, in that study
[ 131, liquid drops were deposited from the top, by means of a syringe. There
are essentially two methods for such a drop deposition. Either the drops are
allowed to fall onto the surface or else they are grown while the syringe needle
is immersed in the drop. Since ADSA requires a complete drop profile, in the
latter procedure, the syringe needle would have to be withdrawn from the drop;
this procedure would, just as with the falling drop, cause vibrations, which
could cause the actual contact angle to assume a value between advancing and
receding.
Recently, we have improved the means of measuring contact angles of sessile
drops through improvements of the ADSA technique itself, the preparation of
solid surfaces and the way of growing sessile drops (details are given in the
next section). Therefore, with these improvements in place, we wish to re-
examine the sign and magnitude of line tension reported previously [ 131 by
direct measurement of the dependence of contact angles on the size of sessile
drops.

EXPERIMENTAL

The solid surfaces used in our experiments are FC-721, fluorosurfactant Zonyl
FSC and dimethyldioctadecylammonium coated on molecularly smooth mica
surfaces. The first step in preparing these surfaces is to obtain clean and step-
free mica sheets. To do so, the mica layer was cut to approximately 3 X 3 cm*
pieces and a small hole was drilled in the centre of the mica layer using a needle
of 0.4 mm in diameter. Then the mica layer was carefully split into thin sheets,
and those sheets from the inside of the mica layer were used.
The FC-‘721 surface was prepared by a dip-coating technique [ 151. The 2%
solution of FC-721 (3M Canada Inc.) was placed in a beaker, the clean mica
sheet was then dipped into the solution for approximately 1 min, and pulled
out of the solution at a constant rate of approximately 1.2 cm min-‘; a uniform
hydrophobic FC-721 film was thus coated onto the mica sheet.
The Zonyl FSC surface was obtained through ion exchange between the cat-
ionic Zonyl FSC aqueous solution and the surface of the mica sheet [ 161. The
procedure is the following: The solution of Zonyl FSC fluorosurfactant (DuPont
Inc.), dissolved in double-distilled water, was prepared with a concentration
of 0.004 g/l00 ml (c.m.c. for FSC is 0.005 g/100 ml); the clean mica sheet was
then dipped into the solution, equilibrated for approximately 1 min, and with-
drawn from the solution at approximately 1.2 cm min-“.
The dimethyldioctadecylammonium (DDOA) surface was prepared by us-
ing the Langmuir-Blodgett technique [ 171.The mica sheet was first immersed
in a water-filled Teflon trough. Dimethyldioctadecylammonium bromide
(DDOAB, Eastman Kodak Co.) was dissolved in a mixture of 10% ethanol and
90% hexane (10 mg of DDOAB were used in a 50 ml mixture); 120 ,~l of this
solution was added dropwise onto the air-water interface; upon evaporation of
 199

the solvent an insoluble surface film resulted; this film was compressed until
the surface pressure reached its maximum value. The mica sheet was then
withdrawn from the solution, through the DDOAB surface film, at approxi-
mately 0.2 cm min-?, while the surface pressure was kept constant.
The liquids used in the experiments are dodecane and ethylene glycol (Ald-
rich Chemical Company, Inc. ) . The liquid surface tensions of dodecane and
ethylene glycol were measured using the pendant drop method, ADSA tech-
nique [ 181. At 22”C, for dodecane, yiV= 25.43 2 0.02 mJ mM2;for ethylene gly-
col, yl,=48.09 t 0.06 mJ m-‘. These results show good agreement with the
reported values in the literature [ 191.
To measure the contact angles of sessile drops, the latest version of our axi-
symmetric drop shape analysis (ADSA) [ 18] is employed. Briefly, ADSA is a
numerical procedure to digitize images of drops and then to fit Laplacian curves
through these digitized Rrofiles of drops with surface tension and contact angle
as adjustable parameters. The input for the ADSA program is the density dif-
ference between air and the liquid forming the drop; the output of the ADSA
program consists of the values of surface tension, contact angle, volume of the
sessile drop, liquid-air interface area and the contact radius of the drop on the
solid surface. Compared with other techniques to measure contact angles from
sessile drops, the improved ADSA has higher accuracy and is essentially free
of operator subjectivity.
A diagram of the apparatus used in the measurements is given in Fig. 2. All
the contact angles were measured in air. To start a run of the contact angle
measurements, a sessile drop is grown on a carefully prepared solid surface by
feeding the liquid steadily and very slowly by means of a motor-driven syringe
from the bottom through a small hole in the solid substrate. The reason that
we grow drops from the bottom is to ensure that the contact angles measured
are proper advancing contact angles. In contrast, if one deposits a drop from
the top, there are inevitable vibrations or oscillations of the drop which may
lead to a contact angle intermediate between advancing and receding contact
angle, as explained above. The procedure of growing a drop from the bottom is
not a trivial task. Unless the solid surface is of very good quality, the drop tends
to grow quite asymmetrically. Conversely, as there are still no quantitative

drop

u
syringe

Fig. 2. ~xperimen~l set-up for measuring drop-size dependence of contact angles.

criteria for “good quality” of a solid surface for contact angle measurements,
production of an axisymmetric drop on a solid surface might be considered as
a necessary condition which a “good” surface must fulfill. When the drop has
grown to a certain size, usually when the contact radius of this initial drop is
approximately 1 mm (the radius of the hole in the mica sheet is approximately
0.4 mm), we stop the motor and let the sessile drop relax for approximately 30
seconds to reach equilibrium. A high resolution (Cohu 4800 CCD mono-
chrome) videocamera is employed to take 3 pictures of this sessile drop suc-
cessively at intervals of 30 s. These 3 images of the sessile drop are immediately
stored in the computer and can be digitized by the ADSA program after the
measurements are completed. The volume of the sessile drop is then increased,
and the above procedure is repeated. Usually at the end of one run of the mea-
surement, the contact radius of the sessile drop is approximately 5 to 6 mm.
This upper limit in size is given by the field of the camera lens. For each solid-
liquid system, the above measurements were conducted in duplicate or tripli-
cate, and a fresh solid surface was used for each run. All the experiments were
performed at room temperature (22 * C ) .

RESULTS AND DISCUSSION

Plots of contact angle versus contact radius for the three solid-liquid sys-
tems are given in Fig. 3. Each point in these plots represents the average cal-
culated from the contact angle results of the 3 successively taken images of one
sessile drop and the error bars correspond to 95% confidence limits. It is ap-
parent that for any solid-liquid system, contact angles are reproducible from
run to run to better than 1 degree. The slight differences between runs are due
to the difficulty of exactly duplicating the solid surface.
Figure 3 shows that the contact angles decrease by 3 to 5 degrees as the
contact radius increases from approximately 1 to 5 mm; for large drops the
contact angle size dependence vanishes. Therefore, if one uses the sessile drop
method to measure contact angles as a means of testing wettability, one has to
be aware of this drop size effect on contact angles.
According to the modified Young equation (5), the observed drop size de-
pendence of contact angles can be interpreted in terms of line tension. In our
experiments, all the contact angle measurements were conducted on very care-
fully prepared solid surfaces. On the FC-721 surface, the contact angle hyster-
esis was only 2-3 degrees. The DDOA and Zonyl FSC surfaces, the two surfac-
tant-covered surfaces used in our experiments, are the monolayers of the
DDOA’ and FSC+ on molecularly smooth mica surfaces; the contact angle
hysteresis on these two surfaces was found to be 6-8 degrees. Therefore, in our
experiments, the sessile drops resting on these carefully prepared, smooth, ho-
mogeneous planar solid surfaces are axisymmetric, the three-phase lines can
be expected to be a smooth circle, so that Eqns (3) and (5) are applicable. The
 201

FC-721 / Dodecane

Zonyl FSC / Dodecana

72 ’
86

DDOAB / Ethylene Glycol

7

q run1
l run 2
= run3

0.1 0.2 0.3 0.4 0.5 0.6

Radius ( cm)
Fig. 3. Contact angle 0 versus the contact radius R. The error bars are 95% confidence limits.

modified Young equation in the form of Eqn (5) predicts that, for a given solid-
liquid system, the contact angle will be a linear function of l/R. If the line
tension is positive, then, as R increases, cos 8 will increase, and the contact
angle 8 will decrease. This is just what we have observed in our experiments.
Plots of cos B versus l/R are given in Fig. 4. A least square cube-~tting
technique was employed to fit the points in each run to a straight line; however,
for graphical reasons, such lines are calculated but not plotted in Fig. 4. The
correlation coefficients of all these linear relations are 0.97 or above, as indi-
cated in Fig. 4. These high correlation coefficients indicate that the interpre-
tation of the drop size dependence of the contact angles as being due to line
tension [ Eqn (5) ] is statistically acceptable.
According to Eqn (5)) the slopes of these straight lines fitted for each run in
Fig. 4 will be equal to the ratio - (a/y,,); thus the line tension G can be calcu-
lated from these slopes since we know the values of the liquid surface tension.
202

0.35,
FC-72liDodecana
0.34 e!n
_P*p @I run1 k0.98
0.33 i m . ~"2 r-O.99
.
a
1 l
q
0.32

8
0.31I

.
0.29 J
“b ZonylFSC/Dodecane
P
0.29
-,=. e m run1 rsO.98
.a * run2 kO.99
0.28 I run3 r-0.98
:

0.27 *I,
-I

0.25 .

q
0.24

0.13-

0.12- $+I& DDOAWEthylens Glycol

8 run1 kO.97
0.11- f run2 kO.98
a ' kn . run3 k0.98

z O.lO- .'
0 . .
.!d l .
0.09-
.m

0.081 . , . , . , . , , . , ,
1 2 3 4 5 6 7 8

l/R (cm *’ )
Fig. 4. The interpretation of contact angle dat.aby the modified Young equation r is the correlation
coefficient.

For the three solid-liquid systems in our experiments, the line tension values
are listed in Table 1. We note that the line tension is positive and of the order
of 1 pJ m-l. This is consistent with previous work [ 131 in our laboratory both
in the sign and in the order of magnitude of line tension. Also, by Eqn (5 ), the
values of 6, are calculated from these linear relations and listed in Table 1. It
is interesting to note that the contact angles with R = 4 mm are still approxi-
mately 1 degree larger than the corresponding 0, values.
Generally, the molecular structure of the three-phase transition zone of fiuid-
liquid-liquid systems is quite different from that of solid-liquid-vapour (or
gas) systems. As a result, the order of magnitude of line tensions may well be
very different for these two different types of systems. However, it is interest-
ing to compare the order of magnitude of line tensions in this work with the
 203

TABLE 1

Line tensions derived from the results of the size dependence of contact angles

Wetting liquid Solid surface Line tension kc

&J m-‘1 (deg. 1

Dodecane FC-721 run 1 2.11 68.9

run 2 2.03 69.1

Ethylene glycol Dimethyldioctadecylammonium run 1 4.82 81.9

run 2 4.54 81.9
run 3 6.44 81.5
Dodecane Zonyl FSC run 1 2.77 71.4
run 2 2.54 72.1
run 3 2.92 11.5

order of magnitude of line tensions of solid-liquid-vapour (or gas) systems

reported by other authors. As mentioned previously, the absolute values of line
tensions from the results of Ponter et al. [8-111 are of the order of 1 to 10 ,BJ
m-l; those reported by Good and Koo [ 121 are of the order of 1 to 10 ,uJ m-l;
the line tension values reported by Gaydos and Neumann [ 131 are of the order
of 1 @ m-‘; the line tensions reported here also are of the order of 1 ,uJ m-l.
Therefore, it appears that, for solid-liquid-vapour (or gas) systems, all the
reported line tensions, fall into a narrow range from approximately 1 to 10 @
m-l. However, as long as the question of the sign of line tension is not resolved,
this finding is of uncertain significance.
It is important to emphasize that the experimental results of this work were
obtained on carefully prepared solid surfaces. On some less carefully prepared
FC-721 surfaces which might also have been contaminated by dust, we ob-
served the opposite drop size dependence of contact angles, i.e. the contact
angles increased with the drop size. We are inclined to attribute these obser-
vations to the cor~gations of the three-phase contact circle which may arise
due to the heterogeneity and the roughness of the solid surfaces. As explained
previously, only when the three-phase line on a planar solid surface is a smooth
circle, Eqn (3) and hence Eqn (5) are applicable. Otherwise, one cannot expect
to obtain correct line tension by interpreting the observed dependence of con-
tact angle on the apparent three-phase contact radius in terms of Eqn (5).
This is because, for a corrugated three-phase contact circle, the curvature rcgS
[ Eqn (1) ] of the three-phase line varies from place to place, ruling out the
applicability of Eqns (3 ) and (5 ) . On the other hand, since any experimental
strategy such as ADSA will yield a macroscopic, or “apparent” contact angle,
we may introduce an effective curvature, l/&,, into Eqn (5), instead of the
constant curvature l/R of a smooth three-phase contact circle. The effective
204

curvature of the three-phase contact circle on a planar solid surface may be

defined as:

(6)

where ST is the total length of the three-phase contact circle; 7~~is the local
curvature of the three-phase contact circle and s is the arc length. Then, similar
to Eqn (5), we have

c7 1
cos %=cos 8, -- -
~1”R,rf

Obviously if the three-phase line is a smooth circle, the local curvature legswill
be equal to a constant I/R, and the effective curvature l/Reff will be equal to
l/R; hence, Eqn (7) will revert to Eqn (5).
A hypothetical three-phase contact circle with corrugations is shown in Fig.
5. This three-phase line consists of a number of circular arcs of two different
types and has continuous derivatives of the first and second order. One type of
the circular arcs has a radius RI, the other has a radius R,. According to Eqn
(6)) the effective curvature of this corrugated three-phase contact circle is

Fig. 5. A hypothetical corrugated three-phase contact circle consisting of two types of circular
arcs.
 205

(8)

where S, and S, are the total arc length of the circular arcs of type one and
type two, respectively. From Eqn (8), we see that the sign of the effective
curvature of the corrugated three-phase contact circle will depend on the val-
ues of RI, R2, S,/ST and SJS,. Combining Eqns (7) and (8), we have

(9)

Equation (9) shows that the increase or decrease of contact angles with the
drop size will not only depend on the sign of the line tension but also on the
sign of the effective curvature of this three-phase contact circle. In other words,
even for positive line tension, the contact angle 8 may still increase with the
drop size, as long as the effective curvature in Eqn (9) is negative. While the
above construction is somewhat hypothetical, it seems that, on the basis of
Eqn (8), there is no a priori reason why l/Refr might not be positive in some
cases and negative in others. In view of Eqn (9) it is then plausible that an
increase in contact angle with increasing drop size does not necessarily imply
a negative line tension. Corrugation of the three-phase contact circle may well
cause such an increase, in spite of a positive line tension. In summary, the
proposed model could well accommodate increase, decrease or independence
of contact angle as a function of drop contact radius, for positive values of line
tension.

ACKNOWLEDGEMENTS

This study was supported by the Natural Sciences and Engineering Re-
search Council of Canada (grant No 8278) and by a University of Toronto
Fellowship.

REFERENCES

1 J.W. Gibbs, The Scientific Papers, Vol. 1, Dover, New York, 1961, pp.288
2 L. Boruvka and A.W. Neumann, J. Chem. Phys., 66 (1977) 5464.
3 B.V. Toshev, D. Platikanov and A. Scheludko, Langmuir, 4 (1988) 74.
4 .J. Langmuir, J. Chem. Phys., 1 (1933) 756.
5 N.L. Gershfeld and R.J. Good, J. Theor. Biol., 17 (1967) 246.
6 W.O. Harkins, J. Chem. Phys., 5 (1937) 135.
7 J.A. Wallace and S. Schiirch, J. Colloid Interface Sci., 124 (1988) 452.
8 A.B. Ponter and A.P. Boyes, Can. J. Chem., 50 (1972) 2419.
9 A.P. Boyes and A.B. Ponter, J. Chem. Eng. Jpn., 7 (1974) 314.
10 A.B. Ponter and M. Yekta-Fard, Colloid Polym. Sci., 263 (1985) 1.
11 M. Yekta-Fard and A.B. Ponter, J. Colloid Interface Sci., 126 (1988) 134.
206

12 R.J. Good and M.N. Koo, J. Colloid Interface Sci., 71 (1979) 283.
13 J. Gaydos and A.W. Neumann, J. Colloid Interface Sci., 120 (1987) 76.
14 Y. Rotenberg, L. Boruvka and A.W. Neumann, J. Colloid Interface Sci., 93 (1983) 169.
15 J.K. Spelt, Ph.D. thesis, University of Toronto, 1985.
16 L.J. Gerenser, J.M. Pochan, J.S. Elman and M.G. Mason, Langmuir, 2 (1986) 770.
17 Per M. Claesson, E. Blom Christina, C. Herder Peter and Barry W. Ninham, J. Colloid In-
terface Sci., 114 (1986) 334.
18 P. Cheng, D. Li, L. Boruvka, Y. Rotenberg and A.W. Neumann, Colloids Surfaces, 43 (1989)
151.
19 J.J. Jasper, J. Phys. Chem. Ref. Data, 1 (1972) 841.