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Superhydrophobic materials and coatings: A review

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Rep. Prog. Phys. 78 (2015) 086501 (14pp) doi:10.1088/0034-4885/78/8/086501

Review
Superhy
drophob
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review
John T Simpson1,3,
Scott R Hunter2 and
Tolga Aytug2
1
University of Tennessee,
Knoxville, TW 37996, USA
2
Oak Ridge National
Laboratory, Oak Ridge, TN
37831, USA

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Publishing Ltd
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Rep. Prog. Phys. 78 (2015) 086501 Review

Figure 1. Force diagram of Young’s equation and associated Contact Angle measurement.

Figure 2. Hydrophilic and hydrophobic wetting conditions.

Figure 3. Advancing and receding dynamic contact angles.

about water’s dipole behavior is that water has a tendency

to stick to things, including itself. A surface is classified as
either hydrophilic (loving water) or hydrophobic (scared of
water) by how it interacts, or sticks to water drops. A water
Figure 4. Water drop roll-off angle.
drop will tend to wet a surface that has high surface energy
chemistry (e.g. glass) and will tend to bead-up on a surface Dynamic contact angles (advancing and receding)
that has low surface energy chemistry (e.g. Teflon). If a [4, 47, 48]
water drop has a tendency to stick to itself more than it sticks
to a given surface that surface is called hydrophobic and the Figure 3 shows a water drop on a tilted surface exhibiting
water drop will bead up with a CA greater than 90°. advancing (θa) and receding (θr) contact angles. The differ-
Conversely, if a water drop tends to stick more to a given ence between the advancing and receding CAs is known as
surface than it sticks to itself, that surface is called the contact angle hysteresis (θΔ).
hydrophilic and the drop will have a contact angle of less
than 90°. Note that a water drop that completely wets a
surface will have a contact angle of ~0°, while a drop that Roll-off angle [6, 48]
has no interaction with a surface (no wetting) will bead up
The angle at which a water drop rolls off a tilted flat surface
into a prefect sphere (ignoring gravity) and will have a
is known as the roll-off angle (θR). Generally
contact angle of ~180°. The images in figure 2 show these
superhydrophobic surfaces exhibit roll-off angles less than
conditions.
2
Rep. Prog. Phys. 78 (2015) 086501 Review
5 degrees, but very
high quality superhydrophobic surfaces can exhibit roll-off
angles of less than 1 degree. Figure 4 shows a water drop There are many examples of naturally occurring superhydro-
with a roll-off angle of ~5 degrees. phobic surfaces. These include both plants and insects
surfaces.
Effects of surface roughness or topology on
con- tact angle [49]

If a liquid water drop is placed on a flat, smooth, homoge-

neous surface (substrate), its localized contact angle will
strictly be a function of the liquid’s surface tension and the
surface’s chemistry (surface energy). But, with increased sur-
face roughness, the effective contact angle will either
decrease or increase, depending on the substrate’s surface
chemistry. If the surface chemistry is hydrophilic, then
roughening its surface will decrease its CA. While a surface
with a hydro- phobic surface chemistry will increase its CA
if its surface is roughened. The first sequence shown in
figure 5 below shows a water drop on a hydrophilic cone
spike verses time. It shows the wicking effect of a water drop
in contact with a hydro- philic glass cone spike. The second
sequence in figure 6 shows how a water drop can be repelled
from the cone spike if the cone spike’s surface chemistry is
hydrophobic [11].
Note that the localized contact angle does not change with
time, while the effective contact angle can change
dramatically. In the first case, where the surface chemistry is
hydrophilic, the effective contact angle goes from ~45° to
~0°. And in the case where the surface chemistry is
hydrophobic, the effective con- tact angle goes from ~120° to
~180°. Note that a hydrophilic surface becomes more
hydrophilic and a hydrophobic surface becomes more
hydrophobic when the given surface is rough- ened or its
topography is significantly increased.

Wenzel and Cassie–Baxter regimes [9, 10, 48, 49]

The increase of effective contact angle as a result of surface

roughness and structure topography falls into two regimes,
known as the Wenzel and Cassie–Baxter regimes. While
both regimes describe an increase in contact angle with
increas- ing surface roughness, the Cassie–Baxter regime
comes into effect when there is a trapped air layer within the
roughened or textured surface which causes a substantial
increase in con- tact angle and a significant reduction in roll-
off angle and con- tact angle hysteresis.

Superhydrophobic, ultrahydrophobic [8, 44, 45],

and contact angle hysteresis [48] definitions

When the effective contact angle of water drops is 150° or

higher, the surface is defined as superhydrophobic. The term
ultrahydrophobic has been used to describe a surface that
exhibits both advancing and receding contact angles of
greater than 150°. The difference between advancing and
receding contact angles is referred to as the contact angle
hysteresis [4].

Natural superhydrophobic (SH) surfaces [7, 50, 51]

3
Rep. Prog. Phys. 78 (2015) 086501 Review
be superhydrophobic.

Figure 5. Wicking produced by a hydrophilic surface chemistry

on a spikey surface.

The most notable natural superhydrophobic surface is that

of the lotus leaf. The extreme water repellency exhibited by
lotus leaves is what inspired scientists to initially pursue
research into superhydrophobic phenomena. In fact, the term
‘lotus effect’ is still synonymous with superhydrophobic
behavior. Figure 7 shows another superhydrophobic leaf
from the tennessee state tree, the tulip poplar.

Effects of superhydrophobic surface pinned air

layer [9]

In order for a surface to be superhydrophobic it must

have a high contact angle (θ ⩾ 150°). That generally means
that water drops on the surface have, at least some, air
between them and the surface (i.e. Cassie–Baxter regime
[9]). A high quality superhydrophobic surface will have a
uniform layer of pinned or trapped air that produces a very
high contact angle (approaching 180°), a very low roll-off
angle (approaching 0°), small contact angle hysteresis
(approaching 0°), and will pro- duce an optical mirror effect
when the surface is submerged in water due to total internal
reflections of light reflecting off the pinned air layer.
Figures 8(a) and (b) show the mirror effect on a piece of
wood and a fabric treated with superhydrophobic coatings.
Note that the pinned or trapped air in a high quality
superhydrophobic surface acts as a physical barrier to liquid
water or aqueous solutions but is not a barrier to the air, or
gasses in general. Figure 9 shows a water drop beading up
into a sphere while sitting on a superhydrophobic coated
wire mesh.

Examples of synthetic superhydrophobic surfaces

Engineered and ordered superhydrophobic arrays [1, 11]

Various universities and research institutions [1] have fab-

ricated synthetic superhydrophobic surfaces using micro-
electronics-based photolithography. Figure 10 is an
example a photolithography-based array of silicon rods
fabricated by Bell Labs. The array of one micron diameter
silicon rods were treated with a hydrophobic solution giving
them both the right surface chemistry and micro-structure to
4
 Figure 6. Water repellency produced by a hydrophobic chemistry on a spikey surface.
Figure 7. Tulip poplar leaf showing superhydrophobic behavior.
Figure 8. (a) Left: reflected light from pinned air layer on a
superhydrophobic coated wooden stick. (b) Right: reflected light
from pinned air layer on superhydrophobic fabric.
The result was a superhydrophobic surface with a static con-
tact angle of approximately 160°.
In 2004 researchers at ORNL (Dr John Simpson and Dr
Brian D’Urso) used glass fiber drawing techniques to fabri-
cate an array of glass cone spikes (see figure 11). These
cones had a periodicity of 7 microns and a height of 12
microns [11]. The glass cone array’s surface chemistry was
changed from hydrophilic to hydrophobic by treating the
glass array with a fluorinated silane solution. The silane
solution produced a covalently bonded self-assembled-
monolayer (SAM) on the cones’ surfaces. The treated cone
tips were measured to be less than 10 nm in radius. This
superhydrophobic array of nano- sharp glass cones is the
world’s most water repellent surface ever reported, having a
measured contact angle greater than
Figure 9. Water drop being repelled by superhydrophobic coated
screen door wire mesh. Mess spacing is ~3 mm.
179°. Figure 12 shows an image of a 14 mm diameter glass
disc having approximately 1 million cone spikes surrounded
by water. Note the water meniscus surrounding the disc and
that the SH treated cone array is so water repellent that virtu-
ally no wetting of the disc surface is observed. Researchers at
Oak Ridge National Lab dubbed this phenomena the ‘Moses
effect’.
Engineered disordered superhydrophobic
surfaces [2, 3, 52]
The following micrographs are examples of engineered,
disordered, nanotextured surfaces which are initially
 Figure 10. Superhydrophobic silicon post array.

Figure 13. Nanotextured silica formed from etched phase

separating borosilicate glass.

Figure 11. Glass cone spike array.

Figure 14. Nano-textured fluorinated polymer strands.

Figure 12. ‘Moses Effect’ Image. Superhydrophobic 14 mm

diameter disc having ~1 million cone spikes.

superhydrophilic, but become superhydrophobic when

their surface chemistries are changed from hydrophilic to
hydrophobic by treating the surfaces with a hydrophobic
self-assembled-monolayer (SAM). Figure 13 shows superhy-
Figure 15. Micrograph image of diatomaceous earth.
drophobic nano-structured and nano-porous silica produced
by differential etching phase separated borosilicate glass
[3, 37]. This nano-textured superhydrophobic structure has silicon wafer. Their random cone spike structure had a static
shown contact angles as high as 178°. Figure 14 shows nano- CA of over 170°.
strands of fluorinated polymers having contact angles of
roughly 145°. Note that these polymer strands are easily mat-
Superhydrophobic diatomaceous earth [12]
ted down. When that happens the CA is quickly reduced to
below 130°. Researchers from UCLA [2] fabricated a
Figure 15 is a micrograph of diatomaceous earth (DE).
random array of cone spikes produced by asymmetrically
Diatomaceous earth contains the microscopic skeletal remains
etching a
 angle, superhydrophobic surface requires a hydrophobic

Figure 16. SHDE Contact Angle of ~170°. 5 μl water drop.

of a class of phytoplankton known as diatoms. Diatoms have

a unique feature in that their skeletons are formed of
hydrated silicon dioxide. DE is a natural and plentiful silica-
based material which is easily mined throughout the entire
world. It has both micro and nano-porosity and a nano-
roughness that greatly increase either its water absorption or
its water repel- lency, based on its surface chemistry. Since
its natural surface chemistry is hydrophilic, it is naturally
superhydrophilic. But, if DE is treated with a hydrophobic
silane, it becomes super- hydrophobic because of its
hydrophobic surface chemistry and the amplification effect
of its texture and nano-porosity. This superhydrophobic
nano-porous powder is called super- hydrophobic
diatomaceous earth, or simply SHDE. A surface consisting
of SHDE powder has a typical contact angle of from 160° to
170°, but can be as high as 175° (see figure 16).

Historic limitations of superhydrophobic

surfaces and coatings

For the past ten years or so, researchers have been reporting
on the amazing water repellency behavior of superhydropho-
bic materials and surfaces. But, until recently, none of these
superhydrophobic materials or surface effects made it into
any commercial products. The following is a list of the major
rea- sons why.
1. Cost issues—Except for SHDE, the cost of superhy-
drophobic materials has been relatively high due to the
amount of processing required to create the micro and
nano-structures necessary for superhydrophobic
behavior. For instance, most of the early
superhydrophobic micro and nanostructured surfaces
were produced using pho- tolithography [13–15], which
can itself be a very costly process. But when you
combine the fact that nano-scale photolithography
produces small chip dies that have to be stitched together
in order to cover any significant area, the overall cost and
performance can be prohibitive.
2. Nano structure stability—A high quality, high contact
 surface chemistry with a stable micro and nano topog-
raphy. This is generally not an easy set of requirements
to achieve. For instance, polymers with nano-texture
tend to act like ‘wet noodles’ at the nano-scale (see
figure 14). These polymer strand ‘wet noodles’ tend to
be easily matted down and thus quickly lose their
superhydro- phobic behavior [16].
3. Durability issues- Even if you use high quality superhy-
drophobic particles (like SHDE or functionalized silica
nano-particles), it’s still not easy to bond such particles
to a substrate without significantly degrading or
destroying the superhydrophobic behavior. This tends
to be a classic trade-off condition between durability
and superhydro- phobic behavior [34].
4. Condensation issues—While superhydrophobic
coatings and surfaces repel water, they do not repel
water vapor. If the coating is in a condensation
condition (i.e. the coating temperature is below the dew
point) condensation will occur. When this occurs, the
resulting condensate can result in substantial surface
wetting [17, 18].
5. Impingement issues [22, 23]—The pinned air layer
asso- ciated with superhydrophobic surfaces can be
reduced or eliminated by localized high water pressure.
This can be caused by a localized stream of water or by
simply rub- bing the surface while it is submerged in
water. Because superhydrophobic behavior has
historically been a simple surface effect, any significant
surface impingement quickly produced defective
superhydrophobic behavior at the impingement
location.
Figure 17. Water drop on fully functionalized
superhydrophobic nano-textured silica particles.
Figure 18. Water marbles formed by partially functionalized
6. Surfactant/oil wetting issues—Superhydrophobic behavior
is a result of amplifying (via the surface topography) the
effect of water’s surface tension. If the water’s surface
tension is greatly reduced with a surfactant or with an
oil, superhydrophobic behavior will be greatly reduced
or eliminated and the surface is then easily wetted [24,
25].
Phases of superhydrophobic technology
The previous examples of superhydrophobic materials are
associated with two technology phases of superhydrophobic
surfaces. The first phase deals with basic research of super-
hydrophobic structures conducted at various universities,
national laboratories, and research centers. While this first
phase generated much excitement in the scientific
community, none of the materials were commercially viable
due to either their small scale, lack of durability, or their
poor performance. The second superhydrophobic
technology phase uses some of the first phase materials
(e.g. functionalized nanoparticles [42]) to make
superhydrophobic coatings in a loosely bound top-coat. Note
that this top-coat type of superhydrophobic technology is
strictly a surface effect and is exemplified by Rustoleum’s
‘NeverWet’ product. If the coating’s surface is removed or
damaged, its superhydrophobic behavior is eliminated. While
this technology has proven to be some- what commercially
viable, it is still lacking in applicability and durability.
Recent superhydrophobic technology break- throughs will
likely produce a third and fourth generation of
superhydrophobic/superhydrophilic nano-textured silica particles.
superhydrophobic technologies, which could fulfill the prom-
ise of making superhydrophobic technologies widespread, if
not ubiquitous.
Recent superhydrophobic technology
breakthroughs
Volumetric SH coatings [26–28] (paints, epoxies, and
silicones)
The creation and use of volumetric superhydrophobic coatings
represent a new (third) phase of superhydrophobic technol-
ogy. As of April 2015 there were no commercially available
durable superhydrophobic paints, epoxies, silicones, or other
such superhydrophobic products. That will likely soon change
with the anticipated upcoming introduction of volumetric
superhydrophobic paints and epoxies from some of the lead-
ing US paint companies (estimated to be available in the fall
of 2015). What is meant by ‘volumetric superhydrophobic’ is
a coating that is superhydrophobic throughout the coating’s
entire volume, from its outer surface all the way to the under-
lying substrate. Such a coating will dramatically repel water
even if the coating’s surface gets abraded away. This devel-
opment represents a major breakthrough in superhydrophobic
technology in that it virtually solves superhydrophobic coat-
ings durability problem, which has been the major reason why
superhydrophobic coatings have not achieved widespread
commercial success. This development not only makes
super- hydrophobic coatings much more durable, but it also
expands
the capabilities of superhydrophobic coatings in entirely new
ways (like reducing or eliminating the impingement issues)
The next section will attempt to explain how the creation of
volumetric superhydrophobic came about and the principles
behind it.
Water marbles [29, 46]
Since silica is naturally hydrophilic, nano-textured silica
parti- cles will be super-hydrophilic and are readily wetted
by water drops. If the particles are fully functionalized with a
hydro- phobic silane, the particles will become
superhydrophobic and they will not be wetted by water.
Figure 17 shows a water drop beaded up on such fully
functionalized superhydrophobic par- ticles. But, if the
particles are only partially functionalized, each particle can
simultaneously have both superhydropho- bic and
superhydrophilic areas of behavior. When water drops
interact with these particles, ‘water marbles’ are formed. A
water marble is a drop of water that wets the
superhydrophilic portion of such particles while not wetting
the superhydro- phobic portion of the particles. A water
drop in contact with a large number of such partially
functionalized particles will result in water drops with their
outer surfaces covered with these hydrophilic/hydrophobic
glass particles. The superhy- drophilic portion of the
particles stick to the water drop while its superhydrophobic
portion resides on the outer part of the water drop. Since the
drop’s outer surface is covered with the superhydrophobic
portion of the silica, the water marble itself is
superhydrophobic and will not be wetted by other water
drops. See figure 18.
Resin marbles [26]
The interaction of superhydrophobic nano-textured silica
(e.g. SHDE) with molten powder-coat resins can produce
what researcher at Oak Ridge National Laboratory call ‘resin
marbles’. The powder-coat process uses dry polymer resins
to coat surfaces using an electrostatic process. Once an elec-
trically grounded surface is sufficiently covered with charged
resin particles, the coated surface is placed in an oven where
the resin particles become molten forming a uniformly
coated and cured powder resin surface. A blend of SHDE
and pow- der-coat dry resins will not adversely affect the
electrostatic application process, since the SHDE charges
just like the dry resins particles. But during the curing
process the interac- tion of the SHDE with molten resin acts
much like the water marble forming process in that SHDE
partially wets the resin while most of the SHDE repels the
molten resin. If the pro- portion of SHDE to resin is great
enough (e.g. 25% SHDE to resin), then complete resin
marbles form and the molten resin cures without combining
with other molten resins (see figure 19). The result is a
surface containing cured resin mar- bles that are completely
unbound to other resin marbles or the substrate. If the
proportion of SHDE to resin is reduced (e.g. to 5%) then
much of the molten resins will flow, but will not form a
uniform coating due to the resin-phobic/philic nature of
SHDE. As can be seen from the SEM micrograph image
(figure 20), blended powder coat resins with SHDE can
 Figure 19. ‘Resin marbles’ and close-up image of ‘resin marble’.

Figure 20. Volumetric SH powder coat (left: SEM micrograph showing the micro porosity of the structure. Right: showing the
superhydrophobic behavior of water drops on a 4″ × 4″ superhydrophobic powder coated surface).

Creating a partial resin marble effect paint [28]

If SHDE were to be added to a solvent-based paint, the

Figure 21. Micrograph of volumetric SH paint.
produce a very porous interconnected surface having micro-
porosity due to the limited interaction of the resin marbles.
This micro-porosity extends throughout the entire volume of
the coating. Furthermore, the micro-pore’s outer surfaces are
covered with SHDE which creates a surface nano-porosity
and superhydrophobic effect throughout the entire volume of
the coating.
paint would easily wet the SHDE. As the paint dries, and the
solvent evaporates, the SHDE’s pores and nano-structured
sur- face would be completely filled and covered with the
cured paint. No superhydrophobic behavior would therefore
be pres- ent after the paint dries. But it is possible to create a
volumetric superhydrophobic paint using the same type of
phobic/philic ‘resin marble’ effect. Figure 21 shows such a
paint surface. In order to create the phobic/philic ‘resin
marble’ effect in regular paint one must recreate the same
dual nature of adhea- sion and repulsion of the
superhydrophobic material (in this case SHDE) to the
particular type of paint being used. One way of achieving
this dual repulsion and adheasion particle effect is with the
use of inert solvents, like Fluorinerts (3M brand name). If the
SHDE is first wetted using a low surface energy inert solvent
(like 3M’s Flouroinert), the solvent can effectively protect
the SHDE from being totally engulfed by the paint, thus
keeping its pores and some of its surface free of paint. The
combination of flouroinert and SHDE has the dual adheason
and repulsion characteristic needed to create a pho- bic/philic
‘resin marble’ effect. When the particular paint cures and the
Fluorinert completely evaporates, the result is a volu- metric
superhydrophobic paint having both micro-porosity and
Figure 22. Picture of four different volumetric superhydrophobic paint types. Left to right: water-based latex, water-based acrylic
latex, 1-part epoxy, and oil-based enamel paints on 4″ × 4″ aluminum plates.

nano-porosity throughout its entire volume shown in figure

21. Figure 22 shows four volumetric superhydrophobic
coated plates using different paint types (epoxy paint, oil-
based ena- mal, acrylic latex, and water-based latex paint).

Oleophobic (oil repellant) surfaces using SLIPS [28,

38, 39, 43]

Slippery liquid-infused porous surface(s) (SLIPS) surfaces prevents optical clarity. And, in order to
are surfaces with nano-porosity that have been infused with
low surface energy liquids. These surfaces have shown
exceptional liquid- and ice-repellency, pressure stability and
enhanced optical transparency. It is generally agreed that the
reason why these surfaces are so liquid and ice repellant is
that they cre- ate super-smooth surfaces. One way of
understanding SLIPS behavior is to consider that by infusing
a low surface-energy fluid into a nano-textured and porous
surface, you have effec- tively created a low surface-energy
fluid-modified superhy- drophobic surface. The reason why
a SLIPS surface repels oil has to do with the oil having a
higher surface-energy than the pinned infused fluid. As long
as the low surface-energy fluid remains within the
superhydrophobic nano-texture, any other (higher surface
energy) fluid (like oil or water) will tend to slide off its
surface. Note that a superhydrophobic surface can actually
pin an infused liquid in its pores and on its surface if the
infused liquid and superhydrophobic surface chemistries are
compatible (e.g. if both chemistries are silicon based).

Durable superhydrophobic optical thin films [30–

32] (superhydrophobic technology phase IV)

The fourth phase of superhydrophobic technology will likely

be the development of commercially viable (i.e. durable)
superhydrophobic optical thin films. The three properties
required to make a durable superhydrophobic optical thin
film (namely, durability, optical clarity, and
superhydrophobic behavior) tend to be mutually exclusive
making it inherently difficult to make such a coating. For
instance, superhydropho- bic behavior requires a rough
textured surface which normally scatters light and thus

Figure 23. Micrograph of a nano-textured and nano-porous
volumetric glass thin film surface [33].
make a durable thin film consisting of superhydrophobic
nano- scale or micro-scale particles, a fair amount of binder
(e.g. polyurethane) is required. But, generally binders will
cover and/or fill-in the very pores and textured surfaces
required for superhydrophobic behavior. It is relatively
easy to make a superhydrophobic, optically clear thin film
by either using hydrophobic functionalized silica
Figure 24. SH optical thin film on glass plate covering a business
card.
Figure 25. Water Drop on SH coating.
nanoparticles suspended and dispersed in a solution
containing a small amount of binder (e.g. polyurethane), or
by using a hydrophobic sol-gel process [34]. If such a
solution is uniformly sprayed or applied onto a clear surface
(e.g. glass), the result is a clear superhydrophobic thin film.
Unfortunately, such a film is easily removed with only a
small amount of abrasion.
Recently, researchers at Oak Ridge National Lab (ORNL)
showed that durable, optically transparent, superhydrophobic
thin films are possible using nano-textured and nano-porous-
based thin films instead of the typical fused silica nanopar-
ticle-based thin films. ORNL’s superhydrophobic optical
thin films require a series of process steps that include: glass
sputtering or chemical vapor deposition (CVD), ion milling,
glass phase differential etching, and a hydrophobic silane
treatment. The result of these process steps is a
volumetrically
Figure 26. Half coated periscope window.
superhydrophobic, atomically bonded (durable), optical thin
film. Figure 23 shows a micrograph of such an optical thin
film nano-structured surface. Figure 24 shows a glass plate
with a superhydrophobic optical thin film surface. It is antici-
pated that this technology will be commercially available by
the summer of 2016.
Applications of durable superhydrophobic surfaces
and coatings
With the recent advances in durable superhydrophobic sur-
faces and coatings, there will soon be a large number of exist-
ing products converted into superhydrophobic products. And,
since volumetric superhydrophobic technology adds new superhydropho- bic coatings could greatly reduce or even
functionality to coatings, there will likely be many new eliminate many of the effects of ice storms and aircraft
prod- ucts based on this new functionality. icing. Figure 28, top,

Water repellency

Water repellency is the most obvious application of

superhy- drophobic coatings and surfaces. The complete list
of possible water repellency applications would be
extensive and too long to include in this paper. A partial list
includes clothing that will be both breathable and water
repellant, umbrellas that stayed completely dry, building
materials, paints, epoxies, and silicones. Figure 25 shows a
water drop being repelled and beading up by a
superhydrophobic volumetric painted surface.

Self-cleaning optical windows and lenses [27, 53, 54]

Optically clear superhydrophobic coatings on glasses, win-

dows, and optical lenses will make seeing in foul weather
much easier and cleaning windows will be as simple as
spray- ing them with water. Figure 26 shows a periscope
window that first had its right side coated with an optical
superhydrophobic thin film and then mud was applied to the
entire window. The superhydrophobic area of the window
(right side) repelled the mud and stayed clean, while the
untreated side (left side) gets covered with mud.

Viscous drag reduction [35, 36]

Superhydrophobic paints and epoxies could greatly reduce

the cost of transporting goods by ships and improve the
efficiency of water craft of all kinds due to the reduction of
water drag on the watercraft’s hull. Figure 27 (left and right)
shows a toy boat with and without a thin superhydrophobic
coating on its hull. Notice how high in the water the left
boat sits when it’s treated with a superhydrophobic coating.
While the buoyancy increase produced by coating toy boats
with superhydropho- bic paint doesn’t scale to large
watercraft, there can still be a relatively large viscous water
drag reduction due to the large slip length produced by the
pinned layer of air.
The use of riblets on watercraft is a well-established drag
reduction mechanism. When combined with superhydropho-
bic surfaces significant passive drag reduction is
possible. A recent paper [36] presented by Charlotte Barbier
describes a method to fabricate surfaces that combine both
of these tech- niques in order to increase drag reduction
properties. Samples have been tested with a cone-and-
plate rheometer system, and have demonstrated significant
drag reduction (even in the transitional-turbulent regime). A
sample with 100 μm deep grooves showed drag reduction
from 15 to 20% over a wide range of flow conditions
(including laminar and turbulent regimes), and its slip length
was estimated to be over 100 μm.

Anti-icing [17–21, 38]

Superhydrophobic coatings and oil-modified

 Figure 27. Left: SH coated boat (notice how high the waterline is now), Right: uncoated top boat (note the waterline location).

Figure 28. SH coated power lines in simulated ice storm chamber.

Figure 29. Unfouled oil-modified SH treated 4″ × 4″ epoxy plate. Figure 30. Fouled uncoated 4″ × 4″ epoxy plate.

bottom left, and bottom right shows the results of superhy-

drophobic coatings on power lines in a simulated ice storm.
The uncoated power lines (bottom right) quickly iced over
and developed large icicles, while the superhydrophobic
coatings (bottom left) prevented ice formation and showed
no icicles.
Anti-bio-fouling [37, 38]
Superhydrophobic coatings and oil-modified superhydropho-
bic coatings could reduce or eliminate bio-fouling of ship
hulls, piers, power plant intake systems and other surfaces
Figure 31. Two 6″ × 8″ plates subjected to 1000 h of salt fog chamber testing. Left: shows an epoxy coated plate reference, Right: shows
the same type of plate and coating with a volumetric porous superhydrophobic topcoat. Note that the volumetric superhydrophobic coating
shows no corrosion even though the coating is extremely porous with high permeability.

Figure 32. Left: evaporated seawater in aluminum plate. Right: evaporated seawater in SH treated aluminum plate.

subject to bio-fouling, including barnacles and zebra
mussels. The following pictures show how an oil modified
superhy- drophobic coating can prevent marine bio-fouling.
These two Teflon epoxy plates were submerged in an estuary
at Battelle’s immersion facility in Florida. The plate on the right
(figure 29) was treated with an oil modified
superhydrophobic thin film coating. After three months of
submersion in an aggressive biofouling environment, the
untreated plate (figure 30) was covered with algae and
barnacles. The treated plate showed almost no biofouling
with no barnacle attachment (the light areas are water drops).
the anti-corrosion results get even better [38]. As an example,
figure 31 shows two plates, one coated with an epoxy paint
and one coated with the same epoxy paint which has been
modified to be volumetrically superhydrophobic. Both plates
were placed into a salt-fog chamber and subjected to a salt
fog for 1000 h. While the standard epoxy paint coating
showed heavy corrosion, the volumetric superhydrophobic
epoxy coating showed no corrosion.
Desalination [40, 41]

Evaporative desalination was the first and is generally

Anti-corrosion [26, 28]
Low permeability paint, used as a water and vapor barrier, is
the standard way of protecting metal surfaces from
corrosion. Such paint works well until the paint develops
micro-cracks. At that point, water seeps into the micro-
cracks. From then on the paint, acting as a barrier, actually
holds the water in the micro-cracks, which from that point on
promotes corrosion. Volumetric superhydrophobic coatings
prevent corrosion in an entirely different way. Volumetric
superhydrophobic coat- ings are very porous with very high
permeability. As such, one would believe that these paints
would be terrible at preventing corrosion, but recent salt fog
chamber testing has shown the opposite is actually true. And
when one looks at the low sur- face-energy fluid (oil)-
modified superhydrophobic coatings,
acknowledged to be the easiest way of converting seawater
into freshwater. But virtually all large scale desalination done
in the world uses the more complicated and expensive
method of reverse osmosis desalination. The reason why
evaporative desalination has been abandoned has to do with
the mainte- nance cost involved and corrosive effects of the
salt residue generated by evaporation of saltwater.
Volumetric superhy- drophobic coatings are saltwater-based
corrosion resistant and can greatly reduce or prevent any salt
residue buildup. Therefore it is possible that the use of
volumetric superhy- drophobic coatings could finally make
large scale evaporative desalination commercially viable. As
an example, figure 32 left shows salt residue on an aluminum
pan after seawater was poured into the pan and allowed to
evaporate. Note that the salt residue climbed up and over the
pan and was well bonded
to the pan after evaporation. Figure 32 shows another alumi- ORNL’s superhydrophobic technology licensees
num pan that was first coated with a superhydrophobic coat- Dry Surface Coatings, LLC—Stewart Kennedy
ing before adding seawater and letting it evaporate. After the
salt evaporated, it was noticed that no salt residue climbed up
the pan. In fact, none of the salt actually stuck to the pan, but
instead forming a big salt crystal, which was easily removed
from the pan and discarded.

Summary/observations/predictions

This superhydrophobic materials review paper started off

with the basic nature and characteristics of hydrophobic and
super- hydrophobic behavior and then described four
superhydropho- bic technology phases. The first technology
phase dealt with university, national lab, and corporate
research groups looking into basic properties of
superhydrophobic surfaces and their fabrication using
photolithography. The second superhydro- phobic
technology phase began when the superhydrophobic spray-
on surface-effect coatings became commercially avail- able.
These superhydrophobic surface-effect materials and
coatings produced a lot of scientific and public interest in
superhydrophobic materials, but resulted in a considerable
amount of disappointment when the materials were shown
to be either too expensive or lacked adequate durability. This
paper describes a third and fourth superhydrophobic technol-
ogy phase beginning in 2015 with the introduction of volu-
metric durable superhydrophobic paints, quickly followed by
the introduction of durable and transparent superhydrophobic
optical thin films. It is this author’s belief that the
commercial introduction of durable superhydrophobic
coatings, paints, and surfaces will have a dramatic world-
wide effect on nearly every industry and possibly everyone
on earth.

Acknowledgments

I would like to thank the following associates, collaborators,

and funding agencies:
My research team and supportive management while at Oak
Ridge National Lab
Dr B D’Urso
Dr D Hill
Dr J Wadsworth
My research team and supportive management at University
of Tennessee
S McNeany
Dr R Benson
Dr E Drumm
F Tompkins
Funding Agencies for our superhydrophobic technology
research
DARPA—Leo Christodoulou USMC—
Matthew Koch, Forrest Pilgrim
SOCOM—Shawn Martin
US Army—Picatinny Arsenal
DOE—EERE
 United Protective Technologies—Brent Barbee, Marty on ice adhesion and growth on superhydrophobic
Efird Lowes Corp. surfaces
under dynamic flow conditions Colloid Polym. 291 427–35
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Rep. Prog. Phys. 78 (2015) 086501 Review

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