Current Opinion in Colloid & Interface Science 11 (2006) 193 – 202

www.elsevier.com/locate/cocis

Superhydrophobic surfaces
Minglin Ma, Randal M. Hill ⁎
Institute for Soldier Nanotechnologies and Department of Chemical Engineering, Massachusetts Institute of Technology,
77 Massachusetts Avenue, Cambridge 01239, Massachusetts, USA
Dow Corning Corp., Midland, MI 48686, USA
Available online 11 October 2006

Abstract

Non-wettable surfaces with high water contact angles (WCAs) and facile sliding of drops, called superhydrophobic or ultrahydrophobic, have
received tremendous attention in recent years. New publications have appeared in the last year documenting many new ways to prepare such
surfaces—ranging from application driven work to make robust self-cleaning surfaces to careful model studies of patterned surfaces seeking to
understand the relationship between surface morphology and wettability and droplet sliding. This review summarizes this recent work and looks
ahead to future developments. The emphasis of the review is on the diverse methods that have been developed to make such surfaces.
© 2006 Published by Elsevier Ltd.

Keywords: Superhydrophobic; Water-repellent; Surface; Coating; Self-cleaning; Lotus effect

1. Introduction “superhydrophobic”. However, some natural examples (the wings

Many surfaces in nature are highly hydrophobic and self-
cleaning. Examples include the wings of butterflies [1] and the
leaves of plants such as cabbage and Indian cress [2••]. Some
undesirable plants such as gorse (Ulex europeaus) introduced
into New Zealand, and many common yard weeds have waxy
leaf surfaces that make wetting them with water-based her-
bicides very difficult. The trisiloxane superwetters [3] were
developed for their remarkable ability to wet such hard-to-wet
surfaces and enhance herbicide efficacy. The best known
example of a hydrophobic self-cleaning surface is the leaves of
the lotus plant (Nelumbo nucifera). Electron microscopy of the
surface of lotus leaves shows protruding nubs about 20–40 μm
apart each covered with a smaller scale rough surface of
epicuticular wax crystalloids [4•]. Numerous studies have con-
firmed that this combination of micrometer-scale and nanome-
ter-scale roughness, along with a low surface energy material
leads to apparent WCAs N 150°, a low sliding angle and the self-
cleaning effect [5•]. Surfaces with these properties are called
⁎ Corresponding author. Dow Corning Corp. Visiting Scientist MIT Institute for
Soldier Nanotechnologies 500 Technology Square Fourth Floor Cambridge, MA
02140, USA. Tel.: +1 617 324 6446.
E-mail address: rmhill@mailaps.org (R.M. Hill).
1359-0294/$ - see front matter © 2006 Published by Elsevier Ltd.
doi:10.1016/j.cocis.2006.06.002
of some insects) do not exhibit two length scales and many studies
(for example, [6••,7]) in which nanostructured surfaces were
prepared have found large contact angles and low sliding angles
calling into question the necessity for a double length scale.
Since the group at Kao [8••] first demonstrated artificial
superhydrophobic surfaces in the mid-1990s, a very large
number of clever ways to produce rough surfaces that exhibit
superhydrophobicity have been reported. Besides water repel-
lency, other properties such as transparency and color, an-
isotropy, reversibility, flexibility and breathability have also
been incorporated into superhydrophobic surfaces. The inten-
tion of this article is to provide readers the current status of
studies on superhydrophobic surfaces, concentrating mainly on
publications appearing in the past year. Useful recent reviews
have been published by Nakajima et al. [5•] and Sun et al. [9•].
Quere [10••] critically discussed the surface chemistry of non-
sticking surfaces from the original papers by Cassie and Wenzel
to the present.
Before we go into the details, it is worth pausing to recall
that the lotus plant achieves an apparent WCA N 160° and nil
sliding angle using paraffinic wax crystals containing predom-
inantly –CH2– groups. Nature does not require the lower
surface energy of –CH3 groups or fluorocarbons to achieve
these effects. This plainly demonstrates that extremely low
surface energy is not necessary to achieve non-wetting. Rather,
194 M. Ma, R.M. Hill / Current Opinion in Colloid & Interface Science 11 (2006) 193–202

the ability to control the morphology of a surface on micron and
nanometer length scales is the key. This decoupling of wetting
from simple surface energy opens up many possibilities for
engineering surfaces.
Controlling the wetting of surfaces is an important problem
relevant to many areas of technology. The interest in self-
cleaning surfaces is being driven by the desire to fabricate such
surfaces for satellite dishes, solar energy panels, photovoltaics,
exterior architectural glass and green houses, and heat transfer
surfaces in air conditioning equipment. Non-wettable surfaces
may also impart the ability to prevent frost from forming or
adhering to the surface. The fact that liquid in contact with
such a surface slides with lowered friction suggests applica-
tions such as microfluidics, piping and boat hulls. Most of
these applications involve solid surfaces, but the emergence of
flexible membrane forms should lead to uses in garments and
barrier-membranes—both Cassie and Wenzel were originally
involved in work on waterproofing textiles [11,12]. The non-
wettable character has been claimed in biomedical applica-
tions ranging from blood vessel replacement to wound
management. We assume that unexpected applications will
emerge as the technology to make non-wettable surfaces
matures—nature uses this property in all known ecosystems
from polar bears to ducks to butterflies and water-walkers to
plant leaves.
Techniques to make superhydrophobic surfaces can be sim-
ply divided into two categories: making a rough surface from a
low surface energy material and modifying a rough surface with
a material of low surface energy.
hydrophilicity (dedoped or neutral state) was obtained upon
changing the applied electrochemical potential.
2.2. Silicones
Another well-known material with low surface energy is
polydimethylsiloxane (PDMS). Because of its intrinsic deform-
ability and hydrophobic property, PDMS can readily be
made into superhydrophobic surfaces using various methods
[18–20]. For example, Khorasani et al. [18] treated PDMS
using a CO2-pulsed laser as an excitation source. The WCA for
the treated PDMS was as high as 175° which was believed to be
due to both the porosity and chain ordering on the PDMS
surface (Fig. 2a). Similarly, Jin et al. [19] used a laser etching
method to make a rough surface of PDMS elastomer containing
micro-, submicro- and nanocomposite structures. Such a surface
exhibited a superhydrophobicity with WCA higher than 160°
and sliding angle lower than 5°. Sun et al. [20] recently reported
a nanocasting method to make superhydrophobic PDMS sur-
face. They first made a negative PDMS template using lotus leaf
as an original template and then used the negative template to
make a positive PDMS template—a replica of the original lotus
leaf. The positive PDMS template (Fig. 2b) had the same
surface structures and superhydrophobicity as the lotus leaf.

2. Roughening a low surface energy material

2.1. Fluorocarbons

Fluorinated polymers are of particular interest due to their

extremely low surface energies. Roughening these polymers in
certain ways leads to superhydrophobicity directly [13–15].
For example, Zhang et al. [13] reported a simple and effective
way to achieve a superhydrophobic film by stretching a poly
(tetrafluoroethylene) (Teflon®) film. The extended film con-
sisted of fibrous crystals with a large fraction of void space in
the surface which was believed responsible for the super-
hydrophobicity. Shiu et al. [14] treated a Teflon® film with
oxygen plasma and obtained a rough surface with a WCA of
168°. Due to their limited solubility, many fluorinated
materials have not been used directly but linked [16•] or
blended [17••] with other materials (which are often easy to
roughen) to make superhydrophobic surfaces. Yabu and
Shimomura [16•] prepared a porous superhydrophobic mem-
brane by casting a fluorinated block polymer solution under
humid environment (Fig. 1a). The membrane was also
transparent due to the small pore size. Xu et al. [17••] Fig. 1. SEM images of superhydrophobic surfaces made by roughening
fabricated a double-roughened perfluorooctanesulfonate fluorinated materials. (a) The honeycomb-patterned film (top image and cross
(PFOS) doped conducting polypyrrole (PPy) film by a section) cast from a solution of the polymer shown in the inset under humid
conditions [16•] (reproduced by permission of the American Chemical Society).
combination of electropolymerization and chemical polymer- (b) The PPy porous film made by electro- and chemical polymerization and
ization (Fig. 1b). Interestingly, a reversible switching between transition of hydrophobic states (inset) [17••] (reproduced by permission of
superhydrophobicity (doped or oxidized state) and super- Wiley-VCH).
 M. Ma, R.M. Hill / Current Opinion in Colloid & Interface Science 11 (2006) 193–202 195

Fig. 2. SEM images of superhydrophobic surfaces made by roughening silicone-based materials. (a) PDMS surface treated by CO2-pulsed laser [18] (reproduced by
permission of Elsevier); (b) lotus leaf-like PDMS surface by nanocasting [20]; (c) PS-PDMS/PS electrospun fiber mat and the droplets on it [21•]; (d) PS-PDMS surface
cast from a 5 mg/ml solution in dimethylformamide (DMF) in humid air [22]. (Fig. 2b, c and d are reproduced by permission of the American Chemical Society.)

Given the difference in composition and consequent surface
energy between the lotus leaf (paraffinic wax crystals, –CH2–,
30–32 mN/m) and the PDMS replica (–CH3, 20 mN/m), the
similarity of the hydrophobicity obtained is surprising.
Another way to exploit the low surface energy of PDMS is to
use a block copolymer such as poly(styrene-b-dimethylsilox-
ane) (PS-PDMS). For instance, Ma et al. [21•] made a super-
hydrophobic membrane in the form of a nonwoven fiber mat by
electrospinning a PS-PDMS block copolymer blended with PS
homopolymer (Fig. 2c). The superhydrophobicity with WCA of
163° was attributed to the combination of enrichment of PDMS
component on fiber surfaces and the surface roughness due to
small fiber diameters (150 nm to 400 nm). The flexibility,
breathability and free-standing feature of the membrane are of
particular interest in areas such as textile and biomedical appli-
cations. More recently, Zhao et al. [22] prepared a super-
hydrophobic surface by casting a micellar solution of PS-PDMS
in humid air based on the cooperation of vapor-induced phase
separation and surface enrichment of PDMS block (Fig. 2d).
2.3. Organic materials
Although fluorocarbons and silicones are known as hydro-
phobic materials, nature achieves non-wetting and self-cleaning
using paraffinic hydrocarbons. Recently, several groups have
demonstrated superhydrophobic surfaces made from organic
materials. Lu et al. [23•] proposed a simple and inexpensive
method to produce a highly porous superhydrophobic surface of
polyethylene (PE) by controlling its crystallization behavior. WCA
up to 173° was obtained by adding nonsolvent (cyclohexanone) to
the PE/xylene solution to form nanostructured floral-like crystal
structures (Fig. 3a). Jiang et al. [24••] showed that by electrostatic
spinning and spraying a PS solution in dimethylformamide (DMF)
they obtained a superhydrophobic film composed of porous
microparticles and nanofibers as shown in Fig. 3b. Lee et al. [25]
produced vertically aligned PS nanofibers by using nanoporous
anodic aluminum oxide as a replication template in a heat- and
pressure-driven nanoimprint pattern transfer process. As the aspect
ratio of the PS nanofibers increased, the nanofibers could not stand
upright but formed twisted bundles resulting in a three-dimension-
ally rough surface (Fig. 3c) with advancing and receding WCA of
155.8° and 147.6°, respectively.
Other organic materials such as polyamide [26], polycar-
bonate [27] and alkylketene dimer [28] have also recently been
made into superhydrophobic surfaces. Yan et al. [29•] syn-
thesized a poly(alkylpyrrole) film by electrochemical polymer-
ization—the needle-like poly(alkylpyrrole) structures grown
perpendicularly to the surface of the electrode yielded an
environmentally stable superhydrophobicity (Fig. 3d).
2.4. Inorganic materials
Certain inorganic materials have also been made into super-
hydrophobic surfaces. For example, superhydrophobic surfaces
196 M. Ma, R.M. Hill / Current Opinion in Colloid & Interface Science 11 (2006) 193–202

Fig. 3. SEM images of superhydrophobic surfaces by roughening organic materials. (a) Floral-like crystal structures of PE [23•]; (b) PS surface made by electrostatic
spinning and spraying [24••]; (c) aligned PS nanofibers replicated from nanoporous anodic aluminum oxide [25] (reproduced by permission of the American Chemical
Society); (d) double-roughened poly(alkylpyrrole) film made by electrochemical polymerization. Scare bar: 15 μm [29•]. (Fig. 3a, b and d are reproduced by
permission of Wiley-VCH).

have been produced from ZnO [30••,31] and TiO2 [32]. Fig. 4a
shows SEM image of the ZnO nanorods Feng et al. [30••]
synthesized via a two-step solution method. The ZnO nanorod
films were superhydrophobic due to the surface roughness and the
low surface energy of the (001) plane of the nanorods on the surface
of the film as confirmed by X-ray diffraction (see the inset of Fig.
4a). Interestingly, the superhydrophobicity was transformed to
superhydrophilicity upon UV irradiation which generated electron-
hole pairs and resulted in hydroxyl adsorption in the ZnO surface.
Dark storage of the UV irradiated film for 7 days made it
superhydrophobic again. Similarly, they also obtained TiO2
nanorod films with reversibly switchable wettability (Fig. 4b).

3. Making a rough substrate and modifying it with low

surface energy materials

Methods to make superhydrophobic surfaces by roughening

low surface energy materials are mostly one-step processes and
have the advantage of simplicity. But they are always limited to a
small set of materials. Making superhydrophobic surfaces by a

Fig. 4. SEM of superhydrophobic surfaces by roughening inorganic materials.

(a) Aligned ZnO nanorods prepared by a two-step solution approach. The insets
show the XRD pattern and hydrophobicity transition of the nanorod film [30••]
(reproduced by permission of the American Chemical Society). (b) TiO2
nanorod film and a single papilla at high magnification [32] (reproduced by
permission of Wiley-VCH).
 M. Ma, R.M. Hill / Current Opinion in Colloid & Interface Science 11 (2006) 193–202 197

totally different strategy, i.e., making a rough substrate first and
then modifying it with a low surface energy material, decouples
the surface wettability from the bulk properties of the material and
enlarges potential applications of superhydrophobic surfaces.
There are many ways to make rough surfaces, including
those mentioned above such as mechanical stretching, laser/
plasma/chemical etching, lithography, sol–gel processing and
solution casting, layer-by-layer and colloidal assembling,
electrical/chemical reaction and deposition, electrospinning
and chemical vapor deposition. There are also several methods
commonly used to modify the chemistry of a surface. For
example, covalent bonds can be formed between gold and alkyl
thiols. Silanes are often used to decrease the surface energy.
Physical binding, adsorption and coating can also change the
surface chemistry. In this section, we will focus on the important
techniques reported in the past two years to make rough surfaces
(not necessarily from low surface energy materials) and
subsequent modifications of the surface chemistry. Although
many of these studies are directed towards making practical
surfaces, some important model studies are included here also.
3.1. Etching and lithography
Etching is a straightforward and effective way to make rough
surfaces. Different etching methods including plasma etching
[14,33], laser etching [19,34] and chemical etching [35•,36]
have all been used in the past year to fabricate superhydrophobic
surfaces. For example, Teshima et al. [33] obtained a transparent
superhydrophobic surface from a poly(ethylene terephthalate)
(PET) substrate via selective oxygen plasma etching followed by
plasma-enhanced chemical vapor deposition using tetramethyl-
silane (TMS) as the precursor (Fig. 5a). Qian and Shen [35•]
described a simple surface roughening method by dislocation-
selective chemical etching on polycrystalline metals such as
aluminum (Fig. 5b). After treatment with fluoroalkylsilane, the
etched metallic surfaces exhibited superhydrophobicity.
Lithography (e.g. photolithography, electron beam lithogra-
phy, X-ray lithography, soft lithography, nanosphere lithogra-
phy and so on) is a well-established technique for creating large-
area periodic micro-/nanopatterns [37••,38]. Abdelsalam et al.
[39] conducted a systematic study of the wetting of structured
gold surfaces formed by electrodeposition through a template of
submicrometer spheres and discussed the role of the pore size
and shape in controlling wetting (Fig. 5c). Martines et al. [6••]
fabricated ordered arrays of nanopits and nanopillars by using
electron beam lithography and plasma etching. They obtained a
superhydrophobicity with WCA of 164° and hysteresis of 1° for
a surface consisting of tall pillars with cusped tops (see Fig. 5d
for the SEM image) after a hydrophobization with octadecyl-
tricholorosilane. Composite surfaces with superhydrophobic

Fig. 5. Superhydrophobic surfaces produced by etching and lithography. (a) AFM image of the PET surfaces coated with TMS layer after the oxygen plasma treatment
[33] (reproduced by permission of Elsevier). (b) SEM image of the aluminum surfaces etched with a Beck's dislocation etchant for 15 s at room temperature and the
shape of a droplet on the surface after fluoroalkylsilane coating (inset) [35•]. (c) SEM image of a gold film electrodeposited through a submicrometer sphere template
[39]. (d) SEM image of the nanopillars after hydrophobization the base diameter of the pillars is about 120 nm [6••]. (Fig. 5b, c and d are reproduced by permission of
the American Chemical Society.)
198 M. Ma, R.M. Hill / Current Opinion in Colloid & Interface Science 11 (2006) 193–202

3.3. Layer-by-layer (LBL) and colloidal assembly

LBL self-assembly is a rich process to fabricate conformal

thin film coatings with molecular level control over film thick-
ness and chemistry using electrostatic interaction and hydrogen
bonding. Recently, LBL process has been used by several groups
to make rough surfaces for superhydrophobicity [45–48]. For
example, Zhai et al. [49••] used an LBL technique to create a
pH-sensitive poly(allylamine hydrochloride)/poly(acrylic acid)
(PAH/PAA) multilayer which formed a honeycomb-like struc-
ture on the surface after an appropriate combination of acidic
treatments. After cross-linking the structure, they deposited
silica nanoparticles on the surface via alternating dipping of the
substrates into an aqueous suspension of the negatively charged
nanoparticles and an aqueous PAH solution, followed by a final
dipping into the nanoparticle suspension. Fig. 7a shows the SEM
image of the resultant hierarchically roughened structures.
Superhydrophobicity was obtained after the surface was modified
by a chemical vapor deposition of (tridecafluoro-1,1,2,2-
tetrahydrooctyl)-1-trichlorosilane followed by a 2 h thermal
annealing. LBL self-assembly could also be combined with
electrochemical deposition to prepare superhydrophobic surfaces
as shown by Zhang et al. [45,46,50•] during the past 2 years.
Assembly from colloidal systems has also been demonstrat-
ed to provide right surface roughness for superhydrophobicity
[51•,52••,53]. Ming et al. [52••] prepared a double roughened
Fig. 6. Superhydrophobic surfaces prepared by sol–gel process. (a) SEM image
of the methyltriethoxysilane (MTEOS) sol–gel foam. The insets: phenolphtha-
lein in water on the sol–gel foam heated to 390 °C (left) and 400 °C (right)
[41••] (reproduced by permission of the Royal Society of Chemistry). (b) AFM
image of sol–gel film containing 30 wt.% colloidal silica. Image area: 5 × 5 μm2;
the inset shows surface condensation of water vapor on this film [42]
(reproduced by permission of the American Chemical Society).

and superhydrophilic patterns have also been reported by Notsu

et al. [40] using photolithography.

3.2. Sol–gel processing

Sol–gel processes have been used to fabricate superhydro-

phobic surfaces from a variety of materials [30••,32,41••,42–44].
In most of these investigations, no post-process hydrophobization
was used for the achievement of superhydrophobicity since the
low surface energy materials were already included in the sol–gel
process. For example, Shirtcliffe et al. [41••] prepared porous
sol–gel foams from organo-triethoxysilanes which exhibited
binary switching between superhydrophobicity and superhydro-
philicity when exposed to different temperatures (Fig. 6a). Hikita
et al. [42] used colloidal silica particles and fluoroalkylsilane as
the starting materials and prepared a sol–gel film with super-
liquid-repellency by hydrolysis and condensation of alkoxysilane
compounds (Fig. 6b). Instead of blending low surface energy
materials in the sols, Shang et al. [43] described a procedure to
make transparent superhydrophobic surface by modifying silica-
based gel films with a fluorinated silane. On a similar note, Wu
et al. [44] made a microstructured ZnO-based surface via a wet- Fig. 7. Double-roughened superhydrophobic surfaces made by (a) layer-by-layer
chemical process and obtained the superhydrophobicity after assembly [49••] and (b) colloidal assembly [52••] (reproduced by permission of
coating the surface with long-chain alkanoic acids. the American Chemical Society).
 M. Ma, R.M. Hill / Current Opinion in Colloid & Interface Science 11 (2006) 193–202 199

Fig. 8. SEM images of the superhydrophobic surfaces made by electrochemical reaction and deposition or chemical bath deposition. (a) Dendritic gold cluster formed
on an ITO electrode modified with a polyelectrolyte multilayer [50•]. (b) Copper surface with dual-scale roughness and the droplet on it (inset) [54•] (reproduced by
permission of Wiley-VCH). (c) The copper surface after electrochemical reaction with sulfur gas [55] (reproduced by permission of the Royal Society of Chemistry).
(d) The BCH-LA nanopin films and the contact angle (inset) [56••]. (Fig. 8a and d are reproduced by permission of the American Chemical Society.)

surface consisting of raspberry-like particles which were made
by covalently grafting amine-functionalized silica particles of
70 nm to epoxy-functionalized silica particles of 700 nm via the
reaction between epoxy and amine groups (Fig. 7b). The surface
became superhydrophobic after being modified with PDMS.
3.4. Electrochemical reaction and deposition
Electrochemical reaction and deposition has been extensively
used to prepare superhydrophobic surfaces. For instance, Zhang
et al. [50•] demonstrated that the surface covered with dendritic
gold clusters, which was formed by electrochemical deposition
onto indium tin oxide (ITO) electrode modified with a poly-
electrolyte multilayer, showed superhydrophobic properties
after further deposition of a n-dodecanethiol monolayer. (See
Fig. 8a for typical structures of the gold clusters.) Shirtcliffe et al.
[54• ] prepared a double-roughened copper surface which
resembled “chocolate chip cookies” by electrodeposition and
patterning technique. Further hydrophobization with fluorocar-
bons yielded a superhydrophobicity with WCA of 160°
(Fig. 8b). Cho's group [55] recently described the fabrication
of lotus leaf-like superhydrophobic metal surfaces by using
electrochemical reaction of Cu or Cu–Sn alloy plated on steel
sheets with sulfur gas, and subsequent perfluorosilane treatment
(Fig. 8c). It is worth mentioning that chemical bath deposition
(CBD) has also been used to make nanostructured surfaces. For
example, Hosono et al. [56••] used this technique to fabricate a
nanopin film of brucite-type cobalt hydroxide (BCH) and
obtained a WCA as high as 178° after further modification of
lauric acid (LA) (Fig. 8d).
3.5. Other methods
Electrospinning is powerful technique to make ultrafine fibers
and has been found by several groups to provide sufficient surface
roughnesses for superhydrophobicity [15,21•,24••,57–59••,60].
Electrospinning a hydrophobic material led to superhydrophobi-
city in one step. Ma et al. [59••] showed that an even higher
superhydrophobicity with WCAs up to 175° could be obtained
by applying a thin layer of conformal coating of a fluorinated
polymer to electrospun mats by initiated chemical vapor de-
position (iCVD). This paper contained also a useful discussion of
the impact of fiber morphology on superhydrophobicity (see
Fig. 9a).
200 M. Ma, R.M. Hill / Current Opinion in Colloid & Interface Science 11 (2006) 193–202
Fig. 9. (a) Superhydrophobic surfaces by modifying electrospun fiber mats with
a fluorinated polymer. The plot shows the effect of fiber morphology on the
contact angles [59••]; (b) SEM image of ZnO-coated CNTs. The insets are a
TEM of a single coated CNT and the contact angle on the surface [63]
(reproduced by permission of the American Chemical Society).
Chemical (or physical) vapor deposition (CVD or PVD) has
been widely used for the modification of surface chemistry as well
as the synthesis of nanostructured surfaces [61–63]. Huang et al.
[63] reported a stable superhydrophobic surface composed of
aligned carbon nanotubes (CNTs) synthesized by chemical vapor
deposition on an Fe–N catalyst layer. The superhydrophobicity
was achieved after a thin layer coating of ZnO (see Fig. 9b).
4. Conclusions and perspectives
This is an active research field with many publications
appearing each month dealing with methods to make super-
hydrophobic surfaces and theoretical understanding of the re-
lationship between surface morphology and wettability/sliding.
Theoretical understanding is maturing with models appearing
capable of dealing with more complex forms of surface mor-
phology. Techniques to make non-wettable solid surfaces using
polymers or sol–gel chemistry have been widely documented.
Other types of surfaces, including flexible membrane forms are
receiving more attention. Making such surfaces in a microfluidic
device will probably be demonstrated shortly. Studies that present
results for other aspects such as drag reduction are just beginning
to appear.
Many studies in this area present only superficial results for
wettability and slip—frequently only a contact angle is cited
without contact angle hysteresis or sliding angle values. Details of
methods used to measure these quantities are often not mentioned.
Though central to this topic, the concept of “roughness” is
difficult to reduce to a model that includes all the diverse forms
found in nature or made in the laboratory. While the simple Cassie
and Wenzel models provide a useful framework to understand
high contact angles, a more detailed model will be necessary to
relate hysteresis to roughness. A recent attempt to broaden the
scope of “roughness” has been made by Nosonovsky and
Bhushan [64]. Contact angles N170° have been reported, for
which the Cassie model calculates about 1% contact between the
water and the solid surface [65]. This seems problematic and
demands direct experimental validation. It is worth noticing that
an alternative view of superhydrophobicity or hysteresis from the
perspective of contact line rather than contact area has been
extensively reported in particular by Oner and McCarthy [66••].
A fundamental question about superhydrophobic surfaces
especially for potential applications is the robustness of the
effect. Theoretical modeling of the transition between the het-
erogeneous wetting (Cassie) state and the homogeneous wetting
(Wenzel) state [67,68], hydraulic pressure experiments [69,70]
and water condensation experiments [71] have been reported in
the past year to provide new insight into this problem. Both
Cheng et al. [71] and Jin et al. [72] found high contact angles
and sticky drops, which challenges the perception that rough
surfaces lead to Cassie states.
Acknowledgments
This research was supported in part by the U.S. Army
through the Institute for Soldier Nanotechnologies, under
Contract DAAD-19-02-D-0002 with the U.S. Army Research
Office. The content does not necessarily reflect the position of
the Government, and no official endorsement should be
inferred. The authors would like to acknowledge the support
of Dow Corning Corporation and many useful discussions with
Gregory Rutledge.
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