Guest Commentary
pubs.acs.org/JPCL
Definitions for Hydrophilicity, Hydrophobicity, and
Superhydrophobicity: Getting the Basics Right
S urface is a very important branch of science that touches all
facets of our lives. It has recently attracted a tremendous
amount of attention in both academia and industry due to the
famous self-cleaning effect displayed by the Lotus leaves in
nature.1,2 Research activities on surfaces with special wettability,
superior repellency, and controllable adhesion have been
extremely active, and thousands of papers have been published
annually in recent years.3 Just in 2013, five review articles have
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
already appeared.4−8 Static and dynamic contact angle
measurements are commonly employed to study the wetting,
dewetting, and adhesion characteristics of these surfaces.9
Figure 1 depicts the schematics for the various angles
Downloaded via 103.153.105.43 on November 23, 2023 at 04:39:53 (UTC).
Figure 1. Schematics for the various contact angles: (a) static
(apparent) contact angle θ, (b) sliding angle α, (c) advancing angle θA,
and (d) receding angle θR.
determined from these measurements: static contact angle θ,
advancing angle θA, receding angle θR, and sliding angle α.
Contact angle hysteresis is simply the difference between θA
and θR.
The most recognizable definitions in surface science are
hydrophobicity and hydrophilicity. In the Greek words, hydro
means water, philicity means affinity, and phobicity means lack
of affinity. In the scientific community, we have come to accept
the definition that a surface is hydrophobic when its static water
contact angle θ is >90° and is hydrophilic when θ is <90°.
There is actually very little rationalization as why the surface
switches from being hydrophilic to hydrophobic when θ
changes only 2° from 89 to 91°. What is the molecular origin or
driving force to support this definition? In fact, Gao and
McCarthy reported observing strong adhesion interactions
between water and fluoroalkyl monolayers and Teflon surfaces
in 2008, and they even stated that “Teflon is hydrophilic” in
their article.10 Therefore, there is a definite need for a good
definition in surface science that is supported by technical data.
In 2011, we11 reported a systematic study on the wetting and
adhesion interactions of water with 20 different surfaces (1−
20) using the microbalance in a tensiometer. These 20 surfaces
represent surfaces of all traits, from hydrophilic to hydrophobic
© 2014 American Chemical Society
to superhydrophobic based on common acceptable definitions.
Physically, they vary from atomic smooth to ordinary polymer
films to photolithographic created textured surfaces to rose
petals. The wetting (attractive) interaction was recorded as the
snap-in force by the microbalance when the water droplet and
the surface first make contact. The adhesion force was
measured as the pull-off force when the water droplet and
the surface separate after making contact. A schematic for the
measurement is given in Figure 2.
Figure 2. Schematic of the apparatus and procedures for measuring
the wetting and adhesion interactions between water and various
surfaces.
The snap-in force and the pull-off force were found to
correlate only to the advancing contact angle (θA) and the
receding contact angle (θR), respectively, not to the static
contact angle θ, sliding angle, or contact angle hysteresis. We
concluded from the correlations that θA is a measure for surface
wettability (or repellency) and θR is a measure for surface
adhesion. In this Guest Commentary, linear regression analyses
were performed on these two plots, and reasonably good
correlations were obtained (Figure 3a and b).
The results clearly show that the changes in wetting and
adhesion interactions are gradual and that there is no magic
cutoff at 90° for θ, θA, or θR. On the other hand, upon closer
examination of the plot in Figure 3b, one may notice a clear
divide of the data at θR ≈ 90°. The data on the left-hand side,
surfaces 1−7, 9, 12, and 20, are represented by solid diamonds,
and the data on the right-hand side, surfaces 8, 10−11, and
13−19, are represented by empty squares. As reported earlier,11
we actually observed a small residual water droplet after the
surface and the water separate for surfaces with θR < 90°. The
surface is clean after the water drop retracts from surfaces with
θR > 90°. Photographs and the schematic showing these two
cases are given in Figure 4. The observation of the tiny residual
water droplet after the water and surface separate is indicative
of definite affinity. The clear distinction between surfaces at θR
< 90° and θR > 90° leads us to propose that a surface is
Published: February 20, 2014
686 dx.doi.org/10.1021/jz402762h | J. Phys. Chem. Lett. 2014, 5, 686−688
The Journal of Physical Chemistry Letters
Figure 3. Plots of the (a) snap-in force versus advancing contact angle
and (b) pull-off force versus receding contact angle for water drop with
20 different surfaces. Modified from ref 11. Copyright American
Chemical Society.
Figure 4. Photographs and schematics showing water−surface separation from a hydrophilic (top) and hydrophobic (bottom) surface.
687
Guest Commentary
hydrophilic when θR is < 90° and is hydrophobic when θR is >
90° (Figure 4).
Others have also noticed the shortfall of the general
definition in hydrophilicity and hydrophobicity. van Oss12
proposed to use the free energy of hydration (ΔGsl) as the
measure of hydrophilicity and hydrophobicity. On the basis of
the analysis of the free energy of hydration for a number of
compounds, he found that hydrophobic compounds attract
each other in water when ΔGsl > −113 mJ/m2 and that they
repel each other when ΔGsl < −113 mJ/m2. The value −113
mJ/m2 was proposed to be the cutoff between hydrophobicity
and hydrophilicity. On the other hand, Vogler13 proposed a
cutoff of θ ≈ 65° based on the appearance and disappearance of
long-range hydrophobic interactions. The main shortcoming in
these definitions is the lack of explicit change in surface
property at the cutoff angle. Whether it is the change in the H-
bonding structure or hydrophobic interaction, the change
through the cutoff point is continuous and gradual. On the
other hand, the proposed definition in this Guest Commentary
is based on the actual measured affinity between water and the
surface. For hydrophilic surfaces, their θR’s are <90°. These
surfaces exhibit strong affinities, as indicated by the residual
water droplets in the pull-off experiments, whereas hydrophobic
surfaces are shown to have little affinity with water, and their
θR’s are >90°.
The remaining question is why does the surface change from
hydrophilic to hydrophobic at θR ≈ 90°. It is important to point
out that the plot in Figure 3a indicates that there is always an
attractive interaction between water and the hydrophobic
surfaces even though the attraction is weakening as θA
increases. The fact that no residual water droplet was observed
when θR > 90° can be attributed to the high cohesion of the
water droplet. The water droplet prefers to be in the droplet
state rather than wetting the surface due to the small wetting
energy. In other words, it is the competition between wetting
and droplet cohesion that changes the surface from hydrophilic
to hydrophobic. The importance of liquid cohesion in wetting
was actually discussed in length in Young’s original essay.14
Another commonly used definition in the surface literature is
superhydrophobicity when the surface θ is >150°. As pointed
out by Roach and co-workers earlier,15 this definition appears
only by popular consensus, and there is no technical
dx.doi.org/10.1021/jz402762h | J. Phys. Chem. Lett. 2014, 5, 686−688
The Journal of Physical Chemistry Letters Guest Commentary

rationalization for this definition. On the other hand, from the (10) Gao, L.; McCarthy, T. J. Teflon is Hydrophilic. Comments on
results in Figure 3a, we notice that the wetting interaction for Definitions of Hydrophobicity, Shear versus Tensile Hydrophobicity
surfaces 15−19 is not measurable. The measured snap-in forces and Wettability Characterization. Langmuir 2008, 24, 9183−9188.
(11) Samuel, B.; Zhao, H.; Law, K. Y. Study of Wetting and Adhesion
for these super water-repelling surfaces become zero, indicative
Interactions between Water and Various Polymer and Super-
of their super phobic status. From the intercept of the plot, we hydrophobic Surfaces. J. Phys. Chem. C 2011, 115, 14852−14861.
propose that a surface is superhydrophobic when its θA is (12) van Oss, C. J. Interfacial Forces in Aqueous Media; Marcel
≥145°. Dekker, Inc.: New York, 1994.
It is interesting to note that the magic 90° cutoff has also (13) Vogler, E. A. Structure and Reactivity of Water at Biomaterial
been used to define philicity and phobicity for other liquids in Surfaces. Adv. Colloid Interface Sci. 1998, 74, 69−117.
the surface literature. If phobicity does in fact originate from (14) Young, T. An Essay on the Cohesion of Fluids. Philos. Trans. R.
surface tension, one would expect a different cutoff for a Soc. London 1805, 95, 65−87.
different liquid. Indeed, in a similar study with hexadecane, (15) Roach, P.; Shirtcliffe, N. J.; Newton, M. I. Progress in
Superhydrophobic Surface Development. Soft Matter 2008, 4, 224−
whose surface tension is a lot lower than that of water, 72.3 240.
versus 27.5 mN/m, we found preliminarily that the
oleophilicity−oleophobicity cutoff is at hexadecane θR ≈
125°, and superoleophobicity occurs when the surface
hexadecane θA is ≥165°. The larger cutoff angles for
hexadecane oleophilicity, oleophobicity, and superoleophobic-
ity are consistent with its lower surface tension.
In summary, on the basis of the measured wetting and
adhesion interactions between water and a variety of surfaces,
we propose that a surface is hydrophilic when its water θR is
<90° and that it is hydrophobic when θR is >90°. The driving
force for switching from hydrophilicity to hydrophobicity is the
high surface tension of water. We further define that a surface is
superhydrophobic when its θA is ≥145°, where it has practically
no affinity with water.
Kock-Yee Law
Research and Innovative Solutions, Penfield, New York,
United States

■ ACKNOWLEDGMENTS
The author thanks Dr. Hong Zhao (Xerox) for providing the
raw data for the additional analysis described in this Guest
Commentary and Dr. Robin H. A. Ras (Aalto University) for
pointing out the need for a better definition for super-
hydrophobicity.

■ REFERENCES
(1) Barthlott, W.; Neinhuis, C. The Purity of Sacred Lotus or Escape
from Contamination in Biological Surfaces. Planta 1997, 202, 1−8.
(2) Neinhuis, C.; Barthlott, W. Characterization and Distribution of
Water-Repellent, Self-Cleaning Plant Surfaces. Ann. Bot. 1997, 79,
667−677.
(3) Law, K. Y. Editorial. Nanostructured Coatings, Surfaces and
Films. Surf. Innovations 2013, 1, 57−58.
(4) Kota, A. K.; Mabry, J. M.; Tuteja, A. Superoleophobic Surfaces.
Design Criteria and Recent Studies. Surf. Innovations 2013, 1, 71−83.
(5) Liu, K.; Tian, Y.; Jiang, L. Bio-inspired Superoleophobic and
Smart Materials. Design, Fabrication and Application. Prog. Mater. Sci.
2013, 58, 503−564.
(6) Nishimoto, S.; Bhushan, B. Bioinspired Self-Cleaning Surfaces
with Superhydrophobicity, Superoleophobicity, and Superhydrophi-
licity. RSC Adv. 2013, 3, 671−690.
(7) Celia, E.; Darmanin, T.; de Givenchy, E. T.; Amigoni, S.;
Guittard, F. Recent Advances in Designing Superhydrophobic
Surfaces. J. Colloid Interface Sci. 2013, 402, 1−18.
(8) Drelich, J.; Marmur, A. Physics and Applications of Super-
hydrophobic and Superhydrophilic Surfaces and Coatings. Surf.
Innovations 2013, DOI: 10.1680/si.13.00017.
(9) Zhao, H.; Law, K. Y.; Sambhy, V. Fabrication, Surface Properties,
and Origin of Superoleophobicity for a Model Textured Surface.
Langmuir 2011, 27, 5927−5935.

688 dx.doi.org/10.1021/jz402762h | J. Phys. Chem. Lett. 2014, 5, 686−688