Langmuir l W , l O , 2435-2439 2435

Contact Angle of Water on Polymer Surfaces

T. Yasuda and T. Okuno
Mukogawa Women's University, Nishinomiya 663, Japan
H. Yasuda*
Center for Surface Science & Plasma Technology, University of Missouri-Columbia,
Columbia, Missouri 65211
Received December 2, 1993. I n Final Form: May 6, 1994@

Sessile droplet (advancing and receding) contact angles of water on surfaces of gelatin gel (15% solid),
agar gel (2% solid), and polytetrafluoroethylene(PTFE) film were investigated at 20 "C.The advancing
contact angle of water increases with the postcoagulation time of the gels and reaches a stationary value
(the equilibrium contact angle) in approximately 1h. The value of the advancing contact angle of water
is around 75 and 25" for the gelatin gel and the agar gel, respectively, and 100"for PTFE. The advancing
contact angle is dependent on the relative humidity of air, and the lower the relative humidity, the higher
is the contact angle. The gelatin gel shows a pronounced hysteresis of contact angle (discrepancy between
advancing and receding contact angles),while the agar gel shows very little difference between the advancing
and receding contact angles, partly due to the low advancing angle. Advancing and receding contact angles
are nearly identical for the PTFE surface, and also the surface area under the droplet in the advancing
and receding processes are identical. With gelatin hydrogels, the contact area does not decrease according
to the decrease of drop volume during the receding process (merelyflattens down the profile of the sessile
droplet),whereas the contact area with the agar gel decreaseswith a slight hysteresis effect. "he hysteresis
effect observed with a polymericfilm by the sessile droplet contact anglemeasurement is largely attributable
to the creation of an attractive force between the water and polymer molecules, which results from the
change of the surface configuration to establish a new equilibrium between liquid water and the surface
state of the contacting polymer solid.

Introduction ligands at the top surface) cannot be presumptively

A highly hydrated three-dimensional network of a
hydrophilic polymer is referred to as a hydrogel. Since a
high level of hydrophilicity of the polymer molecules is
required to form such a hydrogel, it is natural to anticipate
that the surface of such a hydrogel would show a rather
low contact angle of water to indicate its hydrophilicity.
In contrast with this anticipation, the surface of a hydrogel
often shows a remarkably high contact angle of water,
indicating the hydrogel-air interface is very hydrophobic.
It has been recognized by many investigators that (1)
the surfaces of gelatin hydrogels as well as (dry)gelatin
films exposed to air show unexpectedly high contact angles
of water,1-8 and (2) there exists a large discrepancy
between the advancing and receding contact angles of
water on hydrogel surfaces (high hysteresis effect of
contact angle of ~ a t e r ) . ~ ~ ~ ~ ~ ~ ~
Holly and Refojogfirst pointed out that the unexpectedly
high contact angle observed with a hydrogel surface is
due to the preferred orientation of hydrophobic moieties
a t the air-hydrogel interface. This implies that (1)the
surface configuration (spatial arrangement of atoms and
@ Abstract published in Advance ACS Abstracts, June 15,1994.
(1)van Oss, C . J.;Zingg, W.; Hum, 0. S.; Neumann, A. W. Polym.
Prepr. (Am. Chem. SOC.,Diu. Polym. Chem.) 1965,4,No. 1, 551.
(2)Braudo, E.;Tolstoguzov,V. B.; Kikitina,E. A. Kolloidn.Zh. 1974,
36,No.2,209.
(3)Baier,R.E.;Zisman, W. A.Adu. Chem. Ser. 1976,145,No. 4,155.
(4)Wolfram, E.;Stergiopulos,Ch.Acta Chim.Acad.Sci. Hung. 1977,
92,No.2,157.
(5)Yasuda, T.;Okuno, T.; Kanazawa, J. Bull. Mukogawa Women's
Uniu. 1981,29,15.
(6)Yasuda, H.; Sharma, A. K; Yasuda, T.J. Polym. Sci., Polym.
Phys. Ed. 1981,19,1285.
(7)Mironjuk, N.V.; Busol, T. F.; Tarasevitch, B. N.; Gojunov, Yu.
predicted by the configuration of polymer molecules, and
(2) the surface properties of polymeric materials are
dictated by the surface configuration but not by the
molecular configuration of the polymer. The latter is a
rephrasing of Langmuih statement made in his publica-
tion in 1938.1°
In contrast to gelatin hydrogels, agar hydrogels show
a consistently lower contact angle with water, which is
more or less expected for a hydrophilic polymer, at the
gel-air interfa~e.'f'~~Such a dramatic difference between
contact angles for a gelatin gel and an agar gel (both made
of highly hydrophilic polymers) was explained by the
difference in the molecular configuration of these two
polymers. Gelatin molecules are randomly-coiled proteins
(denatured collagen) which have a high degree of freedom
to rearrange the distribution of hydrophilic moieties at
the surface, whereas agar molecules are made of polysac-
charides in which hydroxyl groups are located on planar
sugar rings and consequently have much less freedom to
rearrange themselves to change the surface configuration
of a
In recent publications,11J2 the kinetic aspect of the
surface-configurationchange due to the change of contact
medium was investigated by means of CFq plasma surface
labeling, and the concept of the surface-state equilibration
and the consequential equilibrium surface configuration
was presented. The contact angle measurement by a
sessile droplet method has a n inherent feature which is
similar to the liquid water immersion of a surface which
was examined in these papers. Namely, the surface under
a droplet of water will experience the same surface-
~~~ ~

V.; Izmailova, V. N.; Su", B. D. Vysokoml Soedin., Ser. B 1982,24, (10)Langmuir, 1. Science 1958,87,493.
. -. 5-,
No.
- - - -.
. 391. (11)Yasuda,H.;Charlaon,E. J.;Charlson,E.M.;Yasuda,T.;Miyama,
( 8 ) Summ, B. D.; Mashnina, N. V.; Goryunov, Yu. V.; Izmailova, V. M.; Okuno,T. Langmuir 1991,7 , 2394.
A. Kolloidn. Zh. 1986,48,No. 1, 188. (12)Yasuda,T.;Okuno,T.;Miyama,M.;Yasuda,H.Langmuir 1992,
(9) Holley, F. J.; Refojo, M. F. J.Bwmed. Mater. Res. 1976,9,315. 8,1425.
0 1994 American Chemical Society
2436 Langmuir, Vol. 10, No. 7, 1994 Yasuda et al.
configuration change which will occur when a film is
immersed in liquid water. Accordingly, the surface-state
equilibration (at t h e interface between a sessile droplet
a n d the surface) starts to occur as soon as a water droplet
is placed on a surface.
The time scale of the surface-configuration change found
in the previous studies is well within the time scale of
contact angle measurement employed for studies of
advancing a n d receding contact angles. Furthermore
there is no difference between t h e water (droplet) placed
on the surface of a polymer a n d the liquid water in which
a polymer sample w a s immersed. In t h e sessile droplet
contact angle measurement, the surface beyond t h e three
phase contact line is in equilibrium with air,b u t the surface 0 30 60 90 120 150 180 210 240
under the droplet starts to change its surface configuration TIME (min)
in order to establish a new equilibrium surface state as
soon as a droplet is placed on it. Therefore, if the sessile Figure 1. Influence of preconditioning time (time after the
droplet contact angle measurements can be performed in coagulation of gels) on the value of the advancing contact angle
of water on agar and gelatin gels at 20 "C and 65% relative
such a m a n n e r that the increase a n d decrease of the humidity.
amount of water are controlled with respect to time, such
a simple method can provide information pertinent to t h e
ease a n d the extent of surface-configuration change which
occurs as a consequence of wetting of a polymeric surface.
With this point of view, measurements of advancing
a n d receding contact angles were carried out for three
It
typical cases: (1)hydrophobic a n d no surface-configura-
tion change-F'TFE; (2) hydrophilic a n d a high degree of
surface-configuration change-gelatin gel; (3)hydrophilic
@
0.0 .
Roc. -
a n d minimal surface-configuration change-agar gel. 80
Experimental Section
Gelatin Gel. The reagent first grade gelatin (WakoJunyaku,
Japan) was used to prepare the gelatin gels. A 15 weight %
aqueous solution of gelatin was prepared by dissolving gelatin
at an elevated temperature. The gelatin solution was poured (0.5)
into a stainless steel tray and cooled by leaving it in a 0.0 13.5 27.0
temperature- and humidity-controlled room. The thickness of DROPLET VOLUME (ul)
a gel was approximately 0.5 cm. Figure 2. Effect of droplet volume on advancing and receding
Agar Gel. The reagent first grade agar (Wako Junyaku, contact angles of water on a FTFE film.
Japan) was used to prepare an agar gel from a 2 weight % solution
in water by followingthe same procedure used for the gelatin gel
formation.
The concentrations of gelatin and agar solutions were selected
so that the maximum hardness of gels could be obtained.
Water. Water for the measurement of the contact angle was
E
30
purified by a reverse osmosis unit, and the product water was
further treated by an ion-exchange column.
- 20.0

Measurement of Contact Angle. A Kyowa Contact Angle 2

a
Measuring Device, Model CA-D (Kyowa Kaimen Kagaku, KK), a
was used for the measurement of the contact angle of water. All I-
o
samples were preconditioned for 3 h under the environmental
conditions of measurement. According to the results of the
preliminary study, shown in Figure 1, for the influence of time o
after the preparation of gels on the contact angle of water, the
contact angle of water changes as a function of time after the
preparation for roughly 1h and reaches a stationary value in 3 "."
h. A small piece, 2 x 2 x 0.5 cm, of gel was cut out by using a 0.0 13.5 27.0
razor blade and placed on a microscope slide glass for the DROPLET VOLUME @I)
measurement of the contact angle.
A water droplet of 2.7,uL was placed on a surface and a picture Figure 3. Effect of droplet volume on the contact area of a
of the droplet was taken by a camera. A droplet was added every water sessile droplet on a PTFE film.
20 s, and the procedure was repeated 10 times (total 27 pL).
Then 2.7 ,uL of water was withdrawn every 20 s for the humidity (28, 30, 60, and 90%). Unless otherwise noted, the
measurement of the receding contact angle. The contact angle advancing contact angle represents the plateau value which is
of water was measured by using an enlarged image of the independent of the water droplet volume.
developed film. By the photographic approach, an accurate
measurement of the contact angle can be measured with a Results
controlled (intermittent) advancing rate; i.e., the time necessary
to measure the contract angle can be eliminated in the process PTFE. Advancing a n d receding contact angles a r e
of increasing and decreasing the drop volume. shown in Figure 2, a n d t h e contact a r e a as a function of
The measurements of contact angles were carried out in a t h e water droplet volume is shown in Figure 3. The
temperature- and humidity-controlled room. The temperature advancing angle a n d the receding angle are not identical
was kept at 20 "C for all experiments. The relative humidity of (100"versus 90"))b u t they do not depend on the water
the room was changed to investigate the influence of relative droplet volume. The contact areas on both the advancing
Contact Angle of Water on Polymer Surfaces Langmutr, Vol. 10, No. 7, 1994 2437
1.o -1
1.o
: 20% 30XR.H.
: 20°C 0KR.H.
: 20°C 9OXR.H. 0.9 .
I
@ 0.5
v)

s " t 0.7

t
0 +: 20% 28XR.H.
A A: 20% 30XRH.
0 0 : 20'C 6SXR.H.
0 W: 20°C 9OXR.H.
o.6
0.0 0.51 ' a * ' ' * ' ' 1
0.0 13.5 27.0

0.0 13.5 27.0 DROPLET VOLUME (MI)

DROPLET VOLUME (ut) Figure 6. Effect of droplet volume on advancing and receding
Figure 4. Effect of droplet volume on advancing and receding contact angles of water on an agar gel.
contact angles of water on a gelatin gel. 00.0 r

70.0 .

-2
E
60.0.

50.0 *
2a
a 40.0.
F
2I- 30.0.
2
8 20.0'
A A: 20% 3OXR.H.
'
0 0 :20% 65KR.H.
A A :20°C 30XR.H. 10.0 ' 0 W :20% 9OXR.H.
0 0 :20% WXRW
m :2 0 ~OXR.H.
~
0.0 " " " " "

13.5 27.0
DROPLET VOLUME @I)
Figure 8. Effect of droplet volume on the contact area of a
water sessile droplet on a gelatin gel.
and receding processes are nearly identical. In this case
the three phase contact line indeed recedes in the process
of the "receding contact angle" measurement as the water
droplet volume decreases.
Gelatin Gel. Figure 4 depicts contact angles observed
in the advancing and the receding cycles as a function of
the water droplet volume. The advancing angle reaches
a constant value as the water droplet volume increases
beyond 10 p L and remains constant. The constant
advancing angle observed is dependent on the relative
humidity of air and is higher at lower humidity.
The receding contact angle decreases steadily as the
droplet volume is decreased. This decrease is due to the
fact that the contact area of the droplet does not change
according to the droplet volume when water is removed
from the droplet, as shown in Figure 5. In this case the
three phase contact line does not recede as much as one
would expect from the decrease of droplet volume in the
process of the "receding contact angle" measurement, but
actually advances slightly.
Agar Gel. While the values of contact angles are much
smaller, the trends observed with the gelatin gel were
found also with the agar gel, but their extent is much
smaller, as seen in Figures 6 and 7. Because a certain
amount of water is absorbed into the gel and the water
droplet volume is calculated from the amount of water
withdrawn, the receding experiment intercept coordinate
is at a higher water droplet volume than the original
starting point.
Figure 7. Effect of droplet volume on the contact area of a
water sessile droplet on an agar gel.
The contact area remains nearly constant until a certain
amount of water is withdrawn and then decreases with
a further withdrawal of water from the droplet. When
the contact area decreases, the slope of decrease is nearly
the same as that for the increase observed on the advancing
steps.
Discussion
Contact Angle as a Measure of Surface Configu-
ration. These data seem to support the concept of the
surface-configuration change and of the surface-state
equilibration. The surface state of a polymer is in
equilibrium with the surrounding medium. As soon as
the surrounding medium is changed, the surface state of
the polymer will start the process of establishing a new
equilibrium with the new medium. The surface state, in
general, is a complex function of surface configuration,
adsorbed and/or imbibed substances, physical roughness,
etc.
If a polymer has the capability to change the surface
configuration by means of rotational and migrational
rearrangement of functional groups, the surface-state
equilibration can be achieved by changing the surface
configuration according to the new environment. It is
important to recognize that such a change can take place
without appreciable absorption or imbibition of the liquid
in contact. Evey sessile droplet placed on a surface in
order to measure the contact angle interacts with the
surface, and the extent of interaction is dependent on
nature of the liquid and of the surface.
2438 Langmuir, Vol. 10,No. 7, 1994
a
0.5 1 A specific water-polymer interaction takes place mainly
m I
0 : G&th
0 : PTFE
(0.5)
20 50 100
RELATIVE HUMlDlTV (%)
Figure 8. Effect ofrelativehumidity on the advancingcontact
angle of water.
A high contact angle observed with a polymer surface
in the sessile droplet (advancing) contact angle measure-
ment does not necessarily mean that the surface is
hydrophobic; it merely means that the surface configura-
tion in equilibrium with a set of environmental conditions
just before the measurement is in such a way that the
contact angle of water is high. The followingfacts which
have appeared in the literature are also in accordance
with this concept of surface-state equilibration (mainly
by the change of surface configuration).
Wolfram et al. reported that the advancing contact angle
of water on the air-equilibrated surface of a gelatin
hydrogel was ill",whereas on the inner surface (freshly
cut surface) it was only 36". They stated that the polar
interaction is negligible a t the (air-exposed) top surface
but appreciable at the inner surface.
The contact angle measurements with a (dry) gelatin
film are complicated by the swelling effect caused by the
contact with water. Nevertheless, for gelatin films, it has
been reported that contact angle measurements with
various liquids with varying liquid surface tensions
showed a duality of behavior depending the polarity of
the liquids. In other words, two critical surface tensions
can be seen in a Zisman's plot for polar solvents and for
nonpolar solvent^.^
Mironjuk et al. reported that a gelatin film formed on
a germanium plate by a Langmuir-Blodgett process
showed significantly different contact angles with water
when the surface was kept in contact with air (110")and
with benzene (90").
The equilibrium advancing contact angle is a function
of the partial pressure of the water vapor with which a
surface is equilibrated before the contact angle measure-
ment. Figure 8 depicts the dependence of the equilibrium
advancing contact angle on the relative humidity of air.
Dealing with a nearly ideal smooth polymeric surface,
which shows the least hysteresis effect, such as the case
of PTFE, the contact angle should be dependent on the
relative humidity of air, because a different relative
humidity represents a different surrounding medium. This
is the exact case found in this study (see data for PTFE
in Figure 8).
Receding Contact Angles. In a strict sense, the
receding contact angle should be measured at a receding
contact line (the contact line moving toward the center of
a droplet). In many cases, however, it is intuitively
assumed that the decrease of droplet volume would cause
the receding of the contact line. It is often difficult to
judge if the contact line is receding or not during the
measurements. For example, the contact line of a water
droplet on a gelatin gel actually advances in the receding
process. This unexpected phenomenon cannot be detected
by the measurement of contact angle alone. The simul-
Yasuda et al.
taneous measurement of the contact area reveals the
phenomenon.
at the surface underneath the droplet and consequently
does not significantly influence the advancing contact
angle. Once a specific (attractive) interaction is created
between the surface (beneath the water droplet) and water,
the force acts as a resisting force for any change associated
with the interface. The observed slow or the absence of
reduction of the contact area in the receding angle
measuring process is the result of this resisting force. A
similar effect has been reported in the observation of the
ease or reluctance of a water droplet to move on the surface
when the surface with a water droplet is tilted. A water
droplet on a water-proofed fabric, which showed over 90"
contact angle, did not roll down when the plane of the
surface was tilted to the vertical position.13
When the water-polymer interaction is created, the
receding process of a sessile droplet does not reduce the
size of the contact area according to the droplet volume
and the decline of contact angle is observed as a conse-
quence of the flattening of the profile of the sessile droplet.
Thus, dealing with polymeric surfaces, the term "receding
contact angle" in the sessile droplet method could be a
misleading expression of the real phenomena. In such a
case, the receding contact angle should be treated as a
mere phenomenological parameter rather than a ther-
modynamic parameter. The contact angle hysteresis
based on the receding contact angle in this context seems
to be a measure of the perturbability of the polymeric
surfaces. The hysteresis of the contact area also can be
treated as a phenomenological parameter, which has a
practical value of detecting the abnormality in the water
withdrawal process.
Hysteresis in the Measurement of Contact Angles.
Dealing with polymeric surfaces, which are highly per-
turbable in comparison to other surfaces of inorganic
materials, the hysteresis of the contact angle should be
focused on the dependence on the contact time of water
and the surface. In this context, the difference in values
of the advancing and receding contact angles per se is not
the issue. For instance, the differenceexists for the surface
of Teflon reported in this study; however, the difference
is independent of the contact time. Such a discrepancy
may be due to the physical factors of the surface such as
microroughness, and also to the difference in work to
change the droplet volume against (the advancing process)
or with (the receding process) the surface tension of the
liquid.
In contrast to the case of Teflon, the discrepancy
observed for a gelatin gel is dependent on the droplet
volume and consequently on the contact time. If the
surface-configuration change represents a significant
change in hydrophilic-hydrophobic balance, such as the
case of a gelatin gel, a large discrepancy between the
advancing and the receding contact angles would be seen.
Such a change in surfwe configuration is a function of the
contact time.
The reluctance of decreasing contact area observed with
gelatin and agar gels can be explained by the attractive
force created as a consequence of scrambling of hydrophilic
moieties near the surface to cope with the presence of
liquid water. In other words, when an attractive force is
created between the water molecule and the surface, the
reduction of water droplet volume by reducing the contact
area while maintaining the same droplet shape requires
(13)Iriyama, Y.; Yasuda, T.; Cho, D. L.; Yasuda, H. J.App1. Polym.
Sci. 1990, 39, 249.
Contact Angle of Water on Polymer Surfaces
more energy than reducingthe water volume by flattening
the droplet profile while maintaining the same contact
area.
A high degree of segmental mobility is anticipated in
highly swollen hydrogel systems. Consequently,it is very
unlikely that hydrophilic moieties remain at the gel-air
interface because a large amount of water is in the bulk
phase of the gel. Therefore, a hydrogel which shows a
highly hydrophilic gel-air interface should have a mo-
lecular structure that provides a high degree of surface-
configuration stability. The case of an agar gel might
provide an excellent example of this situation. Agar is
made of a polysaccharide molecule which has a planar
sugar ring, on both sides of which hydrophilic -OH groups
are located. Consequently, a certain amount of -OH
groups will be at the gel-air interface regardless of the
orientation and the conformation of polysaccharide mol-
ecules at the interface, which implies a high surface-
configuration stability. Because of this configurational
stability built into the molecular structure of the polysac-
charides, an agar gel has a low contact angle with water
and also a low level of contact angle hysteresis.
If a surface state in which hydrophobic moieties are
aligned at the top surface exposed to air can be created
with very hydrophilic polymer molecules which have no
specific molecular structure to yield high surface-
configuration stability (e.g., gelatin), the placement of
water will cause an immediate and quick change of surface
configuration. This change is seen as the hysteresis effect
of the contact angle.
In fact, most polar groups of hydrophilic polymers
usually do not remain a t the top surface, which is exposed
to air,but are buried in the inner part ofthe surface region.
A recent study on the depth profile of oxygen near the
surface of a copolymer of vinyl alcohol (60) and ethylene
(40) indicated that more oxygen atoms are in the sublayer
of the dry film but more oxygen atoms are found at the
top layer after samples were immersed in water.14 These
results indicate that the distribution of OH groups in the
copolymer near the surface changes as a consequence of
establishing a contact between the surface and water. The
same phenomenon should occur at the surface (beneath
a droplet) when a droplet ofwater is placed on the surface.
A pronounced contact angle hysteresis was indeed ob-
served with surfaces of the copolymer films.
(14)Yasuda, T.;Miyama, M.; Yasuda, H.Langmuir 1994,10, 583.
Langmuir, Vol. 10,No. 7, 1994 2439
The slight increase of contact area in the receding
process observed with a gelatin gel indicates that the
change of surface configuration caused by placing a water
droplet advances beyond the original boundary set by the
three phase line with the time of water-surface contact.
This implies that if a fixed volume water droplet is placed
on a gelatin surface, the advancing contact angle is a
function of time after the droplet is placed and that the
advancing contact angle contains a kinetic factor. Dealing
with polymer surfaces, this aspect should not be ignored.
The contact angle measurement, particularly when
performed with the controlled contact time, provides
important information that is pertinent to the ease and
the extent of surface-configuration change which results
from the liquid water-surface interaction.
Conclusion
An ideal force balance typically envisioned by a drawing
to explain Young's equation exists only for the system in
which the liquid used as a sessile droplet has no specific
interaction with the atoms and molecules which constitute
the surface. For such an ideal situation, a surface must
be unperturbable by the liquid droplet placed on it.
Surfaces of polymeric materials are often highly perturb-
able to such an extent that the general applicability of the
ideal case is questionable.
In many cases, polymer molecules interact with the
liquid used as a sessile droplet and this changes the surface
state of the area beneath the liquid droplet significantly
from that for the dry surface. This change does not
influence the advancing contact angle in many cases but
does create significant effects on the measurement of the
receding contact angle measurement by the sessile droplet
method. Thus, the receding contact angle on a polymer
surface cannot be treated as strictly as the advancing
contact angle can.
Dealing with nonporous, smooth, and homogeneous (in
a macroscopic context) polymer surfaces, the major reason
which accounts for large differences between advancing
and receding contact angles of water is the change of the
surface state of the polymers beneath the water droplet,
which can be largely attributed, in many cases, to the
change of the surface configuration caused by the water-
polymer interaction.