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Department of Mechanical and Industrial Engineering, University of Toronto, 5 King’s College Road,
Toronto, Ontario M5S 3G8, Canada
Equation (1) implies a single, unique contact phase contact line allows direct observation of
angle; in practice, however, contact angle phe- surface quality. In addition, when such proce-
nomena are complicated.29,30 For example, the dures are interpreted by an automated axisym-
contact angle made by an advancing liquid ( u a ) metric drop shape analysis—profile (ADSA-P),
and that made by a receding liquid ( u r ) are not complexities such as dissolution of the polymer by
identical; nearly all solid surfaces exhibit contact the liquid and slip/stick of the three-phase contact
angle hysteresis, H (the difference between u a line, which affect the contact angle interpretation
and u r ): in terms of surface energetics, can be identi-
fied.40 –50 It was found that many of the readily
accepted assumptions in interpreting contact an-
H 5 ua 2 ur (2)
gles are often violated when contact angles are
measured by conventional goniometer tech-
Contact angle hysteresis can be due to rough- niques. These assumptions include the applicabil-
ness and heterogeneity of a solid surface. If ity of Young’s equation and constancy of g lv , g sv ,
roughness is the primary cause, then the mea- and g sl during the experiments. A more complete
sured contact angles are meaningless in terms of discussion of these matters can be found else-
Young’s equation. It is well known that on very where.51
rough surfaces, contact angles are larger than on In previous studies,45,50 low-rate dynamic con-
chemically identical smooth surfaces21; such an- tact angles of various liquids were reported on
gles do not reflect material properties of the sur- two methacrylate polymers: poly(methyl methac-
face; rather, they reflect morphological ones. Mod- rylate) PMMA45 and poly(ethyl methacrylate)
els have been employed to gain a better under- PEMA.50 It was found that g lv cos u changes
standing of contact angle hysteresis.29 –33 smoothly with g lv , on one and the same solid
In general, the experimentally observed appar- surface. Thus, one would expect that the result for
ent contact angle, u, may or may not be equal to a polymer similar to these methacrylate polymers
the Young contact angle, u Y 29,30: (1) On ideal solid should behave similarly or should lie somewhere
surfaces, there is no contact angle hysteresis and in between. Thus, it is the aim of this study to
the experimentally observed contact angle is investigate this expectation for a 30 : 70 copoly-
equal to u Y ; (2) On smooth, but chemically heter- mer of poly(methyl methacrylate) and poly(ethyl
ogeneous solid surfaces, u is not necessarily equal methacrylate), P(MMA/EMA, 30/70).
to the thermodynamic equilibrium angle. Never-
theless, the experimental advancing contact angle,
ua, can be expected to be a good approximation of uY.
This has been illustrated using a model of hetero- MATERIALS (SOLID SURFACE AND
geneous (smooth) vertical strip surfaces.29,30 There- LIQUIDS)
fore, care must be exercised to ensure that the ex-
perimental apparent contact angle, u, is the advanc- Poly(methyl methacrylate/ethyl methacrylate,
ing contact angle in order to be inserted into 30/70) P(MMA/EMA, 30/70) copolymer was pur-
Young’s equation; (3) On rough solid surfaces, no chased from Polysciences (Warrington, PA; cat#
such equality between advancing contact angle and 06532) as fine beads. A 2% P(MMA/EMA, 30/70)/
uY exists. Thus, all contact angles on rough surfaces chloroform solution was prepared using chloro-
are meaningless in terms of Young’s equation. form (Sigma-Aldrich, 99.91% A.C.S. HPLC
While the receding angle on a heterogeneous and grade) as the solvent. Silicon wafers ^100& (Silicon
smooth surface can also be a Young angle, it is Sense, Naschua, NH; thickness: 525 6 50 mi-
usually found to be nonreproducible often because crons) were selected as the substrate for the poly-
of sorption of the liquid into the solid and swelling of mer coating. They were obtained as circular discs
the solid by the liquid.34 of about 10 cm diameter and were cut into rect-
The thermodynamic equilibrium angles on angular shapes of about 2.5 cm 3 5 cm. Each
rough and heterogeneous surfaces are the so- rectangular wafer surface was then soaked in
called Wenzel35 and Cassie36,37 angles, respec- chromic acid for at least 24 h, rinsed with doubly-
tively. They are not equal to u Y ; furthermore, they distilled water, and dried under a heat lamp be-
are not experimentally accessible quantities. fore polymer coating. The P(MMA/EMA, 30/70)-
Recently, we have shown38 – 40 that measuring coated surfaces were prepared by a solvent-cast-
contact angles at very slow motion of the three- ing technique described elsewhere.45– 47
DYNAMIC CONTACT ANGLES AND SOLID SURFACE TENSIONS 2041
symmetry of the drop is enforced by using a cir- drop has started advancing. This suggests that
cular capillary. Results of the liquid surface ten- the liquid has a tendency to stick on the surface.
sion from previous studies are reproduced in Three liquids, 1,1,2,2-tetrabromoethane, 1-bro-
Table I. monaphthalene, and dibenzylamine, were found
In this study, six dynamic contact angle mea- to dissolve the P(MMA/EMA, 30/70)-coated wafer
surements at velocities of the three-phase contact on contact, resulting in irregular and flat drops.
line in the range from 0.1 to 1.0 mm/min were The remaining two liquids all show very complex
performed for each liquid. The choice of this ve- contact angle behavior, as given in Figure 2(a)
locity range was based on previous studies38 – 40 and (b). Figure 2(a) shows the contact angle re-
which showed that low-rate dynamic contact an- sults of diiodomethane, a very commonly used
gles at these velocities are essentially identical to liquid for contact angle measurements.16,17,56 – 61
the static contact angles, for these relatively It can be seen that initially the apparent drop
smooth surfaces. volume, as perceived by ADSA-P, increases lin-
early, and u increases from 40° to 80° at essen-
tially constant R. Suddenly, the drop front jumps
RESULTS AND DISCUSSION to a new location as more liquid is supplied into
the sessile drop. The resulting u decreases
Of the 12 liquids used, it was found that only sharply from 80° to 40°. As more liquid is supplied
seven liquids yielded usable contact angles. They into the sessile drop, the contact angle increases
are water, glycerol, formamide, 2,29-thiodietha- again. Such slip/stick behavior could be due to
nol, 3-pyridylcarbinol, 1,3-diiodopropane, and non-inertness of the surface. Phenomenologically,
1-iodonaphthalene. The remaining five liquids ei- an energy barrier for the drop front exists, result-
ther dissolved the polymer on contact or yielded ing in sticking, which causes u to increase at
nonconstant contact angles during the course of constant R. However, as more liquid is supplied
the experiments. into the sessile drop, the drop front possesses
Figure 1(a)–(g) shows, respectively, typical ex- enough energy to overcome the energy barrier,
perimental results of water, glycerol, formamide, resulting in slipping, which causes u to decrease
2,29-thiodiethanol, 3-pyridylcarbinol, 1,3-diiodo- suddenly. It should be noted that as the drop front
propane, and 1-iodonaphthalene: all contact an- jumps from one location to the next, it is unlikely
gles are essentially constant, as the drop volume that the drop is or will remain axisymmetric.
V increases and hence the three-phase contact Such a non-axisymmetric drop will obviously not
radius R. Increasing the drop volume in this man- meet the basic assumptions underlying ADSA-P,
ner ensures the measured u to be an advancing causing possible errors (e.g., in the apparent sur-
contact angle. These contact angles will be used face tension and drop volume). This can be seen
for the interpretation in terms of solid surface from the slight discontinuity of the apparent sur-
tensions. face tension and drop volume with time, as the
In Figure 1(b)–(e) and (g), the contact angles of drop front sticks and slips. Obviously, the ob-
glycerol, formamide, 2,29-thiodiethanol, 3-pyri- served angles in Figure 2(a) cannot all be the
dylcarbinol, and 1-iodonaphthalene increase ini- Young contact angles; since glv, gsv (and gsl) are
tially at essentially constant R. This is due to the constants, u ought to be a constant because of
fact that even carefully putting an initial drop Young’s equation. In addition, it is difficult to
from above the surface can result in contact an- decide unambiguously at this moment whether
gles somewhere between advancing and receding. or not Young’s equation is applicable at all.
Thus, after reaching the proper advancing angles, Therefore, these contact angles should not be
the drop front starts to advance with essentially used for the interpretation in terms of surface
constant u. It should be noted that the liquid– energetics.
vapor surface tension values calculated by ADSA- A different contact angle pattern can be seen in
P sessile drop are fairly constant, but not as reli- Figure 2(b) for dimethyl sulfoxide (DMSO) where
able as those from pendant drop, as explained g lv and u are not constant. It was observed during
above. The accuracy relies very much on the axi- the experiment that DMSO indeed penetrated
symmetry of the drop profile. It can be seen in into the polymer, causing the polymer film to be
Figure 1(f) that the three-phase line of 1,3-diiodo- removed from the wafer surface. These angles
propane appears to stick on the surface at the cannot be used to determine solid surface tension,
beginning of the experiment, but not once the due to physical reaction. Since the observation
DYNAMIC CONTACT ANGLES AND SOLID SURFACE TENSIONS 2045
forces us to discard the measurement, it is not cific case of water in Table II, a final value of u
necessary to verify our stipulation of dissolu- 5 79.91° 6 0.38° was obtained, by averaging the
tion of the polymer by the liquid. Even if poly- contact angles from different rates of advancing
mer dissolution would not be the cause of the (for different experiments). The 95% confidence
observed pattern, the measurement would have limits calculated in this manner (in Table II)
to be discarded. Obviously, these angles should include all possible errors, due to experimental
be disregarded for the following reasons: (1) glv technique, solid surface preparation, etc. A
is different from that of the pure liquids; (2) summary of the contact angle complexities is
we are unsure whether or not gsl and gsv remain
given in Table III, together with the meaningful
constant and whether Young’s equation is ap-
results from Table II.
plicable.
Disregarding the inconclusive contact angle
The reproducibility of all solid–liquid sys-
tems is very good. They are summarized in Ta- data in Figure 2, we show in Figure 3 the contact
ble II for the seven liquids with usable contact angle results from Table II, by plotting g lv cos u
angles, at different rates of advancing and each vs. g lv , together with the error limits calculated
on a newly prepared surface. It should be noted from the contact angle errors. It can be seen that
that a total of more than 60 freshly prepared all liquids independent of molecular properties
P(MMA/EMA, 30/70)-coated wafers were pre- fall on a smooth curve, in agreement with the
pared and used; more than 4000 images were patterns obtained in previous studies40 –50,62– 65
acquired and analyzed by ADSA-P. In the spe- for other solid surfaces: the values of g lv cos u
2046 KWOK, LI, AND NEUMANN
Table II. Summary of the Advancing Contact Angles (deg.) at Different Rates (mm/min) of Motion of the Three-Phase Contact Line for Liquids Which
37.08 6 0.97a
1-Iodonaphthalene
36.76 6 0.31
37.56 6 0.14
36.32 6 0.14
36.55 6 0.16
38.19 6 0.17
clude that
u
g lv cos u 5 F~ g lv, g sv! (3)
Yielded Constant Contact Angles on a Poly(methyl methacrylate/ethyl methacrylate, 30/70) P(MMA/EMA, 30/70)-Coated Silicon Wafer Surface
and hence, because of Young’s equation
0.748
0.867
0.889
0.951
1.158
Rate g sl 5 g sv 2 F~ g lv, g sv! or g sl 5 f~ g lv, g sv! (4)
44.42 6 1.06a
43.74 6 0.20
44.61 6 0.16
45.60 6 0.35
44.72 6 0.24
43.45 6 0.19
1,3-Diiodopropane
2
(5)
Î
64.39 6 0.52a
64.69 6 0.07
64.87 6 0.16
64.23 6 0.09
64.34 6 0.04
63.80 6 0.17
g sv 2b~glv2gsv!2
cos u Y 5 21 1 2
Formamide
e (6)
g lv
u
g sl 5 u g lv 2 g svu (7)
79.91 6 0.38a
79.82 6 0.15
80.15 6 0.13
80.21 6 0.10
79.45 6 0.05
79.93 6 0.09
g sl 5 g lv 1 g sv 2 2 Îg lvg sv (8)
0.240
0.348
0.462
0.491
0.511
Rate
Table III. Summary of Contact Angle Results for a Poly(methyl methacrylate/ethyl methacrylate, 30/70)
P(MMA/EMA, 30/70)-Coated Silicon Wafer Surface
eq. (3), from which gsv can be calculated. We The gsv values from the equation-of-state ap-
show in Table IV the gsv values calculated from proach for solid–liquid interfacial tensions are
Antonow’s rule,71 Berthelot’s rule,72 and the quite constant (within 6 0.5 mJ/m2), essentially
equation-of-state approach for solid–liquid in- independent of the liquids used: the gsv value of
terfacial tensions,14 [i.e., eq. (6)], which can be P(MMA/EMA, 30/70) was found to be 35.1
understood as a modified Berthelot rule.73 It mJ/m2 with a 95% confidence limit of 6 0.3
can be seen that the values of gsv calculated mJ/m2.
from Antonow’s rule tend to increase from 39.0 It should be noted that the constant b value of
mJ/m2 to 43.0 mJ/m2 as glv increases; the gsv 0.0001247 (m2/mJ)2 used in the above calcula-
values calculated from Berthelot’s rule decrease tions had been obtained only from contact angle
from 35.0 mJ/m2 to 25.0 mJ/m2 as glv increases. data on three well-prepared solid surfaces63: FC-
These variations are more pronounced49,51,66 for 721-coated mica, heat-pressed Teflon (FEP), and
other low-energy polymers (e.g., fluorocarbons). poly(ethylene terephthalate) (PET). Alterna-
tively, the g sv value of P(MMA/EMA, 30/70) can
be determined by a two-variable least-squares
analysis,14 by assuming g sv and b in eq. (6) to be
constant. In this procedure, the computer will
search for that pair of g sv and b values which
provides the best fit of eq. (6) to the seven pairs of
experimental ( g lv , u Y ) data points. This leads to a
b value of 0.0001230 (m2/mJ)2 and a g sv value of
35.1 mJ/m2. It is evident that there is good agree-
ment between the g sv values (35.1 6 0.3 mJ/m2
and 35.1 mJ/m2) determined from the two strat-
egies.
Obviously, because of eq. (6), the contact an-
gles for any liquid can be predicted from the gsv
value obtained from a single point of (glv, uY).
This is illustrated in Table V; from the experi-
Figure 3. The values of g lv cos u vs. g lv for the
mental values of glv and u for 1-iodonaphtha-
P(MMA/EMA, 30/70)-coated wafer surface, for the data
in Table II. Since the values of g lv cos u change lene, eq. (6) yields gsv 5 35.2 mJ/m2. With this
smoothly with g lv at constant g sv , g sl can be expressed value of gsv, the contact angles for the remain-
as a function of only g lv and g sv because of Young’s ing six liquids are calculated from eq. (6) and
equation. listed in Table V. The predicted contact angles
2048 KWOK, LI, AND NEUMANN
Table IV. The Solid–Vapor Surface Tension Values, g sv , of a Poly(methyl methacrylate/ethyl methacrylate, 30/
70) P(MMA/EMA, 30/70)-Coated Silicon Wafer Surface Calculated from Antonow’s Rule, Berthelot’s Rule, and the
Equation-of-State Approach for Solid–Liquid Interfacial Tensions
g sv (mJ/m2)
agree with the experimentally observed ones to with the results for the P(MMA/EMA, 30/70) poly-
within approximately 6 2° (i.e., the accuracy/ mer. The g sv values of PMMA45 and PEMA50 were
reproducibility normally associated with con- found from the equation-of-state approach to be,
tact angle measurements). It is apparent that respectively, 38.5 6 0.5 mJ/m2, and 33.6 6 0.5
surface tensions determine the contact angles mJ/m2, so that the value (35.1 6 0.3 mJ/m2) for
completely; the specific intermolecular forces P(MMA/EMA, 30/70) is intermediate and closer to
which give rise to the surface tensions do not that for PEMA, as expected.
affect the contact angles directly: intermolecu- As Figure 4 stands, there might be two pos-
lar forces determine the surface tensions; the sible concerns: the first one is whether such
surface tensions then determine the contact an- data could simply be represented by straight
gle through Young’s equation. The difference lines; the next one is whether the curves are
between the predicted and measured angles are indeed smooth.
indeed very small and could not even be de- With respect to the first point, statistical
tected if a conventional contact angle technique tools provide a definitive answer. We have per-
were used. formed a least-squares analysis to fit these ex-
The above results indeed reconfirm the validity perimental contact angle data separately with
of the equation of state approach14 to determine linear and, for simplicity, quadratic equations.
solid surface tensions from contact angles. The results are given in Table VI. To illustrate
The fact that g lv cos u changes smoothly with the generality of such patterns, contact angle
g lv for the P(MMA/EMA, 30/70) copolymer should data on other methacrylate polymers46,47 and a
be confronted with the results obtained in previ- FC-722-coated mica surface40 are also used. It
ous studies45,50 for two other methacrylate poly- can be seen in Table VI that, in all cases, the
mers: poly(methyl methacrylate) PMMA,45 and regression coefficients for quadratic equations
poly(ethyl methacrylate) PEMA.50 We show in are better than those of the linear equations
Figure 4 these contact angle results, together and that curvature is indeed present in the
Table V. The Predicted Contact Angles for the Liquids in Table IV, Based Solely on the Contact Angle and
Surface Tension of 1-Iodonaphthalene ( g sv 5 35.2 mJ/m2) Using eq. (6)
Table VI. A Summary of the Regression Results Using Linear and Quadratic Equations (see text)
R 2 (regression coefficient)
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