VISVESVARAYA TECHNOLOGICAL UNIVERSITY

Belagavi -590018

Seminar Report
On

“Superhydrophobic Surface”

Submitted in partial fulfilment for the requirement of the award of the

degree of Bachelor of Engineering in Mechanical Engineering.

Submitted By
Ghanshyam Tiwari
(1RI15ME040)

Under the Guidance of

Prashant H K
Assistant Professor, RRIT

Department of Mechanical Engineering

RR Institute of Technology
RR Layout, Chikkabanavara,
Bengaluru – 560090.
2018-2019
 PKM Educational Trust ®

R. R. Institute of
Technology
Affiliated to VTU Belgaum and Approved by AICTE, New Delhi, Recognized by Govt. of Karnataka,
Accredited by NAAC with ‘B+’
Raja Reddy Layout, Chikkabanavara, Bengaluru – 560090

Department of Mechanical Engineering

Since 1993

CERTIFICATE

Certified that the seminar entitled Superhydrophobic Surface carried out by Mr.
GHANSHYAM TIWARI, USN 1RI15ME040, a bonafide student of R R Institute of
Technology in partial fulfilment for the award of Bachelor of Engineering / Bachelor of
Technology in Mechanical Engineering of the Visvesvaraya Technological University,
Belgaum during the year 2015-2019. It is certified that all suggestions indicated for Internal
Assessment have been incorporated in this Report. The seminar report has been approved
as it satisfies the academic requirements in respect of Seminar prescribed for the said
Degree.

Prashant HK Dr. Channabasavaraj Sandur Dr. MB Manjunath

Asst. Professor Head of Department Principal

 CERTIFICATE

Certified that the seminar entitled “Superhydrophobic Surface” carried out by Mr.
GHANSHYAM TIWARI, USN 1RI15ME040, a bonafide student of R R Institute of
Technology in partial fulfilment for the award of Bachelor of Engineering / Bachelor of
Technology in Mechanical Engineering of the Visvesvaraya Technological University,
Belgaum during the year 2015-2019. It is certified that, he has completed the seminar
satisfactorily

Prashant HK Dr.Channabasavaraj Sandur

Asst. Professor Head of Department

 DECLARATION

I, the undersigned, GHANSHYAM TIWARI, student of 8th semester BE in

Mechanical Engineering, RR Institute of Technology, Bengaluru, hereby declare that the
said technical seminar entitled “Superhydrophobic surface” has been genuinely carried out
by me, and submitted in partial fulfilment for the requirement of the award of BECHELOR
OF ENGINEERING degree in Mechanical Engineering prescribed by Visvesvaraya
Technological University, Belagavi, during the academic year 2018–2019.

Place: Bengaluru GHANSHYAM TIWARI

USN: 1RI15ME040

i
 ACKNOWLEDGEMENT

I would like to acknowledge with much gratitude and thanks for crucial role of my
guide Assistant professor Prashant H K sir who had been aiding his valuable guidance for
preparing this report.

I extend my sincere thanks to Dr. Channabasavaraj S, Head of the Department,

Mechanical Engineering, for his untiring guidance, continuous support and encouragement.

Furthermore, I extend my earnest gratitude and respect to all Teaching and

Nonteaching staff of the department, college and also who have directly or indirectly
supported me for the completion of this report.

Regards,

GHANSHYAM TIWARI

ii
 ABSTRACT
Water fearing surface are called hydrophobic surfaces. The tendency of a surface to
repel a water droplet is called superhydrophobicity. It is the combination of surface
roughness and low-surface-energy modification. A surface is qualified as
superhydrophobic surface only if the surface possesses a high apparent contact angle
(>150°), low contact angle hysteresis (<10°), low sliding angle (<5°). Because of their
versatile use in many applications, such as water-resistant surfaces, antifogging surfaces,
anti-icing surfaces, anticorrosion surfaces etc., many methods have been developed to
fabricate the superhydrophobic surfaces. In this report the fundamental principle of
superhydrophobicity, some of the recent works in preparation of superhydrophobic
surfaces, their potential application and the challenges confronted in their new
applications are reviewed and discussed.

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 CONTENTS

Description Page No.

1. Introduction 1
2. Literature Survey 2
3. Characterization of Superhydrophobic 3-6
Surfaces
4. Methodology 7-15
5. Advantages and Disadvantages 16
6. Application 17-18
7. Challenges 19
8. Conclusion 20
9. References 21

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 Superhydrophobic Surface

Chapter 1

INTRODUCTION
Superhydrophobicity is an effect where roughness and hydrophobicity combine to
generate unusually hydrophobic surfaces, causing water to bounce and roll off as if it were
mercury and is used by plants and animals to repel water, stay clean and sometimes even
to breathe underwater. The effect is also known as “The Lotus Effect” and Ultra
hydrophobicity. The research on superhydrophobic surfaces and the related phenomenon
of high contact angles dates back a long time. On the basis of various experimental data, a
few empirical models have been proposed to illustrate surface wetting properties, such as
the well-known Wenzel and Cassie–Baxter models, which led to the understanding of the
relation between the surface roughness and water repellency. It can be extracted from these
models that the combination of suitable surface roughness and low-surface-energy
materials is responsible for superhydrophobicity Many surfaces in nature are highly
hydrophobic and self-cleaning. The best-known example of a hydrophobic self-cleaning
surface is the leaves of the lotus plant (Nelumbo nucifera). Electron microscopy of the
surface of lotus leaves shows protruding nubs about 20–40 μm apart each covered with a
smaller scale rough surface of epicuticular wax crystalloids. Numerous studies have
confirmed that this combination of micro-meter scale and Nano-meter scale roughness,
along with a low surface energy material leads to apparent WCAs>150°, allow sliding angle
and the self-cleaning effect. Surfaces with these properties are called “superhydrophobic”.

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Chapter 2

LITERATURE SURVEY
 Research on superhydrophobic surfaces received continued but relatively limited
attention before the mid-1990s.
 In 1907, Ollivier observed that contact angles of nearly 180o appeared on surfaces
coated with soot, arsenic trioxide and lycopodium powder. Afterwards, Coghill
and Anderson found in 1923 that after deposition of stearic acids on the rough
surface of galena, this surface showed a high contact angle of about 160o.
 Xi Zhang, a professor of chemistry in 1992 focused on the relation between
contact angles and surface geometry, observations of superhydrophobic
phenomena of Triticum plant leaves, surfaces of ‘ducks’ feathers, and insect
cuticles.
 Barthlott, the discoverer of lotus effect, claimed two things could have caused the
leaf surface to be superhydrophobic: a waxy material and numerous microscopic
bumps. The hydrophobic nature of the waxy material makes the water drops stay
high enough so as to minimize the contact area. This, in turn, increases the contact
angle (the angle between the surfaces of water drop and leaf, in this case), to be
greater than 90o. The bumps take the hydrophobic surface a step further to behave
as superhydrophobic (contact angle greater than 150o). The air trapped between
the spaces of bumps increases the contact angle to be greater than 160o. Because
of the greater contact angle, the drop of water becomes nearly spherical in shape
and rolls across the leaf.
 Since the group at Kao first demonstrated artificial superhydrophobic surfaces in
the mid-1990s, a very large number of clever ways to produce rough surfaces that
exhibit superhydrophobicity have been reported.
 Quere critically discussed the surface chemistry of nonsticking surfaces from the
original papers by Cassie and Wenzel to the present. The lotus plant achieves an
apparent WCAN 160° and nil sliding angle using paraffinic wax crystals
containing predominantly –CH2– groups. Nature does not require the lower
surface energy of – CH3 groups or fluorocarbons to achieve these effects.

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Chapter 3

CHARACTERIZATION OF SUPERHYDROPHOBIC
SURFACE
The characterization of superhydrophobic surfaces is one of the key issues in the
research of superhydrophobic surfaces. Till now, many methods have been developed to
characterize the superhydrophobicity of the surface, such as contact angle, tilt angle and
multi resonance thickness-shear mode sensors (MTSM). Among them, the contact angle
measurement is the main method for the characterization of superhydrophobic surfaces.
When the contact angle (Ɵ) 0<Ɵ < 90, the surface is hydrophilic; when the contact angle
is 90 < Ɵ< 180, the surface is hydrophobic. There is also another opinion of the border
between the hydrophobic and hydrophilic surfaces, which regards 65 as the turning point.
There are numerous studies which define superhydrophobic surfaces as those having
water contact angles close to or higher than 150.

The superhydrophobic states can be further classified considering the contact angle
hysteresis.

3.1 Static Contact Angles of Water:

The static contact angle
measurement of water is often used to
characterize superhydrophobicity. This
phenomenon is caused by the different
fitting modes of the static contact angle,
which are ellipse fitting, circle fitting,
tangent searching, Laplace–Young fitting
and so on the measurements of static contact
angles were carried out by commercial Fig. 3.1
instruments (OCA 20, Data Physics Instruments GmbH, Filderstadt). It should be noted that
the contact angle is influenced by the volume of the water droplet and the gravity force.
superhydrophobic surface under different fitting modes of the static contact angle: (a)
ellipse fitting; (b) circle fitting; (c) tangent searching; (d) Laplace–Young fitting.

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3.1 Contact Angle Hysteresis:

Conventionally, superhydrophobicity means not only a high contact angle, but also
a low hysteresis of the contact angle. The low hysteresis of the contact angle of the
superhydrophobic surface is responsible for the self-cleaning properties, which means that
a water droplet can easily roll off the surface and remove dust from the surface. Self-
cleaning is one of the most important originations of the application and function of
superhydrophobic surfaces. Therefore, many of methods and techniques have been
developed to measure the contact angle hysteresis, including the tilt angle, the
advancing/receding angle, contact angle measurements with surfactant solution, MTSM,
and so on.

3.2 Tilt Angle:

The tilt angle refers to the critical angle between the substrate and the horizontal,
below which the water droplet begins to move upon elevating one end of the substrate.
When the tilt angle of a superhydrophobic surface is lower than 10, it means that this surface
is a self-cleaning surface. It should be pointed out, however, that the tilt angle does not
equal, but reflects, the difference between advancing and receding contact angles. It is
worth pointing out that the combination of micro- and Nano-roughness is helpful for
obtaining surfaces with high contact angle and low tilt angle.

3.3 Contact Angle Measurement with Surfactant Solution:

Using a surfactant solution as a probe to measure contact angle can also reflect the
contact angle hysteresis. Gao and McCarthy and Ferrari et al. have demonstrated that
when adding surfactant molecules to water, the contact angles on some superhydrophobic
surfaces with high hysteresis are decreased. However, for superhydrophobic surfaces with
low hysteresis, the contact angles are similar no matter whether a pure water droplet or a
water droplet with surfactant is used as indicator. Therefore, this method can be used to
distinguish between a self-cleaning surface and a normal superhydrophobic surface.

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3.4 Multi Resonance Thickness-Shear Mode Sensors:

Kwoun and co-workers have introduced a
method, which is called MTSM sensors, to
differentiate superhydrophobic surfaces
exhibiting similar macroscopic contact angles but
different contact angle hysteresis. This measurement
technique work was based on high-frequency shear
acoustic waves generated by a piezoelectric quartz
resonator thickness-shear mode (TSM) sensor to
investigate superhydrophobic surfaces loaded with
liquid media. For the TSM operating in the
frequency range of 1 to 100 MHz, the depth of
penetration is of the order of tens to thousands of Fig. 3.2

nanometres.

When a superhydrophobic surface has a low contact angle hysteresis, the water layer
can only wet the top of the surface and is almost unable to penetrate into the interspaces of
the rough structure. Therefore, the harmonic frequency shift of such a surface is much
smaller than surfaces with higher contact angle hysteresis. Fig. shows Left: Normal
hydrophobic surfaces (contact angle 1) do not have self-cleaning properties. As the surface
is tilted (Ɵ4), the water droplet on such a surface just conveys the dust for a distance along
the surface (Ɵ2 and Ɵ3 are receding and advancing angles, respectively). Right:
Superhydrophobic surfaces have self-cleaning properties. The water droplet rests on the
surface as a spherical shape. When the surface is tilted to a small angle (Ɵ5, the tilt angle),
the water droplet begins to roll off the surface.

3.5 Both Tilt Angle Measurement and MTSM Are Carried Out
on Flat Surfaces:

In order to measure the contact angle hysteresis of a non-planar surface, e.g. gold
thread, which has a larger radius than its tilt angle, they have proposed the following
method. A water droplet hangs from a needle, and then a gold thread is moved to touch

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 Superhydrophobic Surface

the water droplet. If there is almost no contact angle hysteresis, the water droplet just
shifts to one side of the gold thread, but with only a slight deformation of its shape. In
contrast, when there is contact angle hysteresis, the water droplet should adhere to the
surface and cannot move. This fact suggests that the interaction between the water droplet
and the gold thread is much weaker than that between the water droplet and the needle.
Other measurements on contact angle hysteresis. Gao and McCarthy have developed a
method to distinguish the contact angle hysteresis by lowering the superhydrophobic
surface onto a supported droplet and compressing/releasing several times. If the contact
angle hysteresis is low enough, this surface will not adsorb the water droplet after release;
otherwise, a super-hydrophobic surface with high hysteresis has a strong affinity with the
water droplet.

The bouncing drop method is also used to characterize the contact angle
hysteresis. When a liquid drop lands on a solid surface without wetting it, it bounces with
remarkable elasticity. So, the bouncing ability of the water droplet can also reflect the
contact angle hysteresis.

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Chapter 4

METHODOLOGY
Artificial superhydrophobic surfaces are fabricated by combining rough surface
morphology and low-surface-energy coatings. In view of the methods for fabricating
rough surfaces, two general approaches have been developed, including chemical and
physical methods in general. It will be shown that different methods can be used for
fabricating different rough surfaces with their advantages and limitations.

4.1 Wax solidification

Wax solidification was used first by Onda et al. to form a fractal surface. A glass
plate is dipped into melted alkyl ketene dimer (AKD) heated at 90 C, and then cooled
at room temperature in an atmosphere of dry N2 gas. AKD undergoes fractal growth
when it solidifies. AKD is a kind of wax, whose contact angle on a flat surface is 109.
When it forms a fractal surface, the surface wettability changes from hydrophobic to
superhydrophobic with a contact angle as large as 174.59, This is a simple method but
it is limited to a few materials.

4.2 Lithography
Lithography is a useful method for fabricating rough surfaces with regular
structures. For example, O¨ner and McCarthy have employed photolithography to
transfer the patterns of masks onto silicon wafers. Afterwards, a superhydrophobic
surface can be obtained by hydrophobizing the silicon wafer using silanization
chemistry. Chen and co-workers have used the spin-coating of monodisperse
polystyrene beads for lithography to obtain a patterning of large-area periodic
nanosphere arrays. After treatment using oxygen plasma etching, the nanosphere
arrays are coated with 20 nm thick gold film and further modified with octa
decanethiol. In this way, a well ordered, tunable superhydrophobic surface whose
water contact angle can be tuned from 132 to 170 is fabricated. Recently, Nanoimprint
lithography and femtosecond laser pulses have also been developed to form structured
surfaces. Besides the above physical methods, chemical etching is employed for

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surface roughening on polycrystalline metals, such as aluminium, copper, and zinc.

Compared with the physical methods, chemical etching is a simple technique, but it
generates irregular surface structures. In general, the lithography method is too
complicated to form large scale superhydrophobic surfaces.

4.3 Vapor deposition

Carbon nanotube forests are a useful structured matrix for mimicking the lotus
effect and the fabrication of a regular carbon nanotube forest relies on different methods
of chemical vapor deposition (CVD). Although a variety of different methods are
available, plasma enhanced CVD is a technique that produce perfectly aligned and
untangled carbon nanotubes with controlled height and diameter. Lau et al. have created
a superhydrophobic surface using the nanoscale roughness inherent in a vertically
aligned carbon nanotube forest together with a hydrophobic PTFE coating. The
microwave plasma-enhanced CVD, using organosilicon compounds and Ar gas as start
materials at low temperature, has been developed by Wu et al. to prepare ultra-water-
repellent films. The films produced in this way are soft, however, and the mechanical
durability is not satisfied. Then they have improved their method using CO2 as an
additive gas and obtained ultra-water-repellent film with enhanced mechanical
durability. Simple physical vapor deposition (PVD) is also used to generate films of
orderly textured features. For example, superhydrophobic surfaces of n-hexatriacontane
can be obtained directly by PVD.

4.4 Template method

Porous membranes with various diameters can act as templates for the fabrication
of patterned array structures. For example, Jiang et al. have established a simple
extrusion process with an anodic aluminium oxide membrane as the template for the
formation of aligned polyacrylonitrile nanofibers. Aligned nanofibers can be easily
obtained by using templates with different pore diameters, and this process can be
applied to different polymer precursors, such as polyvinyl alcohol. Later on, a simple
‘template rolling press’ method was demonstrated for fabricating well-aligned
polycarbonate nanopillar arrays on a large scale.

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4.5 Polymer reconformation

Polymer reconformation is a simple and inexpensive method for the formation of
rough and porous polymer films, leading to the fabrication of superhydrophobic
surfaces. For example, Erbil et al. selected suitable solvents and temperature to make a
solution of polypropylene for fabrication of a casting film, followed by fast
evaporation of the solvent to roughen the surface. IN this way, a porous gel-like film
was obtained with a contact angle of 160.73. Similar methods can be applied to a
variety of surfaces as long as the solvent mixture does not dissolve the underlying
materials, such as low-density polyethylene and poly (vinyl chloride). Phase
separation can also lead to polymer reconformation which is useful to control the
surface microstructure. For example, Hashimoto et al. have used phase separation of
tetraethyl orthosilicate induced by the addition of an acrylic polymer to fabricate
superhydrophobic thin films with visible light transmission. Later, Xu et al.
demonstrated that a bionic film of micro protuberances covered by a nanostructure of
low-surface-energy polymers can be obtained in a one-step process with the use of
self-aggregation of poly (methyl methacrylate) combined with a nanoscale phase
separation of fluorine-end-capped polyurethane during the solvent evaporation.

4.6 Sublimation
For a sublimable pore-forming material, the sublimation method can be employed
to provide roughness on surfaces. Surface roughness is imparted to boehmite and
silica films by the sublimation of aluminium acetylacetonate (AACA) during
calcination, and transparent superhydrophobic films of these materials are prepared by
subsequent coating with fluoroalkyl silane. Moreover, transparent superhydrophobic
thin films with TiO2 photocatalyst are prepared by utilizing a sublimation material
and subsequent coating of a (fluoroalkyl)silane.

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4.7 Electrohydrodynamic/electrospinning
The electrohydrodynamic technique is an effective method for producing micro-
and Nano-fibres or particles from a variety of materials, which is therefore useful for
fabricating superhydrophobic surfaces. By this simple technique, a lotus-leaf-like
porous microsphere-nanofiber composite film is fabricated, affording
superhydrophobicity without any modification. To form electrospinning fibres requires
starting materials with high molecular weight, which can be polymers, sol–gel systems,
and so on.

4.8 Plasma technique

The plasma technique is a simple way to prepare non-wetting surfaces. It can
provide the as-prepared material with surface roughness and low-surface-energy
coatings simultaneously. Washo introduced the plasma polymer vapor polymerization
process to fabricate superhydrophobic surfaces comprised of PTFE coatings. Later, a
series of works to fabricate fluorinated polymer superhydrophobic coatings via plasma
treatment of the surfaces were reported. Because the surface roughness of the coatings
fabricated by plasma treatment is easily tuned, this method is an appropriate way to
prepare superhydrophobic coatings with special optical properties that have strict
requirements on surface roughness.

4.9 Sol–gel processing

The surface roughness of the materials fabricated via the sol–gel method can be easily
tuned through changing the protocol of the method and the composition of the reaction
mixture. Tadanaga et al. have fabricated alumina thin films with a roughness of 20–50 nm
by immersing porous alumina gel films in boiling water. After depositing a layer of
fluorinated silane, the as prepared coatings exhibit superhydrophobic properties. Later, the
sol–gel method was applied to the fabrication of superhydrophobic surfaces by several
groups. It should be noted that by tuning the scale of the surface roughness, the
superhydrophobic coating fabricated by the sol–gel method can be transparent. Therefore,

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the sol–gel method is another candidate for the fabrication of transparent superhydrophobic
surfaces.

4.10 Electrochemical methods

Electrochemical methods are widely used to form rough structures. For example,
we have electrochemically deposited dendritic gold clusters on the matrix of a
polyelectrolyte multilayer. In this experiment, we observed that the surface roughness of
the gold nanostructures depended on the deposition time and the deposition voltage.
Moreover, by taking advantage of the fact that the electrochemical deposition is
independent of the shape and size of the substrate, we have fabricated superhydrophobic
coatings on gold threads, aimed at mimicking the legs of water striders. Similar methods
can be employed to fabricate superhydrophobic surfaces of silver, zinc oxide, and copper.

Besides electrochemical deposition, many other electrochemical methods also have been
used to form superhydrophobic surfaces, such as anodically oxidized methods, non-electric
chemical plating, electrochemical polymerization, and galvanic cell reactions. Our group
has developed a facile route for the fabrication of a stable superhydrophobic surface on p-
silicon wafer substrates through a galvanic cell reaction, which is accomplished by just
immersing silicon wafers into a mixed solution of HF and AgNO3. Moreover, the
morphologies of the silver micro/nanostructures can be controlled by the concentration of
AgNO3, the solution temperature, and the deposition time.

4.11 Bottom-up approach for the fabrication of Nano-arrays

The bottom-up approach has been widely applied in the synthesis of micro/Nano-
array materials. Solution growth and vapor deposition can both be used for the bottom-
up approach. Since there is plenty of air trapped within array structures grown via the
bottom-up approach, the air–solid composite surface that is required by the
superhydrophobicity of the surface wetting can be satisfied. Jiang et al. have
demonstrated that the aligned carbon nanotube (ACNTs) arrays fabricated through
bottom-up growth can be used to form superhydrophobic coatings after modification of
fluorinated silane layer. A similar protocol has been adopted by the same group to
fabricate honeycomb-like and rice-like ACNT structures on the surface to render it

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superhydrophobic. The latter has an anisotropic property that can cause the water
droplet to roll off the surface in a certain direction. With the bottomup approach, some
other array structures, such as aligned ZnO nanorods arrays and lauric acid modified
brucite-type cobalt hydroxide arrays48 have been fabricated to render the wetting
property of the surface superhydrophobic.

4.12 Hydrothermal synthesis

Hydrothermal synthesis is a well-known method for the fabrication of Nano/micro-
scale materials. We have fabricated rose-like microstructures by a direct in-situ
hydrothermal synthesis method. A glass substrate is immersed into a mixture solution
of SiO2: 1/70 Al2O3: 7/20 Na2O: 3/2 methanol: 40 H2O in a Teflon-lined stainless-
steel autoclave and then, the stainless-steel autoclave is sealed and kept at 160 C in a
constant temperature oven for a given time. We observe that the morphology of the as-
prepared zeolite surface is controlled by the reaction time and the composition of the
reactant. Later, our group fabricated a rough organic surface with superhydrophilicity
which was prepared by polymerization and carbonization of glucose.

4.13 Layer-by-layer methods

The layer-by-layer (LbL) technique has been widely to achieve various
Nano-/microstructures, and it has also been used in the fabrication of
superhydrophobic surfaces. The first example of a superhydrophobic coating
created using the LbL technique was reported by Shiratori and co-workers. They
assembled a polyelectrolyte multilayer containing SiO2 nanoparticles through the
LbL process, and then heated the multilayer film to 650 C to create a suitable surface
morphology for superhydrophobicity. Later, Zhang et al. Rubner et al. Schlenoff et
al. and Shen et al. developed the LbL technique further for fabricating various
superhydrophobic surfaces. It should be pointed out that this method can be used to
fabricate superhydrophobic surfaces on non-planar surfaces.

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4.14 Low-surface-energy modifications on rough surfaces

In general, two main approaches have been developed to generate superhydrophobic
surfaces. One is to increase directly the surface roughness of low-surface-energy materials,
as described above; the other is to fabricate a suitable surface roughness with certain
materials and then to modify the as-prepared surface with low-surface-energy materials.
The latter method is no longer limited to low-surface-energy materials but it can extend the
formation of superhydrophobic surfaces to many systems. Till now, various low-surface-
energy coatings (Fig. 4) have been developed to modify organic and inorganic rough
surfaces, leading to fabrication of superhydrophobic surfaces.

4.14.1. Self-assembled monolayer of alkanethiols

Self-assembled monolayers (SAMs) are molecular assemblies that are

formed spontaneously by the immersion of an appropriate substrate into a solution
of an active surfactant in an organic solvent. Alkanethiols is a kind of active
surfactant bearing a hydrophobic alkyl chain and a thiol group as a surface anchor.
Nuzzo and Allara were the first to introduce SAMs of alkanethiols on gold surfaces.
Furthermore, Whitesides et al. developed microcontact lithography to form
patterned surfaces on the basis of SAMs for adjusting the surface wetting properties.
We have employed n-dodecanethiol to modify the rough surface of gold or silver
aggregates, fabricated by electrochemical deposition. This experiment shows that
the contact angles can reach around 156 with a droplet of 4 mL after modification
by SAMs of n-dodecanethiol on the silver aggregates.

Fig. 4.14.1 (a)

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Examples of surface reactive molecules for low-surface-energy modifications. From

left to right: long alkyl chain thiols, long alkyl chain Thiols bearing benzoic acid
(MUABA), alkyl or fluorinated organic silanes, long alkyl chain fatty acids, and alkyl
chain modified aromatic azides.

Fig. 4.14.1 (b)

The introduction of the low-surface-energy coating can lead to not only the
formation of superhydrophobicity but also the fabrication of a superhydrophobic
surface which is responsive to the environment. For example, we have designed and
synthesized a new surface reactive molecule, an alkanethiol bearing a benzoic acid
group (MUABA). The change of conformation may be essential for the large change
of contact angle with PH. Under PH 1 conditions, the non-polar phenyl groups of
the monolayer are likely to be located at the outermost surface of the MUABA
SAMs in contact with water; under pH 13 conditions, the carboxylic acid groups
ionize, inducing a change in the monolayer arrangement exposing the carboxylate
groups to the water phase. After modification of the rough surface with this
compound, it exhibits large changes in contact angle as a function of the pH, from
nearly superhydrophobic to superhydrophilic, as shown in Fig. above.

4.14.2. Self-assembled monolayer of organic silanes:

SAMs of organic silanes were first introduced by Sagiv. Taking advantage

of the hydrophobicity of its alkyl chain, an organic silane was used to modify
surfaces bearing hydroxyl groups, such as silicon wafers, glass slides, silicon

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nanoparticles and zeolite, to create low-surface-energy coatings. For example, we

have shown that after modification of a SAM of octyltrimethoxysilane on the
surface of rose-liked microstructures, the surface wetting can undergo a remarkable
change from superhydrophilicity to superhydrophobicity with a contact angle as
high as 154 and a tilt angle lower than 3. Besides alkyl silanes, perfluorinated silanes
are also widely used to adjust the surface wetting properties.

4.14.3. Self-assembled monolayer of fatty acids

Fatty acid is another important active surfactant to obtain low surface-energy

coatings in the fabrication of superhydrophobic surfaces. Zhou and co-workers have
used lauric acid to modify the surface of brucite-type cobalt hydroxide, and obtained
a superhydrophobic surface. By modifying copper surfaces with fatty acids bearing
different lengths of alkyl chain, surface wetting ability with different contact angles
can be obtained.

4.14.4. Surface modification with aromatic Azide

Although the above three SAM methods can be used to introduce low-
surface-energy coatings on many rough substrates, they are all difficult to apply on
organic surfaces. We have developed a simple and convenient method to provide
stable low-surface-energy coatings on organic surfaces, by use of surface-reactive
molecule of 4-azido-Ndodecylbenzamide. This molecule bears an alkyl chain as a
hydrophobic tail and an azide group as the reactive surface anchor, which can
anchor to almost all kinds of organic surfaces by surface photoreaction. After the
hydrophobic modification, rough organic surfaces can change their surface wetting
properties from superhydrophilicity to superhydrophobicity.

4.14.5. Spin-coating perfluoro nonane

Besides the above chemical methods, low-surface-energy materials can be directly

spincoated on rough surfaces. Liu and co-workers have obtained superhydrophobic
surfaces of aluminium and its alloys by spin-coating perfluorononane and vinyl
terminated polydimethyl siloxane.

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Chapter 5

ADVANTAGES & DISADVANTAGES

Advantages:
1. Water repellent and dust repellent. Water repellent surface, which is good where
water phobicity is needed like water condensation system, car windshield etc.
2. Protects the material from the corrosion (Acid rain).
3. It prevents the fabrics from wetting.
4. The artificial method of producing superhydrophobic surface is simple.
5. Low cleaning and maintenance requirement.
6. Retains the quality of surface.
7. Ecologically beneficial and biologically safe.
8. Resistant against: Dirt, Algae, Scales etc.

Disadvantages:
1. The only disadvantage of Superhydrophobic surface is that it is bit costly.
2. They are not suitable for large-scale production.
3. Mechanical durability of superhydrophobic surfaces is another critical issue.
4. The precise control of surface protrusions, spacing, size and geometry is crucial to
establish a stable Cassie state and to achieve high liquid repellency.

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Chapter 6

APPLICATION

6.1 Anti-icing
Icephobicity is one area where superhydrophobicity can effectively be applied. For
example, ice adhesion or formation may modify the effective shape of the aircrafts which
in turn modify the aerodynamic properties of air flow. Thus, icing affects the reliability of
aircrafts. Not only is anti-icing essential for aircraft applications, but it can also be
extended for other applications, such as ships, wind turbines, refrigerators, air-
conditioners etc. Icephobicity can be defined as the properties of surfaces that prevent
icing of water, and if ice is formed, weaken adhesion (between ice and surface) for easy
removal. Normal force and/or shear force are the two major elements that allow de-icing,
if ice is formed. Higher contact angle and low contact angle hysteresis are responsible for
normal force and shear force, respectively. In most cases, icephobic surfaces will have the
shear strength between 150 and 500 kPa, although normal stress is also used. The
superhydrophobic surfaces are not always effective as anti-icing materials. Though ice
accretion of superhydrophobic surfaces can be delayed compared to that of flat
hydrophobic surfaces, it damages the surface microstructure gradually during icing and/or
de-icing, reducing the anti-icing properties.

6.1 Self-cleaning surfaces:

The true self-cleaning surface is one that combines superhydrophilicity and
photocatalytic behaviour to break down the dirt and wash it away. The use of the term, self-
cleaning surface, is not appropriate for superhydrophobic surfaces, which are extremely dry
and repel water drops. These surfaces do not actually clean themselves; when the water
drops roll over the surface, they wash away the dirt. Self-cleaning surfaces can be used in
solar applications. Formation of dust particles is a common problem on solar panels that
reduce the solar cell efficiency. Use of transparent self-cleaning surface could prevent the
accumulation of dust particles. A microshell array of PDMS (polydimethylsiloxane) layer,
with a contact angle of 151o and contact angle.

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6.3 Biomedical applications:

Platelet adhesion on artificial material implants may cause blood coagulation and
thrombosis. This leads to functional failure of artificial organ implants, artificial blood
vessels and other medical devices that contact with blood. Blood-compatible materials are
thus required. However, existing materials strongly rely on chemical and biological
treatments and only limited materials are available. If superhydrophobicity is introduced,
nearly all platelets are repelled from artificial implants. Polycarbonate urethane is widely
used in biomedical applications due to its biostability and moderate blood compatibility
and biostability. Sun et al. developed a superhydrophobic material on fluorinated alkyl
side-grouped polycarbonate urethane with carbon nanotubes using the dip coating
method. The contact angle of greater than 163 was achieved. The prepared
superhydrophobic surface showed excellent antiadhesion to platelets and superior blood
compatibility. These superhydrophobic materials may play important role in the future
biomedical applications.

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Chapter 7

CHALLENGES
For industrial applications the methods to fabricate superhydrophobic or
superamphiphobic surfaces need to be reproducible, cheap and scalable. Compared to
superhydrophobic surfaces, it is much more demanding to fabricate overhang structures
that are required to achieve superamphiphobicity. The precise control of surface
protrusions, spacing, size and geometry is crucial to establish a stable Cassie state and to
achieve high liquid repellency. The lower the surface tension of the liquid becomes the
more careful these parameters need to be chosen. The durability of the superhydrophobic
should be high. The coating should resist UV exposure, acidic and basic solutions and
common solvents. This depends mostly on the chemical nature of the coating’s materials.
The most challenging factor for industrial application is the long-term mechanical stability
of the surface. In general, overhang structures show weaker mechanical resistance towards
shearing than pillars or pyramidal shapes. During abrasion, not only the structure will
change its geometry, but also the surface chemistry may change from hydrophobic to
hydrophilic. This increases adhesion and therefore increases contact angle hysteresis.

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Chapter 8

CONCLUSION
In this report, the fundamentals, recent research works, some of the potential
applications and challenges of superhydrophobic surfaces were reviewed. Not only
restricted to water-repellency, researchers have successfully developed superhydrophobic
surfaces for a variety of applications, such as self-cleaning, antifogging, anticorrosion,
antibiofouling, omniphobic, icephobic, water resistant fabrics, drag reduction, biomedical
applications and much more. Since there are a large number of fabrication methods,
producing a superhydrophobic surface is not a problem. However, superhydrophobic
surfaces are not without problems. It is noteworthy to visit the following points for further
investigation.

 With plenty of fabrication methods, producing a superhydrophobic surface is no

surprise, but ensuring robustness of such a surface for a variety of problems and
mechanical durability is a big concern.
 Self-cleaning properties is an already achieved function of a superhydrophobic
surface. The next generation superhydrophobic surfaces must be multifunctional;
that is, they must combine the self-cleaning properties with additional functions,
such as optical transparency, superoleophobicity, Icephobicity, antibiofouling, and
low-cost coating.
 Superhydrophobicity is generally obtained on the outer surface modification, and if
the outer surface is abraded or eroded, superhydrophobicity is lost, and that leads to
disappointments. Volumetric superhydrophobic materials are the ones that show
superhydrophobicity throughout their entire volume, from the outer surface to the
inner surface. No significant research work in volumetric superhydrophobicity was
found until 2015, and investigation should be accelerated toward the development
of volumetric superhydrophobic materials.

They are not suitable for large-scale production. These reasons have prevented
superhydrophobic surfaces from being commercially successful so far. Research should be
directed toward large-scale fabrication methods that use less expensive and environmental
friendly raw materials.

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