Invited Feature Article

pubs.acs.org/Langmuir

Bioinspired Structured Surfaces

Bharat Bhushan*
Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics, The Ohio State University, Columbus, Ohio 43210-1142,
United States

ABSTRACT: Nature has evolved objects with desired functionality using commonly found
materials. Nature capitalizes on hierarchical structures to achieve functionality. The
understanding of the functions provided by objects and processes found in nature can guide
us to produce nanomaterials, nanodevices, and processes with desirable func-
tionality. Various natural objects which provide functionality of commercial interest have
been characterized to understand how a natural object provides functionality. We have
modeled and fabricated structures in the lab using nature’s route and developed optimum
structures. Once it is understood how nature does it, optimum structures have been fabricated
using smart materials and fabrication techniques. This feature article provides an overview of
four topics: Lotus effect, rose petal effect, gecko feet, and shark skin.

1. INTRODUCTION nature using nanofabrication techniques for commercial applica-

Nature has gone through evolution over the 3.8 billion years
since life is estimated to have appeared on earth. Nature has
evolved objects with desired functionality using commonly
found materials. These function on the macroscale to the molec-
ular scale. The understanding of the functions provided by
objects and processes found in nature can guide us to produce
nanomaterials, nanodevices, and processes with desirable func-
tionality. Biologically inspired design or adaptation or deriva-
tion from nature is referred to as “biomimetics”. It means
mimicking biology or nature. “Biomimetics” is derived from the
Greek word biomimesis. Other words used include bionics,
biomimicry, and biognosis. The field of biomimetics is highly
interdisciplinary. It involves the understanding of biological
functions, structures, and principles of various objects found in
nature by biologists, physicists, chemists, and material scientists
and the design and fabrication of various materials and devices
of commercial interest from bioinspiration.
Biological materials are highly organized from the molecular
scale to the nanoscale, microscale, and macroscale, often in a hierar-
chical manner with intricate nanoarchitecture that ultimately makes
up a myriad of different functional elements. Nature uses commonly
found materials. The properties of the materials and surfaces result
from a complex interplay between the surface structure and the
morphology and physical and chemical properties. Many materials,
surfaces, and devices provide multifunctionality. Molecular scale
devices, superhydrophobicity, self-cleaning, drag reduction in fluid
flow, antifouling, energy conversion and conservation, reversible
adhesion, aerodynamic lift, materials and fibers with high mechanical
strength, biological self-assembly, antireflection, structural coloration,
thermal insulation, self-healing, and sensory aid mechanisms are
some of the examples found in nature which are of commercial
interest.1,2
Various features found in natural objects are on the nanoscale.
The major emphasis on nanoscience and nanotechnology since
the early 1990s has provided a significant impetus in mimicking
tions. Biomimetics has spurred interest across many disciplines.
Various biomimetics-inspired materials and objects are being
fabricated in laboratories around the world, and some have found
industrial applications.
In this feature article, an overview of four topics as shown in
Figure 1 is provided: Lotus effect, rose petal effect, gecko feet,
and shark skin. Each section starts with an introduction fol-
lowed by some recent contributions to the field and a summary
with future directions. The objective of our research is to select
objects from nature which provide functionality of commercial
interest. We characterized natural objects to understand how
they provide functionality, modeled them, and fabricated struc-
tures in the lab using nature’s route and developed optimum
structures using our models. Nature has a limited toolbox
and uses rather basic materials and routine fabrication methods.
Once we understand how nature does it, we then fabricate
optimum structures using smart materials and fabrication
techniques.
2. LOTUS EFFECT
Superhydrophobic surfaces with a high static contact angle above
150° and contact angle hysteresis (the difference between the
advancing and receding contact angles) of less than 10° exhibit
extreme water repellence and self-cleaning properties.3 At a low
value of contact angle hysteresis, water droplets may roll in
addition to sliding, which facilitates the removal of contaminant
particles. Surfaces with low contact angle hysteresis have a low
water roll-off (tilt) angle, which denotes the angle to which a
surface must be tilted for water droplets to roll off. Super-
hydrophobic and self-cleaning surfaces are of interest for vari-
ous applications including self-cleaning windows, windshields,
Received: August 30, 2011
Revised: December 20, 2011
Published: January 10, 2012

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Figure 1. Montage of four examples from nature.
exterior paints for buildings and navigation of ships, utensils, roof
tiles, textiles, solar panels, and applications requiring a reduction
of drag in fluid flow, e.g., in micro/nanochannels. They also
exhibit antifouling which is of interest such as in membranes
used for desalination and water purification. These surfaces
can also be used for energy conversion and energy conserva-
tion. Condensation of water vapor from the environment and/or
process liquid film can form menisci, leading to high adhesion
in devices requiring relative motion.4 Superhydrophobic sur-
faces are needed to minimize adhesion between a surface and a
liquid.
A model surface for superhydrophobicity and self-cleaning is
provided by the leaves of the Lotus plant (Nelumbo nucifera)
(Figure 1, top left).5−9 The leaf surface is very rough due to so-
called papillose epidermal cells, which form asperities or
papillae. In addition to the microscale roughness, the surface of
the papillae is also rough with submicrometer-sized asperities
composed of 3-D epicuticular waxes. The waxes of the Lotus
are tubules, but on other leaves waxes also exist in the form of
platelets or other morphologies. Lotus leaves have hierarchical
structures, which have been studied by Bhushan and Jung.8 The
water droplets on these surfaces readily sit on the apex of the
nanostructures, because air bubbles fill the valleys of the struc-
ture under the droplet. Therefore, these leaves exhibit consider-
able superhydrophobicity. The water droplets on the leaf surfaces
remove any contaminant particles present when they roll off,
leading to self-cleaning. It has been reported that nearly all
superhydrophobic and self-cleaning leaves consist of an intrinsic
hierarchical structure.6 Water on such a surface forms a spherical
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droplet, and both the contact area and the adhesion to the
surface are dramatically reduced.3
Based on the so-called Lotus effect, one of the ways to increase
the hydrophobic property of the surface is to increase surface
roughness, so roughness-induced hydrophobicity has become a
subject of extensive investigations. Wenzel10 suggested a simple
model predicting that the contact angle of a liquid with a rough
surface is different from that with a smooth surface. Cassie and
Baxter11 showed that a gaseous phase including water vapor,
commonly referred to as “air” in the literature, may be trapped in
the cavities of a rough surface, resulting in a composite solid−
liquid−air interface, as opposed to the homogeneous solid−
liquid interface. These two models describe two possible wetting
regimes or states: the homogeneous (Wenzel) and the composite
(Cassie−Baxter) regimes.
2.1. Modeling of Contact Angle for a Liquid in
Contact with a Rough Surface. As stated earlier, super-
hydrophobic and self-cleaning surfaces should have both a high
contact angle and a low contact angle hysteresis. Liquid may
form either a homogeneous interface with a solid or a composite
interface with air pockets trapped between the solid and liquid.
In this section, mathematical models which provide the
relationships between roughness and contact angle are discussed.
2.1.1. Homogeneous (Wenzel) Interface. Consider a rough
solid surface with a typical size of roughness details smaller than
the size of the droplet as shown in Figure 2 (left). For a droplet
in contact with a rough surface without air pockets, referred to
as a homogeneous interface with complete wetting, the contact
angle is given as10
cos θ = R f cos θ0 (1)
where θ is the contact angle for the rough surface, θ0 is the
contact angle for the smooth surface, and Rf is a roughness
factor defined as the ratio of the solid−liquid area ASL to its
projection on a flat plane, AF
ASL
Rf =
AF (2)
The model predicts that a hydrophobic surface (θ0 > 90°)
becomes more hydrophobic with an increase in Rf, and a
hydrophilic surface (θ0 < 90°) becomes more hydrophilic with
an increase in Rf.
2.1.2. Composite (Cassie−Baxter) Interface. For a rough
surface, a wetting liquid will be completely absorbed by the
rough surface cavities while a nonwetting liquid may not pene-
trate into surface cavities, resulting in the formation of air
pockets, leading to a composite solid−liquid−air interface as
shown in Figure 2 (middle). Cassie and Baxter11 extended the
Wenzel equation for the composite interface, which was
originally developed for the homogeneous solid−liquid inter-
face. For this case, there are two sets of interfaces: a solid−
liquid interface with the ambient environment surrounding the
droplet and a composite interface involving liquid−air and
solid−air interfaces. In order to calculate the contact angle for
the composite interface, Wenzel’s equation can be modified by
combining the contribution of the fractional area of wet
surfaces and the fractional area with air pockets (θ = 180°)
cos θ = R f cos θ0 − fLA (R f cos θ0 + 1) (3)
where f LA is the fractional flat geometrical area of the liquid−air
interface under the droplet. In this regime, a hydrophobic
smooth surface can be changed to superhydrophobic with an
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Figure 2. Schematic of a liquid droplet in contact with smooth and rough solid surfaces (left), schematic of the formation of a composite solid−
liquid−air interface for a rough surface (middle), and schematic of a tilted surface (with tile angle α) with a moving liquid droplet (θadv and θrec are
advancing and receding contact angles, respectively), showing the definition of contact angle hysteresis.
increase in Rf but a lower value as compared to that for the
Wenzel regime. Even for a hydrophilic surface, the contact
angle increases with an increase of f LA, and at a high value of
f LA, a surface can become hydrophobic. However, the value of
f LA required may be unachievable, or the formation of air pockets
may become unstable. Using the Cassie−Baxter equation, the
value of f LA at which a hydrophilic surface could turn into a hydro-
phobic one is given as12
R f cos θ0
fLA ≥ for θ0 < 90°
R f cos θ0 + 1 (4)
High Rf can be achieved by both micropatterns and nano-
patterns. For a high f LA, a nanopattern is desirable because
generation of the liquid−air interface depends upon the ratio of
the distance between two adjacent asperities and the droplet
radius. Furthermore, nanoscale asperities can pin liquid droplets
and thus prevent liquid from filling the valleys between
asperities. Transition between Wenzel and Cassie-Baxter
regimes is dependent upon the size of the droplet and the
pitch values of the micro/nanopattern.13
2.1.3. Contact Angle Hysteresis. The contact angle hysteresis
is another important characteristic of a solid−liquid interface. If a
droplet sits over a tilted surface (as shown in Figure 2, right), the
contact angle at the front and back of the droplet corresponds to
the advancing contact angle and the receding contact angle,
respectively. The advancing angle is greater than the receding
angle, which results in contact angle hysteresis. Contact angle
hysteresis occurs due to surface roughness and heterogeneity.
Although for surfaces with the roughness carefully controlled on
the molecular scale it is possible to achieve a contact angle
hysteresis as low as <1°, hysteresis cannot be eliminated com-
pletely, since even atomically smooth surfaces have a certain
roughness and heterogeneity. The contact angle hysteresis is a
measure of energy dissipation during the flow of a droplet along
a solid surface. Surfaces with low contact angle hysteresis have a
very low water roll-off angle, which denotes the angle to which a
surface must be tilted for water droplets to roll off. A low water
roll-off angle is important in liquid flow applications such as in
micro/nanochannels and surfaces with self-cleaning ability.
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Nosonovsky and Bhushan3 derived a relationship for contact
angle hysteresis as a function of roughness, given as
cos θadv0 − cos θrec0
θadv − θrec = (1 − fLA )R f
− sin θ
cos θrec0 − cos θadv0
= ( )
1 − fLA R f
2(R f cos θ0 + 1) (5)
For the homogeneous interface, f LA = 0, whereas for a com-
posite interface f LA is a nonzero number. It is observed from eq
5 that, for a homogeneous interface, increasing roughness (high Rf)
leads to increasing contact angle hysteresis (θadv − θrec), while
for a composite interface, an approach to unity of f LA provides
both a high contact angle and a small contact angle hysteresis.
Therefore, the composite interface is most desirable for super-
hydrophobicity and self-cleaning.
2.1.4. Stability of a Composite Interface and Role of
Hierarchical Structure. Stability of the composite interface is
an important issue.14−17,3 Even though it may be geometrically
possible for the system to become composite, it may be energet-
ically possible for the liquid to penetrate into the valleys between
asperities and form a homogeneous interface.
The formation of a composite interface is a multiscale phenom-
enon which depends upon the relative sizes of the liquid
droplet and roughness details. A composite interface is metas-
table, and its stability is an important issue. Even though it may
be geometrically possible for the system to become composite,
it may be energetically profitable for the liquid to penetrate into
the valleys between asperities and form the homogeneous inter-
face. The composite interface is fragile and can be irreversibly
transformed into the homogeneous interface, thus damaging
superhydrophobicity. Many authors have investigated the stabil-
ity of artificial superhydrophobic surfaces and showed that whether
the interface is homogeneous or composite may depend on the
history of the system, in particular whether the liquid was applied
from the top or condensed at the bottom. Nosonovsky and Bhushan3
have identified mechanisms which lead to the destabilization of the
composite interface, namely, the capillary waves, condensation and
accumulation of nanodroplets, and surface inhomogeneity. They also
reported that a convex surface leads to a stable interface and high
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contact angle. They have suggested the effects of a droplet’s weight
and curvature among the factors which affect the transition. It has
been demonstrated that a combination of microroughness and nano-
roughness (multiscale roughness) with convex surfaces can help to
resist destabilization by pinning the interface. High asperities resist the
capillary waves, while nanobumps prevent nanodroplets from filing
the valleys between asperities and pin them. The effect of roughness
on wetting is scale dependent, and mechanisms that lead to the
destabilization of a composite interface are also scale-dependent. To
effectively resist these scale-dependent mechanisms, it is expected that
a multiscale roughness (such as a hierarchical structure) is optimum
for superhydrophobicity.
2.1.5. Ideal Surfaces with Hierarchical Structure. For
stability of a composite interface, the structure of an ideal hierar-
chical surface is shown in Figure 3. The asperities should be high
Figure 3. Schematic of the structure of an ideal hierarchical surface.
Microasperities consist of circular pillars with diameter D, height H,
and pitch P. Nanoasperities consist of pyramidal nanoasperities of
height h and diameter d with rounded tops.18 Copied with permission
from Phil. Trans. R. Soc.
enough so that the droplet does not touch the valleys. As an
example, for a droplet with a radius on the order of 1 mm or
larger, based on the transition model between the Wenzel and
Cassie−Baxter regimes, a value of H on the order of 30 μm, D
on the order of 15 μm, a P on the order of 130 μm is
optimum.13,18 Nanoasperities can pin the liquid−air interface and
thus prevent liquid from filling the valleys between asperi-
ties. They are also required to support nanodroplets, which may
condense in the valleys between large asperities. Therefore,
nanoasperities should have a small pitch to handle nanodroplets,
less than 1 μm down to a few nanometers in radius. The values
of h on the order of 10 nm and d on the order of 100 nm can be
easily fabricated.
2.1.6. Oleophobic/philic Surfaces. Oleophobic surfaces have
the potential for self-cleaning and antifouling from biological
and organic contaminants both in air and in underwater ap-
plications.19,20 A model for predicting the contact angle of water
and oil droplets has been presented by Jung and Bhushan.20 The
surface tension of oil and organic liquids is lower than that of
water. So, to make the surface oleophobic in a solid-air-oil inter-
face, a material with a surface energy lower than that of oil should
be used. Based on the model, it is found that, for a hydrophilic
surface, an oleophobic surface in the solid−water−oil interface
can be created if γOA cos θO is lower than γWA cos θW. γOA and
γWA are surface tensions of oil−air and water−air interfaces,
respectively, and θO and θW are contact angles when in contact
with oil and water, respectively. For a hydrophobic surface and
an oleophobic surface in a solid−air−oil interface, an oleophobic
surface in solid−water−oil interface can be created if γOA cos θO
is higher than γWA cos θW.
To validate the model for predicting the oleophobic/philic
nature of the surfaces, flat and micropatterned surfaces with
varying pitch values were produced by soft lithography.
n-Pefluoroeicosane (C20F42) with low surface energy (6.7 mN/m)
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was deposited by thermal evaporation to produce superhydro-
phobic and oleophobic flat and micropatterned surfaces. For
water and oil droplets in three-phase interfaces, the experimental
observations showed that there is a good agreement between the
measured contact angle and the predicted values of models. It is
also found that the transition can occur for hydrophobic and
oleophobic micropatterned surfaces with a larger distance bet-
ween pillars.
2.2. Fabrication and Characterization of Micro-, Nano-,
and Hierarchical Structured Surfaces. In this section, we
describe measurements of the wetting properties of micro-,
nano-, and hierarchical structured surfaces fabricated using
different techniques.
2.2.1. Fabrication using Nature’s Route of Hierarchical
Surfaces. We first fabricated hierarchical structured surfaces
using nature’s route. A two-step molding process was used to
replicate microstructures, and the self-assembly of wax platelets
and tubules was used to create different nanostructures. Then,
measurements of the wetting properties of micro-, nano-, and
hierarchical structures fabricated using these techniques were
made.18
A two-step molding process was used to fabricate several
structurally identical copies of a micropatterned Si surface and
Lotus leaves. The technique was used to mold a microstruc-
tured Si surface with pillars of 14 μm diameter and 30 μm
height with 23 μm pitch fabricated by photolithography. This
micropatterned geometry was selected as it provides a super-
hydrophobic surface.18 Before replication of the Lotus leaf, the
epicuticular wax tubules were removed in areas of approximately
6 cm2. To remove the wax, a two-component fast-hardening glue
was applied on the upper side of the leaves and was carefully
pressed onto the leaf. After hardening, the glue with the embedded
waxes was removed from the leaf, and the same procedure was
repeated. A polyvinylsiloxane dental wax was used to create a
negative replica, and epoxy resin was then used to create a positive
replica of microstructured masters. A nanostructure on top of the
microstructure replica was created by self-assembly of synthetic
and plant waxes deposited by thermal evaporation. Tubule
forming waxes, which were isolated from Nelumbo nucifera leaves,
in the following referred to as Lotus, were used to create tubule
structures. After coating, the specimens with the wax were placed
in a desiccator at room temperature for crystallization. For the
plant waxes which are a mixture of aliphatic components, different
crystallization conditions were chosen.
Figure 4 shows the scanning electron microscope (SEM)
micrographs of hierarchical structures with microstructured
replicas covered with a nanostructure of Lotus wax tubules. The
recrystallized Lotus wax shows tubular hollow structures, with
random orientation on the surfaces. Their shapes and sizes show
only a few variations. The tubular diameter varied between 100
and 150 nm, and their length varied between 1500 and 2000 nm.
They have a morphology comparable to that of the Lotus leaf.
To study the effect of various structures on superhydro-
phobicity, static contact angle, contact angle hysteresis, and tilting
angle were measured on flat, microstructured Lotus replica, and
hierarchical surfaces. Additionally, fresh Lotus leaves were inves-
tigated to compare the properties of the fabricated structures with
the original biological model. Figure 5 shows that the hierarchical
structured Lotus leaf replica showed a static contact angle of 171°,
a contact angle hysteresis of 2°, and tilt angles of 1−2°, with
properties most favorable as compared to the micro- and nano-
structures. The fresh Lotus leaf surface investigated here showed a
static contact angle of 164°, a contact angle hysteresis of 3°, and a
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Figure 4. SEM micrographs taken at 45° tilt angle (shown using three magnifications) of hierarchical structure using Lotus replica and
micropatterned silicon pillars and evaporated Lotus wax (0.8 μg/mm2) after storage for seven days at 50 °C with ethanol vapor.18 Copied with
permission from Phil. Trans. R. Soc.
tilting angle of 3°, which suggests that the artificial hierarchical
surfaces showed a higher static contact angle and lower contact
angle hysteresis. The structural differences between the original
Lotus leaf and the artificial Lotus leaf produced here are limited to
a difference in the length of the wax tubules, which are 0.5 to 1 μm
longer in the artificial Lotus leaf.18
Adhesive force measured using a 15 μm radius borosilicate
tip in an atomic force microscope (AFM) also shows a similar
trend as the wetting properties for the artificial surfaces (Figure 5).18
Adhesion force of the hierarchical surface structure was lower than
that of micro- and nanostructured and flat surfaces because the
contact between the tip and surface was lower as a result of the
contact area being reduced. However, for the fresh Lotus leaf,
there is moisture within the plant material which causes softening
of the leaf, and so when the tip comes into contact with the leaf
sample, the sample deforms, and a larger area of contact between
the tip and sample causes an increase in the adhesive force.4
In order to measure the self-cleaning efficiency of hierarchical
structured surfaces, various structures were contaminated using
silicon carbide (SiC) particles in two different size ranges of 1−
10 μm and 10−15 μm.18 For the cleaning test, the specimens
with the contaminants were subjected to water droplets using a
microsyringe. It was reported that the most particles (70−80%)
remained on smooth surfaces, and 50−70% of particles were
found on microstructured surfaces. Most particles were removed
from the hierarchical structured surfaces, but approximately 30%
of the particles remained. A clear difference in particle removal,
independent of particle sizes, was only found in flat and nano-
structured surfaces, where larger particles were removed with
higher efficiency. Observations of the droplet behavior during the
movement on the surfaces showed that droplets were rolling
only on the hierarchical structured surfaces. On flat, micro-, and
nanostructured surfaces, the droplets first applied were not mov-
ing, but the continuous application of water droplets increased
the droplet volume and led to a sliding of these large droplets.
During this, some of the particles had been removed from the
surfaces. However, the rolling droplets on hierarchical structures
did not collect the dirt particles trapped in the cavities of the
microstructures. The data clearly show that hierarchical
structures have superior cleaning efficiency.
All the results presented in this section concerning
superhydrophobicity, adhesion, and self-cleaning show that
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structures created using nature’s route exhibit properties com-
parable to that of Lotus leaves. This suggests that we under-
stand how nature provides functionality.
To simulate impact and oscillation of liquid droplets on
hierarchal structured surfaces such as during rain and vibrating
situations, respectively, bouncing droplet experiments and
vibrating droplet experiments have been performed to investi-
gate the transition from the composite interface to the homo-
geneous interface by Bhushan.9 Bouncing and vibrating droplet
experiments show that, in hierarchical structured and nano-
structured surfaces with certain crystal densities, wetting did
not occur up to 1.5 m/s. In microstructured surfaces, due to the
larger distance between the pillars, composite interface was
destroyed above a certain critical velocity in bouncing droplet
experiments and above a certain inertia force of the droplet on
the surfaces in vibrating droplet experiments.
2.2.2. Mechanically Durable CNT-Composite Hierarchical
Structured Surfaces. Various attempts have been made to
fabricate mechanically durable structures using multiwalled carbon
nanotube (CNT) arrays with high mechanical strength.21−24 A
simpler approach is to use CNT composites. CNT composites
were deposited on flat epoxy resin and a microstructure to create
nano- and hierarchical structures using a spray method. Jung and
Bhushan25 measured the static contact angle and contact angle
hysteresis on nano- and hierarchical structures with CNT. For
static contact angle and contact angle hysteresis, after introducing
the CNT nanostructure on top of the micropatterned Si replica, a
high static contact angle of 170° and low contact angle hysteresis
of 2° were found for the hierarchical structures. Both nano- and
hierarchical structures created with CNT showed superhydropho-
bicity and self-cleaning ability.
To investigate the durability of the nanostructure fabricated
using CNT, Jung and Bhushan25 conducted wear tests by
creating wear scars with a 15 μm radius borosilicate ball using
an AFM for 1 cycle at two normal loads of 100 nN and 10 μN
using AFM. Figure 6 shows surface height maps before and
after wear tests for nanostructures with CNT. As the normal
load of 100 nN was applied on the nanostructure with CNT,
the wear scar induced on the surface was not found or could
not be measured. It was also hard to quantify a wear depth on
the nanostructure with CNT scanned with a borosilicate ball.
With increasing the normal load to 10 μN, it was found that the
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Figure 5. Bar chart showing the measured static contact angle, contact
angle hysteresis, and tilt angle on various structures. The bar chart also
shows adhesive forces for various structures measured using a 15 μm
radius borosilicate tip. Hierarchical structures were fabricated using
Lotus and micropatterned Si replicas superimposed with nanostruc-
tures of Lotus wax tubules. The error bar represents ±1 standard
deviation.18 Copied with permission from Phil. Trans. R. Soc.
wear depth on the nanostructure with CNT was not signi-
ficantly changed, but the morphology of the CNT differed
slightly from that before the wear test. It can be interpreted that
the individual CNT might be expected to slide or bend by the
borosilicate ball applied by high normal load of 10 μN during
the test process.
Ebert and Bhushan26 used a mixture of microscale and nano-
scale SiO2 particles to create hierarchical structure patterns on
flat epoxy substrates. In addition, hierarchical structure was
created by depositing nanoscale SiO2 particles onto micro-
patterned epoxy substrates. The data showed that the structures
are superhydrophobic and self-cleaning with low adhesion and
high mechanical durability.
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Figure 6. Surface height maps before and after wear tests with a 15 μm
radius borosilicate ball at 100 nN and 10 μN for nanostructures with
CNT using an AFM.25 Copied with permission from ACS Nano.
2.3. Summary. Surfaces with micro-, nano-, and hierarchical
structures have been produced by replication of the micro-
structure of a Lotus leaf and by self-assembly of wax platelets
and tubules (Lotus) to create nanostructures. The influence of
micro-, nano-, and hierarchical structures on static contact
angle, contact angle hysteresis, tilt angle and air pocket forma-
tion, adhesive force, as well as efficiency of self-cleaning, has
been studied. It has been shown that for micro-, nano-, and
hierarchical structures, introduction of roughness increased the
hydrophobicity of the surfaces. Micro-, nano-, and hierarchical
structures led to a high static contact angle, e.g., for Lotus wax
on the order of 160°, 167°, and 173°, respectively. Contact
angle hysteresis for the hierarchical structure was the lowest,
about 3°. Structured surfaces provide air pocket formation. For
a hierarchical structure, air pockets inside the grooves under-
neath the liquid reduce the contact area between the liquid and
the surface, resulting in the reduction of contact angle
hysteresis, tilt angle, and adhesive force. Hierarchical structure
provides self-cleaning property even at low tilt angle.
To develop Lotus-inspired mechanical durable surfaces, CNT-
composite and micro- and nanoparticle composite hierarchical
structures have been fabricated. They exhibit high durability for
industrial applications.
3. ROSE PETAL EFFECT
Unlike the Lotus leaf, some rose petals, scallions, and garlic exhibit
superhydrophobicity with high contact angle hysteresis.27−29 While
a water droplet can easily roll off the surface of a Lotus leaf, it stays
pinned to the surface of these leaves. The different behavior of
wetting between the Lotus leaf and the rose petal can be explained
by the different designs in the surface hierarchical micro- and nano-
structure. Since the rose petal’s micro- and nanostructures have a
larger pitch value than the Lotus leaf, the liquid is allowed to impreg-
nate between the microstructure and partially penetrates into the
nanostructure. This is referred to as the Cassie impregnating wetting
regime, in which the wetted surface area is less than that in the
Wenzel regime but greater than that in the Cassie−Baxter regime.
Such an explanation implies that the extent of contact angle hys-
teresis increases with increasing wetted surface area, which is governed
by surface micro- and nanostructures. In the case of scallion and
garlic leaves, contact angle hysteresis is high due to hydrophobic
defects responsible for contact line pinning. Superhydrophobic
surfaces with high adhesion have various potential applications, such
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Figure 7. Bar charts showing the static contact angle and contact angle hysteresis, and adhesive force and coefficient of friction measured using
15 μm radius of borosilicate tip measured on two rose petal surfaces with low and high adhesion (adapted from ref 29).

as the transport of liquid microdroplets over a surface without slid- the superhydrophobic surface with high adhesion due to the
ing or rolling, the analysis of very small volumes of liquid samples, lower real area of contact between the tip and petal sample.
and for the inside of an aircraft surface to minimize the falling of Table 1 presents the surface height parameters for the
condensed water droplets onto passengers. microbumps present on the two leaves. In order to understand
Bhushan and Her,29 for the first time, found that rose petals
can have either low or high adhesion. They measured the static Table 1. Microbump Map Statistics for Rose Petals
contact angle, contact angle hysteresis, adhesive force, and coef- with Superhydrophobicity and High Adhesion
ficient of friction. Based on the understanding of the relevant and Low Adhesion, Measured in Dried Leaves
mechanisms, artificial superhydrophobic surfaces with high and Using AFM29
low adhesions were fabricated.
Peak-to-
3.1. Characterization and Measurement of Two Kinds base (P−B) Peak
of Rose Petals and Their Underlying Mechanism. Figure 1 height Midwidth radius Bump density (1/10 000
(top right) shows optical micrographs of water droplets on the (μm) (μm) (μm) μm2)
Rosa, cv. Bairage petal. As a water droplet is deposited on its Rosa, cv. 6.8 16.7 5.8 23
Bairage
surface, a high static contact angle (152°) is observed on the (High
petal. When the petal is turned upside down, the water droplet adhesion)
does not drop down, which suggests high adhesion. In the case Rosa, cv. 8.4 15.3 4.8 34
of a droplet on the Rosa, cv. Showtime petal (not shown), it Showtime
(Low
also has a high static contact angle (167°), but the droplet easily adhesion)
rolls off the surface with a small tilt angle (6°).
Figure 7 shows the static contact angle, contact angle hysteresis, the mechanisms for the microstructures of the two super-
adhesive force, and coefficient of friction measured using a 15-μm- hydrophobic rose petals with different adhesive force, Figure
radius borosilicate tip in an AFM for two superhydrophobic rose 8 shows schematics of the petals’ hierarchical structures and
petals with high and low adhesion. Both leaves had high contact schematics of water droplet contact with petal surfaces. Pitch
angles, whereas contact angle hysteresis is extremely high for Rosa, value (or bump density) and peak-to-base (P−B) height of
cv. Bairage. microstructures are different in the two petals. On the
The adhesive force of Rosa, cv. Bairage is higher than that of superhydrophobic surface with low adhesion (Rosa, cv.
Rosa, cv. Showtime. Adhesive force arises from several sources: Showtime), its microstructure has a smaller pitch value and a
the presence of a thin liquid film, such as an adsorbed water larger P−B height compared to the superhydrophobic sur-
layer, that causes meniscus bridges to build up around the face with high adhesion (Rosa, cv. Bairage). A smaller value
contacting and near contacting bumps, and real area of contact of the ratio of pitch value (P) and P−B height (H) may lead
and surface energy effects.4 For fresh petals, there is moisture to the Cassie−Baxter regime. If the value of P/H is de-
within the plant material, which causes softening of the petal, creased, it leads to an increase in the propensity of air pocket
and so when the tip comes into contact with the petal sample, formation between microstructures, so the water droplet
the sample deforms, and a larger area of contact between the tip cannot touch its bottom and minimize the contact area be-
and sample causes an increase in the adhesive force. The coef- tween the droplet and the surface, resulting in high static
ficient of friction was measured on petal surfaces at a sliding contact angle, low contact angle hysteresis, and low adhesion.
velocity of 2 μm/s. The coefficient of friction for the super- In the case of the superhydrophobic surface with high
hydrophobic surface with low adhesion is lower than that for adhesion, its large pitch value and small P−B height leads
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Langmuir
Figure 8. Schematic illustrations of petals’ hierarchical structure and schematics of a water droplet contacting petal surfaces. Left column shows the
schematic for Rosa, cv. Bairage with a superhydrophobic and high adhesion surface, and right column shows Rosa, cv. Showtime with a
superhydrophobic and low adhesion.29 Copied with permission from Langmuir.
to a decrease in contact area, and water can penetrate to
the bottom. This is responsible for a decrease in the static
contact angle and an increase in contact angle hysteresis
and high adhesion.
3.2. Fabrication of Surfaces with High and Low
Adhesion. From the understanding of real rose petals, artificial
superhydrophobic surfaces with high and low adhesion were
fabricated by Bhushan and Her.29 The microstructure had 23
and 105 μm pitch values with the same diameter (14 μm) and
height (30 μm). To fabricate the nanostructure, various masses
of n-hexatriacontane were coated on a microstructure. The
nanostructure was formed by three-dimensional platelets of
n-hexatriacontane. Platelets were flat crystals grown perpendicular
to the surface. They were randomly distributed on the surface,
and their shapes and sizes showed some variation. When different
masses (0.1 and 0.2 μg/mm2) of wax were applied, the density of
the nanostructure changed. Different pitch values and masses of
wax were used to provide hierarchical structured surfaces with
high and low adhesion.
The static contact angle and contact angle hysteresis were
studied as a function of the mass of n-hexatriacontane on
hierarchical structures with different pitch values is shown in
Figure 9a. In the surface with a 23 μm pitch value, while the
mass of n-hexatriacontane is changed, there are only small
changes in the static contact angle and contact angle hysteresis
values, which means that they are always in the Cassie−Baxter
wetting regime. Droplets did not adhere with any sample.
On the surface with a 105 μm pitch value, as the mass of
n-hexatriacontane was increased, the static angle increased, and
the surface became superhydrophobic (static contact angle is
152°) at 0.2 μg/mm2 (labeled as regime B2). Contact angle
hysteresis peaked out at 0.1 μg/mm2 to a value of 87° (labeled
as regime A) with a minimum value at 0.2 μg/mm2. The
comparison of regime A is made with regime B1 in the 23 μm
pitch sample at the same mass of the wax.
Figure 9b shows droplets on surfaces with regimes B1, B2,
and A indicated in Figure 9a. For 105 μm, at 0.1 μg/mm2,
there is complete wetting (regime A). The droplet adhered to
the surface at a tilt angle of 90° or turned upside down for
regime A. No air pockets were formed, which is believed to be
responsible for high contact angle hysteresis and high adhesion.
At 0.2 μg/mm2, the proximity of features in the nanostructures
allow air pocket formation leading to low contact angle
hysteresis and low adhesion (regime B2). Air pockets were also
observed in regime B1, responsible for low contact angle
hysteresis and low adhesion.
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Schematics of the effect of nanostructure on the propensity
of air pocket formation are shown in Figure 10 (regime A and
B2 in Figure 9a). When a microstructure has the same pitch
value and a nanostructure has low density (regime A), water
could impregnate between microstructures, but it is still not
completely wetted into the nanostructure, resulting in
increasing static contact angle and adhesion. However, a high
density of nanostructures (regime B2) prevents the transition
from the Cassie−Baxter to the Wenzel regime and an increased
propensity of air pocket formation between micro- and
nanostructures.
3.3. Summary. The fabrication of a superhydrophobic
hierarchical surface with high and low adhesion to mimic the
rose petal consists of a microstructured substrate with two
different pitch values (23 and 105 μm) coated with various
masses of wax (for nanostructure). In the surface with a 23 μm
pitch value, while the mass of n-hexatriacontane is changed,
there are only small changes in contact angle and contact angle
hysteresis values. In the surface with a 105 μm pitch value, high
contact angle hysteresis (87°) with a superhydrophobic (static
contact angle is 152°) state at 0.1 μg/mm2 mass of n-
hexatriacontane is found. When n-hexatriacontane (0.2 μg/
mm2) is applied on the microstructure (105 μm pitch value), a
droplet on the surface also reveals a high static contact angle
(168°) with low contact angle hysteresis (4°), and trapped air
pockets can be seen.
For a microstructure with large pitch values and a small peak-
to-base (P−B) height and a nanostructure with low density,
water could impregnate between microstructures, but it is still
not completely wetted into the nanostructure, resulting in high
contact angle hysteresis and high adhesion while maintaining a
high static contact angle. However, the high density of a
nanostructure even for a larger pitch value may prevent the
transition from the Cassie−Baxter to the Wenzel regime and
may lead to an increased propensity of air pocket formation
between micro- and nanostructures with low adhesion.
4. GECKO FEET
The leg attachment pads of several animals including many
insects, spiders, and lizards are capable of attaching to and
detaching from a variety of surfaces and are used for
locomotion, even on vertical walls or across the ceiling.30,31,9
Biological evolution over a long period of time has led to the
optimization of their leg attachment systems. This dynamic
attachment ability is referred to as reversible adhesion or smart
adhesion.31 The attachment pads of geckos have been the most
widely studied due to the fact that they have the highest body
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Langmuir Invited Feature Article

Figure 9. (a) Static contact angle and contact angle hysteresis measured for hierarchical structures as a function of mass of n-hexatriacontane with
two different pitch values (23 and 105 μm). (b) The left set of images show droplets on hierarchical structures with 23 μm pitch and
n-hexatriacontane (0.1 μg/mm2) (regime B1), and on a hierarchical structure with 105 μm pitch and n-hexatriacontane (0.2 μg/mm2) (Regime B2).
In both cases, trapped air pockets can be observed. The right-hand set of images show a droplet on a hierarchical structure with 105 μm pitch and n-
hexatriacontane (0.1 μg/mm2) (regime A) which shows less trapped air with high adhesion since the droplet does not drop down when the substrate
is vertically inclined or turned upside down (adapted from ref 29).

mass and exhibit the most versatile and effective adhesive

known in nature.
There are two kinds of attachment padsrelatively smooth
and hairy. The first kind are relatively smooth pads, so-called
arolia and euplantulae, which are soft and deformable and are
found in some amphibians, such as tree frogs, torrent frogs,
cockroaches, grasshoppers, and bugs. They are able to attach to
and move over wet or even flooded environments without
falling.32 Tree frog toe attachment pads consist of a hexagonal
array of flat-topped epidermal cells about 10 μm in size separat-
ed by approximately 1-μm-wide mucus-filled channels; the
flattened surface of each cell consists of submicrometer array of
nanopillars or pegs of approximately 100−400 nm diameter.
The toe pads are made of an extremely soft, inhomogeneous
material; epithelium itself has an effective elastic modulus of
about 15 MPa, equivalent to silicone rubber. The pads are per-
manently wetted by mucus secreted from glands that open into
the channels between epidermal cells. They attach to mating
surfaces by wet adhesion.32 They are capable of climbing on
wet rocks even when water is flowing over the surface.33 During
walking, the squeezing is expected to occur rapidly. Torrent
Figure 10. Schematic illustrations of droplets on hierarchical structure
frogs can resist sliding even on flooded surfaces. The surface of with two nanostructures with 0.1 μg/mm2 (top) and 0.2 μg/mm2
their toe pads is similar to that of tree frogs with some changes (bottom) with 105 μm pitch. Mass of n-hexatriacontane changes the
in the structure to handle the large flow of water.34 density of nanostructure (Regime A and B2 in Figure 9(a)). Nano-
The second kind are the hairy types which consist of long structures play an important role in contact area between water and
deformable setae and are found in many insects (e.g., beetles, underlying substrate (adapted from ref 29).

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Langmuir
flies), spiders, and lizards. The microstructures utilized by
beetles, flies, spiders, and geckos have similar structures. As the
size (mass) of the creature increases, the radius of the terminal
attachment elements decreases. This allows a greater number of
setae to be packed into an area, hence increasing the linear
dimension of contact and the adhesion strength.
The attachment pads of geckos have been the most widely
studied due to the fact that they have the higher body mass and
exhibit the most versatile and effective adhesion in nature.35−41
The explanation for the adhesion properties of gecko feet can
be found in the surface morphology of the skin on the toes of
the gecko. The skin is composed of a complex hierarchical
structure of lamellae, setae, branches, and spatulae. Figure 1
(bottom left) shows a SEM micrograph of a gecko foot, show-
ing the hierarchical structure down to the nanoscale.42 Figure 11
shows a schematic of the structure. The gecko attachment
system consists of an intricate hierarchy of structures beginning
with lamellae, soft ridges 1−2 mm in length that are located on
the attachment pads (toes) that compress easily so that contact
can be made with rough bumpy surfaces. Tiny curved hairs
known as setae extend from the lamellae with a density of
approximately 14 000 per square millimeter. These setae are
typically 30−130 μm in length, 5−10 μm in diameter, and are
composed primarily of β-keratin with some α-keratin
component. At the end of each seta, 100 to 1000 spatulae
with typically 2−5 μm in length and a diameter of 0.1−0.2 μm
branch out and form the points of contact with the surface. The
tips of the spatulae are approximately 0.2−0.3 μm in width, 0.5
μm in length, and 0.01 μm in thickness and garner their name
from their resemblance to a spatula.
Figure 11. Schematic of the three layer hierarchy of gecko seta with three levels of branches: seta level, middle level, and spatula level. ρ represents
the number of spatulae.31 Copied with permission from J. Adhesion Sci. Technol.
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The attachment pads on two feet of the Tokay gecko have an
area of about 220 mm2. About three million setae on their toes
that branch off into about three billion spatula on two feet can
produce a clinging ability of about 20 N (vertical force required
to pull a lizard down a nearly vertical (85°) surface)40 and allow
them to climb vertical surfaces at speeds over 1 m/s with the
capability to attach and detach their toes in milliseconds.
In isolated setae, a 2.5 μN preload yielded adhesion of 20 to
40 μN, and thus the adhesion coefficient, which represents
the strength of adhesion as a function of preload, ranges from 8
to 16.43
4.1. Adhesion Mechanisms. It is known that van der
Waals attraction is the dominant adhesion mechanism. Typical
rough, rigid surfaces are able to make intimate contact with a
mating surface only over a very small portion of the per-
ceived apparent area of contact. In fact, the real area of
contact is typically 2 to 6 orders of magnitude less than the
apparent area of contact.44,45,4 Autumn et al.46 proposed that
divided contacts serve as a means for increasing adhesion.
The surface energy approach can be used to calculate adhe-
sion force in the dry environment in order to calculate the
effect of division of contacts. Spatula is considered as a hemi-
sphere with radius, R, adhesion force of a single contact, Fad,
based on the so-called JKR (Johnson-Kendall-Roberts) theory47
is given as
3
Fad = πWadR
2 (6)
where Wad is the work of adhesion (units of energy per unit
area). Equation 6 shows that adhesion force of a single contact
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Langmuir Invited Feature Article

is proportional to a linear dimension of the contact. For a

contact area divided into a large number of contacts or setae, n,
the radius of a divided contact, R1, is given by R1 = R/√n (self-
similar scaling).48 Therefore, the adhesion force of eq 6 can be
modified for multiple contacts such that

3 ⎛ R ⎞
F ′ad = πWad⎜ ⎟n = n Fad
2 ⎝ n⎠ (7)

where F′ad is the total adhesion force from the divided contacts.
Thus, the total adhesive force is simply the adhesion force of a
single contact multiplied by the square root of the number of
contacts.
For contact in a humid environment, the meniscus (or capil-
lary) forces further increase the adhesion force.4 The attractive
meniscus force (Fm) consists of a contribution by both Laplace
pressure and surface tension. The contribution by Laplace pres-
sure is directly proportional to the meniscus area. The other
contribution is from the vertical component of surface tension
around the circumference. This force is proportional to the
circumference, as is the case for the work of adhesion.4
4.2. Peeling. Although geckos are capable of producing
large adhesion forces, they retain the ability to remove their feet
from an attachment surface at will by peeling action. The orien-
tation of the spatulae facilitates peeling. Autumn et al.43 were
the first to experimentally show that the adhesion force of
gecko setae is dependent on the three-dimensional orientation
as well as the preload applied during attachment. Due to this
fact, geckos have developed a complex foot motion during
walking.49,50 First, the toes are carefully uncurled during detach-
ment. The maximum adhesion occurs at an attachment angle of
30°the angle between a seta and the mating surface. The
gecko is then able to peel its foot from surfaces one row of setae
at a time by changing the angle at which its setae contact a
surface. At an attachment angle greater than 30°, the gecko will
detach from the surface.
4.3. Adhesion Enhancement during Contact with
Rough Surfaces. Geckos are able to climb and remain attached
to surfaces with different roughnesses ranging from smooth glass
windows to painted walls and tree bark. Hierarchical structure pro-
vides adhesion enhancement during contact with rough surfaces.
In order to study the effect of the number of hierarchical levels in
the attachment system on attachment ability, models with one,
two, and three levels of hierarchy were simulated (Figure 12).31
Figure 13 shows the calculated spring force−distance curves for
the one-, two-, and three-level hierarchical models in contact
with rough surfaces of different values of root-mean-square (rms)
amplitude σ ranging from σ = 0.01 μm to σ = 30 μm at an applied
load of 1.6 μN, which was derived from the gecko’s weight. When
the spring model is pressed against the rough surface, contact
between the spring and the rough surface occurs at point A; as the
spring tip presses into the contacting surface, the force increases
up to point B, B′, or B″. During pull-off, the spring relaxes, and the
spring force passes an equilibrium state (0 N); tips break free of
adhesion forces at point C, C′, or C″ as the spring moves away
from the surface. The perpendicular distance from C, C′, or C″ to
zero is the adhesion force. The data show that adhesion forces for
various levels of hierarchy are comparable when in contact with a
smooth surface. However, the adhesion force for the three level is
the largest when in contact with a rough surface. Thus, multilevel
hierarchy facilitates adaptability to various rough surfaces.
4.4. Fabrication of Biomimetic Gecko Skin. Based on
the studies reported in the literature, the dominant adhesion
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Figure 12. One-, two-, and three-level hierarchical spring models for
simulating the effect of hierarchical morphology on interaction of a
seta with a rough surface. In this figure, lI, II, III are lengths of
structures, sI is space between spatulae, kI, II, III are stiffnesses of structu-
res, I, II, and III are level indexes, R is radius of tip, and h is distance
between upper spring base of each model and mean line of the rough
profile.31 Copied with permission from J. Adhesion Sci. Technol.
mechanism utilized by gecko and spider attachment systems
appears to be van der Waals forces. The hierarchical struc-
ture involving complex divisions of the gecko skin (lamellae-
setae-branches-spatulae) enable a large number of contacts between
the gecko skin and the mating surface. These hierarchical fibril-
lar microstructured surfaces would be capable of reusable dry
adhesion and would have uses in a wide range of applications
from everyday objects such as adhesive tapes, fasteners, toys,
microelectronic and space applications, and treads of wall-
climbing robots. In the design of fibrillar structures, it is neces-
sary to ensure that the fibrils are compliant enough to easily
deform to the mating surface’s roughness profile, yet rigid
enough to not collapse under their own weight. Spacing
between the individual fibrils is also important. If the spacing is
too small, adjacent fibrils can attract each other through inter-
molecular forces which will lead to bunching. The development
of nanofabricated surfaces capable of replicating this adhesion
force developed in nature is limited by current fabrication
methods. Many different techniques have been used in an
attempt to create and characterize bioinspired adhesive tapes.
Attempts are being made to develop climbing robots using
gecko inspired structures.51
Lee and Bhushan52 fabricated hierarchical-structured super-
hydrophobic surfaces using a porous membrane as a template.
By changing the density and diameter of nanofibers, surfaces
with either Lotus effect or gecko effect could be fabricated.
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Langmuir
Figure 13. Force−distance curves of one-, two-, and three-level
models in contact with rough surfaces with different σ values for an
applied load of 1.6·μN.31 Copied with permission from J. Adhesion Sci.
Technol.
Figure 14 shows the SEM micrographs of selected micro-, nano-,
and hierarchical structures made from polypropylene. The figure
also shows the contact angle, contact angle hysteresis, and
adhesive force data. It can be seen that all structured surfaces are
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Figure 14. SEM micrographs and measured contact angles, contact
angle hysteresis, and adhesion forces of various samples with micro-,
nano-, and hierarchical structures made of polypropylene (adapted
from ref 52).
superhydrophobic governed by air pocket formation on the
surfaces. The oriented fibers of 100 and 600 nm diameter
exhibited the gecko effect (high adhesion) due to their high
fiber densities and large contact areas. Whereas the oriented
fibers of 5 and 14 μm exhibited the Lotus effect due to their
smaller fiber density.
4.5. Summary. The adhesive properties of geckos and other
creatures such as flies, beetles, and spiders are due to the
hierarchical structures present on each creature’s hairy
attachment pads. Geckos have developed the most intricate
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Langmuir
adhesive structures of any of the aforementioned creatures.
The attachment system consists of ridges called lamellae that
are covered in microscale setae that branch off into nanoscale
spatulae, about three billion spatulae on two feet. The so-called
division of contacts provides high dry adhesion. Multiple-level
hierarchically structured surface construction plays an impor-
tant role in adapting to surface roughness bringing the spatulae
in close proximity with the mating surface. These structures, as
well as material properties, allow the gecko to obtain a much
larger real area of contact between its feet and a mating surface
than is possible with a nonfibrillar material. Two feet of a Tokay
gecko have about 220 mm2 of attachment pad area on which
the gecko is able to generate approximately 20 N of adhesion
force. Although capable of generating high adhesion forces, a
gecko is able to detach from a surface at willan ability known
as smart adhesion. Detachment is achieved by a peeling motion
of the gecko’s feet from a surface.
There is a great interest among the scientific community to
create surfaces that replicate the adhesion strength of gecko
feet. These hierarchical fibrillar microstructured surfaces would
be capable of reusable dry adhesion and would have uses in a
wide range of applications from everyday objects such as
adhesive tapes, fasteners, toys, microelectronic and space
applications, and treads of wall-climbing robots.
5. SHARK SKIN
Nature has created ways of reducing drag in fluid flow, evident
in the efficient movement of fish, dolphins, and sharks. The
mucus secreted by fish causes a reduction in drag as they move
through water, and also protects the fish from abrasion by mak-
ing the fish slide across objects rather than scrape and disease
by making the surface of the fish difficult for microscopic
organisms to adhere to.53 It has been known for many years
that, by adding as little as a few hundred parts per million guar,
a naturally occurring polymer, friction in pipe flow can be
reduced by up to two-thirds. The compliant skin of the dolphin
has also been studied for drag reducing properties. By
responding to the pressure fluctuations across the surface, a
compliant material on the surface of an object in a fluid flow
has been shown to be beneficial. Though early studies showed
dramatic drag reduction benefits, later studies have only been
able to confirm 7% drag reduction.54
Another set of aquatic animals which possesses multipurpose
skin is fast-swimming sharks. The skin of fast-swimming sharks
protects against biofouling and reduces the drag experienced by
sharks as they swim through water.55 The tiny scales covering
the skin of fast-swimming sharks, known as dermal denticles
(skin teeth), are shaped like small riblets and aligned in the
direction of fluid flow (Figure 1, bottom right). Shark skin in-
spired riblets have been shown to provide a drag reduction
benefit up to 9.9%.56 The spacing between these dermal den-
ticles is such that microscopic aquatic organisms have difficulty
adhering to the surface. Slower sharks are covered in dermal
denticles as well, but not those which are shaped like riblets or
provide any drag reduction benefit.
5.1. Mechanisms of Fluid Drag. Fluid drag comes in
several forms, the most basic of which are pressure drag and
friction drag. Pressure or form drag is the drag associated with
the energy required to move fluid out from in front of an object
in the flow, and then back in place behind the object. Much of
the drag associated with walking through water is pressure drag,
as the water directly in front of a body must be moved out and
around the body before the body can move forward. The
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Invited Feature Article
magnitude of pressure drag can be reduced by creating strea-
mlined shapes. Friction or viscous drag is caused by the interac-
tions between the fluid and a surface parallel to the flow, as well
as the attraction between molecules of the fluid. Friction drag is
similar to the motion of a deck of cards sliding across a table.
The above discussion of friction drag assumes all neighboring
fluid molecules move in the same relative direction and
momentum transfer occurs between layers of fluid flowing at
different velocities. Fully developed turbulent flow is commonly
said to exhibit complete randomness in its velocity distribution,
but there exist distinct regions within fully developed turbulent
flow that exhibit different patterns and flow characteristics.57
While organization is evident in the viscous sublayer, the layer
closest to the surface, the outer layers of the turbulent boundary
layer are chaotic and disorganized. Much of this chaotic motion
above the viscous sublayer is caused by the outward bursting of
the streamwise vortices that form at the surface in the viscous
sublayer. Streamwise vortices (vortices which rotate about axes
in the direction of mean velocity) dominate the viscous sublayer.
As these vortices rotate and flow along the surface, they naturally
translate across the surface in the cross-flow direction. The
interaction between the vortices and the surface, as well as be-
tween neighboring vortices that collide during translation initiate
bursting motions where vortices are rapidly ejected from the sur-
face and into the outer boundary layers. As vortices are ejected,
they tangle with other vortices and twist such that transient
velocity vectors in the cross-stream direction can become as large
as those in the average flow direction.57 The translation, bursting
of vortices out of the viscous sublayer, and chaotic flow in the
outer layers of the turbulent boundary layer flow are all forms of
momentum transfer and are large factors in fluid drag. Reducing
the bursting behavior of the streamwise vortices is a critical goal
of drag reduction, as the drag reduction possibilities presented by
this are sizable.
A flow visualization technique was used to capture cross-
sectional images, shown in Figure 15, of the streamwise vortex
formations above both flat-plate and riblet surfaces.58 The streaky
structure that was seen in the horizontal cross section was
representative of local average velocity flows and is caused by the
interactions between the neighboring vortices. The average cross-
stream wavelength of these high- and low-speed streaks, the added
widths of one high speed streak and one low speed streak, is equal
to the added diameters of two neighboring vortices and has been
measured at 70−100 wall units.57,59 It is useful to use nondimen-
sional length values to better compare studies performed in dif-
ferent flow conditions. Dimensionless wall units, marked +, are
used for all length scales, which are calculated by multiplying the
dimensional length by Vτ/ν. For example, s+ = sVτ/ν, where s+ is
the nondimensional riblet spacing, s is the dimensional riblet
spacing, ν is the kinematic viscosity, and Vτ = (τ0/ρ)0.5 is the wall
stress velocity, for which ρ is the fluid density and τ0 is the wall
shear stress. The 70−100 wall units data just reported correspond
to a vortex diameter of 35−50 wall units. Flow visualizations
shown in Figure 15 show vortex cross sections and relative length
scales demonstrating vortex diameters smaller than 40 wall units.58
The small riblets that cover the skin of fast-swimming sharks
work by impeding the cross-stream translation of the
streamwise vortices in the viscous sublayer. The mechanism
by which the riblets interact with and impede vortex translation
is complex, and the entirety of the phenomena is not yet fully
understood. On a practical level, impeding the translation of
vortices reduces the occurrence of vortex ejection into the outer
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Langmuir
Figure 15. Turbulent flow visualization of streamwise vortices in a vertical cross-section over flat-plate and riblet surfaces. All experiments were
performed using atomized olive oil in air (adapted from ref 58).
boundary layers as well as the momentum transfer caused by
tangling and twisting of vortices in the outer boundary layers.
In the turbulent flow regime, fluid drag typically increases
dramatically with an increase in surface area due to the shear
stresses at the surface acting across the new, larger surface area.
However, as vortices form above a riblet surface, they remain
above the riblets, interacting with the tips only and rarely
causing any high-velocity flow in the valleys of the riblets. Since
the higher velocity vortices interact only with a small surface
area at the riblet tips, only this localized area experiences high
shear stresses. The low velocity fluid flow in the valleys of the
riblets produces very low shear stresses across the majority of
the surface of the riblet. By keeping the vortices above the riblet
tips, the cross-stream velocity fluctuations inside the riblet
valleys are much lower than the cross-stream velocity fluctua-
tions above a flat plate.58 This difference in cross-stream
velocity fluctuations is evidence of a reduction in shear stress
and momentum transfer near the surface, which minimizes the
effect of the increased surface area.
5.2. Optimization of Riblet Geometry. Most studies are
done by changing the nondimensionalized riblet spacing, s+, by
varying only fluid velocity and collecting shear stress data from
a shear stress balance in a wind tunnel or open flow channel
with oil and water. Measured shear stress is compared to shear
stress over a flat plate and plotted against the calculated s+ value
for the flow conditions. In this manner, a performance curve is
1711
Invited Feature Article
created for a riblet array with a specific set of characteristic
dimensions. The use of nondimensional characteristic dimen-
sions for riblet studies, namely nondimensional spacing, s+, is
important for comparison between studies performed under
different flow conditions. Nondimensionalization accounts for
the change in size of flow structures like vortex diameter, which
is the critical value to which riblets must be matched. Experi-
ments have been carried out with various types of riblets, surface
materials and in air, oil, and water.60−62,56,59 Under the same
nondimensionalized flow conditions, riblet arrays sharing charac-
teristic dimension ratios create similar performance curves whether
they are made of different materials, are tested in different fluids, or
fabricated at a different scale.
Sawtooth, scalloped, and blade riblets shown in Figure 16
have been studied. When comparing the optimal drag reduction
geometries for sawtooth, scalloped, and blade riblets shown in
Figure 16, it is clear that blade riblets provide the highest level
of drag reduction, scalloped riblets provide the second most,
and sawtooth riblets provide the least benefit.
More recently there have been studies which have investigated
the drag reduction properties of riblet-topped shark scales as
both a static structure63 and a flexiblepossibly controllable
member.64 Using the scales molded in epoxy resin from the skin
of the Spiny Dogfish (Squalus acanthias), shown in Figure 17a,
Jung and Bhushan63 have reported a decrease in pressure drop
corresponding to a decrease in fluid dragversus a smooth
dx.doi.org/10.1021/la2043729 | Langmuir 2012, 28, 1698−1714
Langmuir Invited Feature Article

Figure 16. Drag reduction comparison for sawtooth, scalloped, and

blade riblets with optimum h/s values. All experiments were performed
using oil as the test fluid in an open channel (adapted from ref 56).

surface in a rectangular flow cell flow experiment. Pressure drop

from inlet to outlet of a channel is a measure of drag with a large
pressure drop occurring as a result of high drag (Figure 17b). In
addition, some decrease in pressure drop was realized in a similar
experiment using segmented aligned riblets fabricated on acrylic
compared to a smooth acrylic test section (Figure 17b).
5.3. Application of Riblets for Drag Reduction. The
dominant and perhaps only commercial market where riblet tech-
nology for drag reduction is commercially sold is competitive swim- Figure 17. (a) SEM micrographs of shark skin replica patterned in
wear. The general population became aware of shark skin’s drag epoxy and segmented blade-style riblets fabricated from acrylic, and
reduction benefits with the introduction of the FastSkin suits by (b) comparison of pressure drop in a closed rectangular channel
flow over a flat epoxy surface and epoxy with shark skin replica
Speedo in 2004. Speedo claimed a drag reduction of several percent surface and over flat acrylic surface and segmented blade riblets. All
in a static test compared to other race suits. However, given the experiments were performed using water. Data are compared with
compromises of riblet geometry made during manufacturing, it is the predicted pressure drop function for a hydrophilic surface
hard to believe the full extent of the drag reduction. (adapted from ref 63).

1712 dx.doi.org/10.1021/la2043729 | Langmuir 2012, 28, 1698−1714

Langmuir
It is clear that creating surface structures by weaving threads
is difficult. As a result, riblet geometries woven from thread
have limited options of feasible riblet shapes. By the pattern
woven into the FastSkin swimsuits, riblets are formed which
resemble wide blade riblets with small grooves on top. The
larger riblets are formed by the macro weaving pattern, and the
smaller riblets are created by the individual weaves of thread
aligned with the macro riblets. Dean and Bhushan55 reported
that unstretched riblets are tightly packed. As the fabric stret-
ches, the riblet width and spacing increase. The associated de-
crease in h/s ratio depends on the dimensions of each swimmer’s
body, which is another compromising factor in the design.
Riblet thickness is also a factor considered in the design.
Aside from the limitations imposed by the weaving patterns
available, flexibility in the riblet tips will hinder the fabric’s
ability to impede the cross-stream translation of streamwise
vortices. Thicker riblets are probably needed, used for strength, and
cause a decrease in the peak drag reduction capability compared to
thinner riblets.
5.4. Summary. Fluid drag in the turbulent boundary layer
is in large part due to the effects of the streamwise vortices
formed in the fluid closest to the surface. Turbulence and associa-
ted momentum transfer in the outer boundary layers is in
large part due to the translation, ejection, and twisting of these
vortices. Additionally, the vortices also cause high velocities at
the surface which create large shear stresses on the surface. Two
mechanisms of riblet drag reduction are believed to be
dominant. First, riblets impede the translation of the stream-
wise vortices, which causes a reduction in vortex ejection and
outer layer turbulence. Second, riblets lift the vortices off of the
surface and reduce the amount of surface area exposed to the
high velocity flow. By modifying the velocity distribution, riblets
facilitate a net reduction in shear stress at the surface.
Various riblet shapes have been studied for their drag reduc-
ing capabilities, but sawtooth, scalloped, and blade riblets are
most common. By varying flow properties or riblet geometries,
optimization studies have been performed. Drag reduction by
riblet surfaces has been shown to be as high as nearly 10% given
an optimal geometry of h/s ∼0.5 for blade riblets. The
maximum reliable drag reduction provided by scalloped
riblets and sawtooth riblets is about 6% at h/s ∼0.7 and 5%
at α ∼60°, respectively. Commercial applications of riblets
include competition swimsuits, which use a thread-based
riblet geometry.
6. OUTLOOK
The emerging field of biomimetics is already gaining a foothold
in the scientific and technical arena. It is clear that nature has
evolved and optimized a large number of materials and struc-
tured surfaces with rather unique characteristics. Nature capi-
talizes on hierarchical structure using basic materials to provide
functionality of interest. As we understand the underlying mech-
anisms, we can begin to exploit them for commercial appli-
cations. Significant advancements in nanofabrication allow one
to replicate structures of interest in biomimetics using smart
materials. The commercial applications include nanomaterials,
nanodevices, and processes. These include surfaces with
superhydrophobicity, self-cleaning, and low or high adhe-
sion, with reversible adhesion, and low drag surfaces, to
name a few.
1713
■
Invited Feature Article
AUTHOR INFORMATION
Corresponding Author
*E-mail: bhushan.2@osu.edu.
■
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