A Review On Self-Cleaning Coatings

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A review on self-cleaning coatings

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FEATURE ARTICLE
A review on self-cleaning coatings
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Published on 02 September 2011 on http://pubs.rsc.org | doi:10.1039/C1JM12523K
V. Anand Ganesh,* Hemant Kumar Raut, A. Sreekumaran Nair and Seeram Ramakrishna*
Received 3rd June 2011, Accepted 13th July 2011
DOI: 10.1039/c1jm12523k
This review article summarizes the key areas of self-cleaning coatings, primarily focusing on various
materials that are widely used in recent research and also in commercial applications. The scope of this
article orbits around hydrophobic and hydrophilic coatings, their working mechanism, fabrication
techniques that enable the development of such coatings, various functions like Anti-icing, Electrowetting, Surface switchability and the areas where selfcleaning technology can be implemented.
Moreover, different characterization techniques and material testing feasibilities are also analyzed and
discussed. Though several companies have commercialized a few products based on self-cleaning
coating technology, much potential still remains in this field.
1. Introduction
Many technologies existing in todays world have been derived
from nature. Self-cleaning technology is one amongst them. Many
surfaces in nature exhibit self-cleaning properties. The wings of
butterflies1 and the leaves of plants, such as cabbage and lotus, are
a few examples. Because of the extensive range of applications,
from window glass cleaning, solar panel cleaning and cements to
textiles, this technology received a great deal of attention during
the late 20th century and now numerous research works are going
Healthcare and Energy Materials Laboratories, National University of

Singapore, 2 Engineering Drive 3, Singapore. E-mail: anandganesh@nus.
edu.sg; seeram@nus.edu.sg; Tel: +065 6516 8596
Mr. Anand Ganesh Venkatesan

is pursuing Doctoral Degree at
the National University of Singapore. His present research
work is on self-cleaning hydrophilic and hydrophobic coatings
on glass and solar modules at
Professor
Seeram
Ramakrishnas Healthcare and
Energy Materials (HEM)
Laboratory, NUS. He graduated with a first class honours
degree in Mechatronics EngiV: Anand Ganesh
neering from Anna University,
Chennai. His research interests
include the development of
photochromic and self-cleaning coatings, biomimetic nanostructures, surface modification and solar energy.
16304 | J. Mater. Chem., 2011, 21, 1630416322
on around the world to develop highly efficient and durable selfcleaning coating surfaces with enhanced optical qualities. Apart
from the wide range of applications, this technology also offers
various benefits, which include reduction in maintenance cost,
elimination of tedious manual effort and also reduction in the time
spent in cleaning work.
Self-cleaning coatings are broadly classified into two major
categories: hydrophilic and hydrophobic. Both of the categories
clean themselves by the action of water. In a hydrophilic coating,
the water is made to spread (sheeting of water) over the surfaces,
which carries away the dirt and other impurities, whereas in the
hydrophobic technique, the water droplets slide and roll over the
surfaces thereby cleaning them. However, the hydrophilic coatings using suitable metal oxides have an additional property of
Mr. Hemant Kumar Raut is

currently pursuing Doctoral
Degree at the National University of Singapore (NUS). His
current research work includes
fabrication and characterization
of anti-reflective coatings on
glass and solar modules at the
Healthcare and Energy Materials
(HEM)
Laboratory,
NUS. With a Bachelors in
Mechanical Engineering, his
research interests lay in the field
Hemant Kumar Raut
of nanotechnology, photonic
nanostructures (biomimetic),
interferential
antireflective
coatings, solar energy and coating technology. He has experience
in the field of industrial component designing and manufacturing,
steel processing and finite element modeling.
This journal is The Royal Society of Chemistry 2011
View Article Online
chemically breaking down the complex dirt deposits by sunlightassisted cleaning mechanism. This review will discuss the materials, processes, mechanisms and characterization involved in
self-cleaning coatings. Further, the review will highlight the
challenges still to be met along with recent innovations in this
direction.

2. Self-cleaning effect
The self-cleaning phenomenon is related to the surface contact
angle. It is the angle formed at the three phase boundary (solid/
liquid/vapour) between the surfaces of the liquid drop to the
surface of the solid. In general, if the contact angle is <90 the
solid surface is termed as a hydrophilic surface. When the contact
angle (CA) is >90 , the surface is defined as a hydrophobic
surface. Similarly, a surface with a water contact angle
approaching zero is classified as ultra (super) hydrophilic and
a surface with a contact angle >150 is usually categorized as
ultra (super) hydrophobic (Fig. 1).
3. Hydrophobic and superhydrophobic coatings

3.1.
Natures lead
Nature is the source of inspiration for many researchers around

the world to develop aesthetic self-cleaning functional systems.
The lotus flower is referred to the symbol of purity in Asian
religions. Ward et al.,2 first observed this phenomenon and
described the fact that, although the lotus leaf rises from muddy
water, it is clean and remains untouched by dirt and other
pollutants. The mystery behind this mechanism was unfolded
after the invention of the SEM in mid 1960s.3 Studies made using
SEM revealed that the surfaces, which appear to be macroscopically smooth, exhibit microscopic roughness on different
scale lengths.46 These surfaces, along with the presence of
epicuticular wax crystalloids, make the leaves superhydrophobic.
Dr A. Sreekumaran Nair is
currently a research fellow at the
Healthcare and Energy Materials (HEM) Laboratory of
National University of Singapore. He graduated with a PhD
in Chemistry from Indian Institute of Technology (IIT)
Madras (2006) and subsequently became a JSPS postdoctoral fellow (20062008) in
Japan. His research interests
include development of materials
A: Sreekumaran Nair
for energy conversion and
storage, catalysts for solar
hydrogen,
nanotechnologybased environmental remediation and probing charge transport
mechanism in monolayer-protected clusters and 3-D superlattices.
Fig. 1 A schematic representation of hydrophilic, hydrophobic and

ultra (super) hydrophobic surfaces.
These findings led the way for the fabrication of various biomimetic superhydrophobic surfaces inspired by nature. The results
of the research work conducted by Guo et al.7 disclosed that
there are two major types of surface microstructures in plant
leaves with superhydrophobicity: (i) hierarchical micro and
nanostructures, (ii) unitary micro-line structures. This revelation
Dr
Seeram
Ramakrishna,
FREng, FNAE, FAAAS is
a Professor of Materials Engineering and Director of HEM
Labs (http://serve.me.nus.edu.
sg/seeram_ramakrishna/) at the
National University of Singapore. He is an acknowledged
global leader for his pioneering
work on science and engineering
of
nanofibers
(http://
researchanalytics.thomsonreuters.
com/m/pdfs/grr-materialscience.
Seeram Ramakrishna
pdf). He authored five books
and over four hundred peer
reviewed international journal
papers, which attracted over 12 000 citations with an h-index of
52. Web of Science places him among the top one percent of
materials scientists worldwide. He is an elected international fellow
of major professional societies in Singapore, ASEAN, India, UK
and USA.
J. Mater. Chem., 2011, 21, 1630416322 | 16305
View Article Online

paved way for the development of several synthetic methods to

mimic the natural superhydrophobic surfaces.
3.1.1. Plant leaves with hierarchical structure. Fig. 2 shows
SEM images of hierarchical structures present in three different
plant leaves. Fig. 2a and b are SEM images of lotus leaf at low
and high magnifications, which show the uniformly textured
surface with 310 mm sized flanges and valleys tinted with a 70
100 nm sized wax like material (Fig. 2a). A lot of nanorod like
structures with an average diameter of about 50 nm are randomly
distributed on the subsurface layer (Fig. 2b).
This textured surface helps the lotus leaf to exhibit superhydrophobic property. The water contact angle observed is
around 162 (inset of Fig. 2b).8,9 Fig. 2c and d show the SEM
images of rice leaf. The top surface of the leaf posses the papillae
with an average diameter of about 58 mm and they are arranged
in one-dimensional order (Fig. 2c). The sub layer of the surface
consists of innumerable nanopins that are proportionally well
distributed to enhance the air trapping mechanism in the surface
(Fig. 2d). The water contact angle (WCA) exhibited by this
surface is 157 (inset of Fig. 2d). Like lotus and rice leaves, taro
leaf also shows superhydrophobicity (Fig. 2e and f). Compared
to the above two plant leaves, taro leaf possesses distinct
microstructures (10 mm) that are distributed in their corresponding nest like caves (Fig. 2e). A higher magnification SEM
image (Fig. 2f) shows the presence of harmoniously distributed
Fig. 2 SEM images of natural superhydrophobic surfaces with hierarchical structures.6 (a) and (b) are the SEM images of lotus leaf with low
and high magnifications, respectively, and the inset of (b) is a water CA
on it with a value of about 162 ; (c) and (d) are the SEM images of rice
leaf with low and high magnifications, respectively, and the inset of (d) is
a water CA on it with a value of about 157 ; (e) and (f) are the SEM
images of taro leaf with low and high magnifications, respectively, and
the inset of (f) is the water CA on it with a value of about 159 .
16306 | J. Mater. Chem., 2011, 21, 1630416322
Fig. 3 The SEM images of biomimetic superhydrophobic surfaces made

by replicating the lotus leafs surface structure with lotus leaf as the
template. (a) The positive replica with poly(dimethylsiloxane) (PDMS),
and the inset is a visualization of the advancing and receding CAs on the
surface.9 (b) A photopolymer replica with UV-nanoimprint lithography
and the inset is the magnified image.10
nanopins on its surface along with the formed microstructure.

The WCA observed in this leaf is around 159 (inset of Fig. 2f).
Inspired by the enthralling hierarchical structures exhibited by
nature, Ji et al.10 successfully replicated a superhydrophobic
surface using lotus leaf as a template. He employed a nanoscale
casting technique instead of conventional microfabrication or
chemical synthesis (Fig. 3a). The SEM image shows a surface
morphology very similar to lotus leaf with small papillae
protrusions of an average diameter of 6 mm. The space between
the microstructured valleys and protrusions are textured by
intricate nanostructures. Similarly, two other kinds of lotus leaf
replicas (PDMS replica and photo polymer replica) were fabricated by polymer casting and UV nanoimprint lithography.11
Fig. 3b shows the SEM image of the morphology obtained.
Besides lotus leaf, other plant leaves can also be used as
a template for fabricating superhydrophobic surfaces. Taro leaf
is used as a template to produce a superhydrophobic surface with
polystyrene film.12 Though these intriguing structures can be
replicated as an artificial surface using lotus leaf as a template,
there are still limitations due to the size of the lotus leaf and the
complexity of the surface morphology. Accordingly, developing
other superficial techniques to fabricate superhydrophobic
surfaces is indispensable and still remains a challenge for
researchers.
3.1.2. Plant leaves with unitary structure. Fig. 4 shows the
SEM images of unitary structures exhibited by different plant
leaves. On the rear face of ramee leaf (Fig. 4a), uniformly
distributed slick fibers with a diameter of 12 mm can be seen
forming a unitary structure that is different from the surfaces of
the aforementioned plant leaves with hierarchical structures.
This unique structure is also found on the surfaces of Chinese
watermelon shown in Fig. 4c and d. Surprisingly, the surface
morphologies of ramee leaf and Chinese watermelon are similar
and both exhibit a WCA of 159 . This discovery clearly
explains that the hierarchical structure is not the only necessary
condition to exhibit superhydrophobicity.
Ding and Shing et al.13 fabricated superhydrophobic surfaces
by electrostatic layer-by-layer deposition of electrospun nanofibrous membranes (Fig. 5). By this method, cellulose acetate
fibers were made to form a unitary structure that is similar to that
of ramee leaf (Fig. 5a). These fibers showed a smooth surface
(Fig. 5a) showing superhydrophobicity (inset of Fig. 5a). After
View Article Online

3.2. Materials and mechanism to produce hydrophobic and

superhydrophobic coatings
Inspired by the superhydrophobic properties exhibited by
nature, researchers around the world started working on developing technologies to produce surfaces with extremely low
surface energies and also to control the morphology of
the surface on a micron and nanometre scale. This idea of
controlling surface morphology opens up many possibilities for
developing a variety of engineered surfaces.
Techniques to produce hydrophobic and superhydrophobic
surfaces can be broadly classified into two categories: a) making
a rough surface from a low surface energy material; b) modifying
a rough surface with a material of low surface energy.
Fig. 4 SEM images of natural superhydrophobic surfaces with a unitary

structure.6 (a) and (b) are the SEM images of the ramee leaf rear face with
low and high magnifications, respectively, and the inset of (b) is a water
CA on it with a value of about 164 ; (c) and (d) are the SEM images of the
Chinese watermelon surface with low and high magnifications, respectively, and the inset of (d) is the water CA on it with a value of about 159 .
Fig. 5 SEM images of biomimetic superhydrophobic surface with

unitary structure similar to that of ramee leaf. (a) Cellulose acetate
fibrous membranes by electrospinning, showing a unitary structure and
superhydrophilicity,13 (b) FAS-modified cellulose acetate fibrous
membranes, showing superhydrophobicity13 (c) and (d) SEM images of
PPFEMA-coated fibers and corresponding droplet images (inset).14
the fluoroalkylsilane (FAS) modification, the cellulose acetate

exhibited superhydrophobicity with WCA 140 . Rutledge et al.14
coated electrospun materials consisting of either uniform or
beads-on-string fibers with a thin layer of hydrophobic poly
(perfluoroalkyl ethyl methaacrylate) (PPFEMA) by an iCVD
(initiated Chemical Vapour Deposition) process. The experimental results showed that the bead-on-string morphology has
improved superhydrophobicity (WCA around 175 ) when
compared to the bead-free fibers (Fig. 5c and d).
3.2.1. Roughening the surface of low surface energy material

3.2.1.1. Silicones. PDMS (polydimethylsiloxane) belongs to
a group of organosilicon compounds, commonly known as silicones. The intrinsic deformability and hydrophobic properties of
PDMS makes it a highly suitable material for producing superhydrophobic surfaces. Various methods are practised to produce
superhydrophobic surfaces using PDMS. For example, Khorasani et al.15 did surface modification on PDMS using a CO2
pulsed laser as an excitation source to introduce peroxide groups
onto the PDMS surface (Fig. 6a and b). These peroxides are
capable of initiating graft polymerization of 2-hydroxyethyl
methacrylate (HEMA) onto the PDMS. The water contact angle
(WCA) of the treated PDMS was measured to be 175 . The
reason for such an increase in WCA was due to the porosity and
chain ordering on the surface of PDMS. Jin et al.16 used a PDMS
elastomer containing micro and nanocomposite structures to
produce superhydrophobic surfaces. They employed laser
etching to induce roughness on the PDMS surface. The surface
produced by this technique exhibited WCA as high as 160 and
sliding angle lower than 5 .
Ma et al.17 used an electrospinning technique to produce
superhydrophobic membranes. The electrospun fibres (Fig. 7)
made of a PS-PDMS block blended with a PS (polystyrene)
homopolymer reached a WCA of about 163 . The large WCA is
because of the combined effect of enrichment of the fiber surfaces
by the PDMS component and the surface roughness due to the
small diameter of the fibers (150400 nm). Recently, Zhao et al.18
produced a superhydrophobic surface by a casting technique.
The process of casting a micellar solution of PS-PDMS in the
presence of humid air resulted in a superhydrophobic surface
(Fig. 8) with a WCA of about 163 .
3.2.1.2. Fluorocarbons. Fluorinated polymers are attracting
lots of interest these days because of their extremely low surface
energies. Roughening these polymers will result in superhydrophobic surfaces. Zhang et al.19 achieved superhydrophobicity by stretching a Teflon (polytetrafluoroethylene)
film. The superhydrophobic property achieved is due to the
presence of fibrous crystals with large fractions of void space on
the surface. Shiu et al.20 produced a rough surface on Teflon by
treating it with oxygen plasma. The WCA obtained by this
technique was 168 . Because of the limited solubility, many
fluorinated materials have not been used directly but linked with
other rough materials to make superhydrophobic surfaces.
J. Mater. Chem., 2011, 21, 1630416322 | 16307

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Fig. 8 A SEM image of a PS-PDMS surface cast from a 5 mg mL1

solution in dimethylformamide (DMF) in humid air.18
Fig. 6 (a) A schematic illustration of laser induced graft polymerization.15 (b) A SEM image of a PDMS surface treated with a CO2 pulsed
laser.15
Yabu and Shimomura21 produced a honeycomb-like microporous transparent polymer film with 500 nm to 50 mm sized
pores by casting a polymer solution under humid conditions. In
this process, the fluorinated glass substrate was placed over the
substrate holder. A metal blade was fixed perpendicular to the
substrate and the gap between the blade and the substrate was
adjusted to about 100 mm. Fluorinated copolymer solution was
supplied between the blade and the substrate. Humid air (relative
humidity around 60% at room temperature) was supplied to the
solution surface with a flow velocity of 10 L min1. The formation of the honeycomb-patterned film was observed by an optical
microscope. The transparent honeycomb-patterned films
produced by this method (Fig. 9a and b) exhibited superhydrophobic properties with a WCA of about 160 .
3.2.1.3. Organic materials. Although silicones and fluorocarbons are extensively used to produce superhydrophobic
surfaces, recent research works have proved that hydrophobicity
can be obtained using paraffinic hydrocarbons as well. Lu et al.22
proposed a simple and inexpensive method for forming a superhydrophobic coating using low-density poly ethylene (LDPE).
In this method, a highly porous superhydrophobic surface of PE
was produced by controlling the crystallization time and nucleation rate (Fig. 10). A WCA of about 173 was obtained by this
method. Jiang et al.23 showed that a superhydrophobic film can
be obtained by electrostatic spinning and spraying of PS solution
in dimethylformamide (DMF). The surface obtained was
composed of porous microparticles and nanofibers (Fig. 11).
Recent research work showed that alkylketene,24 polycarbonate25 and polyamide26 also exhibit superhydrophobic
properties.
Fig. 7 A SEM image of a PS-PDMS/PS electrospun fiber mat and the

droplets on it.17
16308 | J. Mater. Chem., 2011, 21, 1630416322
3.2.1.4. Inorganic materials. Superhydrophobic properties

have been exhibited by a few inorganic materials as well. Recent
research work conducted on materials like ZnO and TiO2

View Article Online
Fig. 11 A SEM image of the PS surface produced by electrostatic

spinning and spraying.23
Fig. 9 (a) A schematic illustration of honeycomb patterned21 film

preparation. (b) The honeycomb-patterned film (top image and crosssection) cast from a solution of the polymer, shown in the inset, under
humid conditions.21
Fig. 10 A SEM image of the flower-like crystal structure of PE.22
resulted in the production of films with reversibly switchable

wettability. Feng et al.27 synthesized ZnO nanorods by a two-step
solution method (Fig. 12). XRD study showed that the ZnO
nanorod films were superhydrophobic due to the low surface
energy of the (001) plane of the nanorods on the surface of the
film. When the film is exposed to UV radiation, electronhole
pairs were produced resulting in the adsorption of hydroxyl
group on the ZnO surface. Consequently, the superhydrophobic
property of the film is converted to superhydrophilic. Dark
storage of the UV irradiated film for a week made it superhydrophobic again.
3.2.2. Making a rough surface and modifying the surface with
material of low surface energy. This section primarily focuses on
various techniques reported in the past few years to fabricate
rough surfaces and subsequently modifying the surface chemistry
to produce superhydrophobic membranes.
Fig. 12 A SEM image of aligned ZnO nanorods prepared by a two-step

solution approach.27
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3.2.2.1. Wet chemical reaction and hydrothermal reaction.

Wet chemical reaction is a straightforward technique that can
effectively control the dimensionality and morphology of the
nanostructures (nanoparticles, nanowires and mesoporous
inorganics) produced.2830 This method was widely used in the
fabrication of biomimetic superhydrophobic surfaces on metal
substrates like copper, aluminium and steel. Jiang et al.31 used
chemical composition method to produce a superhydrophobic
surface on copper substrate. The substrate was immersed into ntetradecanoic acid solution for about a week, which resulted in
surface modification of the substrate, which then exhibited
superhydrophobicity. Zhang et al.32 employed a surface roughness technique by etching polycrystalline metals with acidic or
basic solution of fluoroalkylsilane. After treating with fluoroalkylsilane, the etched surfaces exhibited superhydrophobicity
(Fig. 13a and b).
Superhydrophobic surfaces on nickel substrates were created
by employing a wet chemical process in which monoalkylphosponic acid reacts with Ni to produce flowery microstructures constituting a continuous slipcover.33 A stable
superhydrophobic surface is produced on a copper substrate by
using oxalic acid as a reaction reagent and then chemical modification is done using poly(dimethysiloxane) vinyl terminated
(PDMSVT) (Fig. 13c).34 A layer of interconnected Cu(OH)2
nanowires was generated on a Cu plate by immersing it into the
mixture of NaOH and K2S2O8 solution. After chemical modification with dodecanoic acid, the surface exhibited superhydrophobicity (Fig. 13d).35 Hao et al.36 fabricated a biomimetic
superhydrophobic surface on magnesium alloy by microarc
Fig. 13 SEM images of biomimetic superhydrophobic surfaces fabricated by wet chemical reaction. (a) and (b) SEM images of the etched steel
and copper alloy treated with fluoroalkylsilane, respectively, both
showing good superhydrophobicity (inset);32 (c) a SEM image of copper
immersed in 0.5 wt% oxalic acid for 57 days and treated with PDMSVT,
showing superhydrophobicity (inset);34 (d) a SEM image of a copper plate
immersed in an aqueous solution of 2.0 M NaOH and 0.1 M K2S2O8 for
60 min, showing good superhydrophobic properties after dodecanoic
acid modification (inset).35
16310 | J. Mater. Chem., 2011, 21, 1630416322
oxidation pre-treatment and chemically modifying the surface

with PDMSVT with spin coating.
The hydrothermal technique is a recently developed method
that uses a bottom up route in efficiently fabricating functional
materials with different patterns and morphologies.3740 Nanolamellate structures on titanium were produced by an in situ
hydrothermal synthesis method (Fig. 14a).41 The obtained
superhydrophilic surface is converted to a superhydrophobic
surface by chemical modification using PDMSVT (inset of
Fig. 14a). Li et al.42 established a new technique in which they
used an inorganic precursor route to produce superhydrophobic
complex metal oxide monoliths by selective leaching of a selfgenerated MgO sacrificial template from the sintered two phase
composites (Fig. 14b). A superhydrophobic surface with an array
of spiral Co3O4 nanorods was produced by a hydrothermal
method in which Co(NO3)2$6H2O is used as a resource under
basic conditions (Fig. 14c).43 In recent years, an array of zinc
nanorods exhibiting superhydrophobicity was fabricated due to
its potential applications in short-wavelength lasing, gas sensors,
catalysts and piezoelectric materials.4446 For example, Hou
et al.46 synthesized superhydrophobic ZnO nanorod film on
a zinc substrate by oxidizing zinc metal and subsequently
modifying the surface using n-octadecyl thiol (Fig. 14d). Both
these techniques are time saving and scalable. The flexibility and
simplicity of these methods help in producing morphologies of
reasonable shape and size.
Fig. 14 The biomimetic superhydrophobic surfaces constructed by

hydrothermal reactions. (a) The shape of a water droplet (about 10 mg)
on the surface with nanolamellate structures of CaTiO3 (inset) by using
an in situ hydrothermal synthesis on titanium, showing a water CA of
about 160 (inset);41 (b) a typical SEM image of MgAl2O4 monolith
obtained through a novel single-source inorganic precursor route, and
after chemical modification with n-octadecanoic acid, the surface shows
superhydrophobicity (inset);42 (c) a SEM image of the spiral Co3O4
nanorod arrays on a glass slide, and after chemical modification, the
surface shows good superhydrophobicity with a water CA of about
162 (Inset);43 (d) a SEM image of the prepared ZnO, overview of
the cross section on zinc substrate, and after chemical modification, the
surface shows superhydrophobic with a water CA of about 153
(inset).46

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3.2.2.2. Electrochemical deposition. Electrochemical deposition is widely used to develop biomimetic superhydrophobic
surfaces since it is a versatile technique to prepare microscale and
nanoscale structures.4752 Bell et al.53 employed a galvanic
deposition technique on metals to deposit metallic salts solution,
which resulted in the formation of superhydrophobic surface
with WCA of about 173 (Fig. 15a). The surface produced can
effortlessly float on a water surface similar to pond skaters
(Fig. 15b). Jiang et al.54 employed electrochemical deposition
method, inducing long chain fatty acids to produce micro and
nanoscale hierarchical-structured copper mesh that exhibited
superhydrophobicity and superoleophilicity (Fig. 15c). Superhydrophobic 3D porous copper films were fabricated by using
hydrogen bubbles as the dynamic template for metal electrodeposition.55 Since the films were electrodeposited and grew within
the interstitial spaces between the hydrogen bubbles, the pore
diameter and wall thickness of the porous copper films were
successfully tailored by adjusting the concentration of the electrodeposition electrolyte, as shown in Fig. 15d. The magnified
SEM image (inset of Fig. 15d) clearly shows the porous structure
with numerous dendrites in different directions forming a strong
film.
3.2.2.3. Lithography. Lithography is a conventional technique used to create micro- and nanopatterns. Different lithographic techniques that are in practice are: a) photolithography,
b) electron beam lithography, c) X-ray lithography, d) soft
lithography, and e) nanosphere lithography and so on.5665 Notsu
et al.66 used a photocatalytic lithography technique on composite
(gold) surfaces to fabricate superhydrophilic and superhydrophobic patterns. Martines et al.67 employed the technique
of electron beam lithography and plasma etching to produce an
Fig. 15 Biomimetic superhydrophobic surfaces fabricated by electrochemical deposition. (a) A water drop (8 mm3) on a silver/heptadecafluoro-1-decanethiol (HDFT) superhydrophobic surface deposited on
a copper substrate;53 (b) a metallic model pond skater (body length
28 mm) of copper legs treated with silver and HDFT;53 (c) a SEM image
of the deposited films on one copper mesh knitted by about 55 mm wires
as substrates, and the surface shows superhydrophobicity after chemical
modification with n-dodecanoic acid;54 (d) a SEM image of porous
copper films created by electrochemical deposition at a 0.8 A cm2
cathodic current density in 0.5 M H2SO4 and 0.1 M CuSO4 for 45 s.55
array of nanopits and nanopillars on the surface of the material.

When this surface was hydrophobized with octadecyltricholorosilane, it exhibited superhydrophobic properties with a WCA
reaching up to 164 (Fig. 16a and b).
3.2.2.4. Self-assembly and layer-by-layer (LBL) methods.
The self-assembly and layer-by-layer (LBL) assembly techniques
are based on sequential adsorption of a substrate in solutions of
oppositely charged compounds. These techniques continues to be
the most popular and well-established methods for the formation
of multilayer thin films. Self-assembly and layer-by-layer deposition are inexpensive techniques in which micro- and nanoscale
superhydrophobic structures can be easily fabricated with finely
controlled surface morphologies.6880 Jiang et al.68 fabricated
conducting superhydrophobic rambutan-like surface with hollow
spheres of aniline by self-assembly technique in the presence of
perfluorooctane sulfonic acid (PFOSA). Arrays of carbon
nanotubes are constructed on the cotton substrate to replicate
the lotus leaf structure.69 In order to control the assembly of
carbon nanotubes on cotton fibers, these fibers are modified by
treated carbon nanotubes as macro-initiators. Dong et al.,70
Luzinov et al.71 and Rotello et al.72 adapted a new method to
convert hydrophobic surfaces into superhydrophobic surfaces.
In this method, a magnetic material (FePt) with varying degree of
fluorinated ligands is deposited over the surface to exhibit
superhydrophobicity. Superhydrophobic films with dual-scaled
roughness were also produced by assembling silica micro and
nanospheres by electrostatic adsorption technique (Fig. 17a).73
Rawlett et al.74 synthesized superhydrophobic surface by
employing the breath figure method (Fig. 17b) in which an array
of microscale pores are produced in polymer matrices through
spontaneously assembly of water vapour condensation.
Lee et al.75 synthesized an adjustable dual-size roughness
surface consisting of raspberry-like particles by the assembly of
silica particles (Fig. 17c). Bionic superhydrophobic coatings were
produced by decorating silver nanoparticles on a monolayer
Fig. 16 The superhydrophobic surfaces produced by lithography techniques. (a) A SEM image of nanopits and nanopillars produced by
electron beam lithography and plasma etching.67 (b) A SEM image of the
nanopillars after hydrophobization. The base diameter of the pillars is
about 120 nm.67
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silicate multilayers on a silica-coated substrate (Fig. 19a). This

assembly was then treated with fluorine to exhibit superhydrophobicity. Zhai et al.80 used a LBL technique to mimic the
superhydrophobic behaviour of the lotus leaves by creating
a honeycomb-like structure of a polyelectrolyte (poly (allylamine
hydrochloride)/poly (acrylic acid)) (PAH/PAA) multilayer
surface coated with silica nanoparticles. This highly textured
multilayer surface is treated with semi-fluorinated silane to
achieve superhydrophobic properties (Fig. 19b).
Fig. 17 The biomimetic superhydrophobic surfaces fabricated by selfassembly methods. (a) SEM image of microsphere array assembled by
300 nm silica spheres, showing superhydrophobicity with a water CA of
about 161 and the scale bars are 50 mm and 5 mm, respectively;73 (b)
a three-dimensional AFM image of silicone pillars formed on breath
figure templates in a humidity chamber at 73% relative humidity;74 (c)
a SEM image of a raspberry-like particulate film fabricated by assembling
one layer of 35 nm silica particles on a large silica particulate film
prepared using LangmuirBlodgett (LB) deposition;75 (d) a SEM image
of the superhydrophobic coating fabricated by layer-by-layer method on
a flat glass substrate with a water CA of about 168 .76
array of polystyrene microspheres (Fig. 17d).76 Stable superhydrophobic surfaces are produced by deposition of nanosized
silica particles on a glass substrate with the formation of a self
assembled monolayer of dodecyltrichlorosilane on the surface of
the film.77 Ming et al.78 also synthesized raspberry-like particles
using amine groups. In this process, amine-functionalized silica
particles of size 70 nm and epoxy-functionalized silica particles of
size 700 nm were covalently grafted through the reaction between
epoxy and amine groups (Fig. 18a and b). The surface exhibited
superhydrophobicity after being modified with PDMS. The
WCA achieved by this technique was about 165 .
Zhang et al.79 fabricated a superhydrophobic surface by LBL
deposition of poly(diallyldimethylammonium chloride)/sodium
Fig. 18 The biomimetic superhydrophobic surfaces fabricated by layerby-layer methods: (a) preparation of superhydrophobic films based on
raspberry-like particles.78 (b) AFM 3D images for PDMS-covered epoxybased films containing raspberry-like particles.78
16312 | J. Mater. Chem., 2011, 21, 1630416322
3.2.2.5. Electrospinning technique. Electrospinning is

a dominant technique for synthesizing fine nanofibers. This
technique is widely used by several research groups to provide
sufficient surface roughness for inducing superhydrophobicity.
Electrospinning a hydrophobic material will directly result in
superhydrophobicity. Ma et al.81 employed electrospinning and
chemical vapour deposition techniques to produce superhydrophobic surfaces. In this process, poly (caprolactone) (PCL)
was first electrospun and then it was coated with a thin layer of
hydrophobic polymerized perfluoroalkyl ethyl methacrylate
(PPFEMA) by chemical vapor deposition (CVD) (Fig. 20). The
WCA obtained by this process was about 175 .
3.2.2.6. Etching and chemical vapour deposition. Plasma
etching processes and CVD have been extensively used with
polymers to fabricate functional surfaces with different
morphologies.8285 Engineered surfaces exhibiting hydrophilic
and hydrophobic properties are synthesized by plasma-based
Fig. 19 The biomimetic superhydrophobic surfaces fabricated by layerby-layer methods. (a) A SEM image of the silica-coated surface, showing
good superhydrophobicity after chemical modification;79 (b) Doubleroughened superhydrophobic surfaces made by layer-by-layer80
assembly.
Fig. 20 A SEM image of electrospun nanofibers (a) before (b) after

iCVD coating.81

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Fig. 23 SEM images at (a) low and (b) high magnifications of the copper
surface etched with a modified Livingstons dislocation etchant for 24 h at
ambient temperature.91
Fig. 21 The biomimetic superhydrophobic surfaces constructed by

plasma etching. (a) A SEM image of the rough surface after 3 min of SF6
etching, showing superhydrophobicity;86 (b) an AFM image of an O2plasma treated PMMA sample;87 (c) an optical image showing the pulsed
plasma deposited poly(glycidyl methacrylate) array reacted with 50 mm
amino-polystyrene microspheres;88 (d) a SEM image of Si nanowires
grown on the Si islands with Au cluster on the tips of the nanowires
treated by plasma etching, the scale bar is 5 mm.89
techniques to obtain different surface topographies (Fig. 21a).86

Gogolides et al.87 employed nano-rinse and a mass production
amenable plasma process to fabricate superhydrophobic poly
(methyl methacrylate) (PMMA) surfaces under low pressure
conditions in high density plasma reactor (Fig. 21b). Garrod
et al.88 analyzed the stenocara beetles back and replicated the
surface by employing a micro-condensation process using
plasma chemical patterns. The micro textures are designed and
constructed over Si surfaces and they exhibited superhydrophobic behavior with WCA of about 174 (Fig. 21d).89
Teshima et al.90 produced a transparent superhydrophobic
surface by a novel method consisting of two dry processing
techniques. In this method, nanotexture was first formed on
a poly(ethylene terephthalate) (PET) substrate via selective
oxygen plasma etching followed by plasma enhanced chemical
vapour deposition using tetramethylsilane as the precursor
(Fig. 22). The surface fabricated by this process showed a WCA
greater than 150 .
Qian and Shen91 developed a simple surface roughening
method using a chemical etching technique on three
Fig. 22 AFM images of the PET surfaces90 (a) treated with oxygen
plasma, (b) coated with FAS layer (low-temperature CVD) after the
oxygen plasma treatment and (c) coated with TMS layer (PECVD) after
the oxygen plasma treatment.
polycrystalline metals (aluminium, copper and zinc) to make

superhydrophobic surfaces. The principle behind this technique
was the use of dislocation etchant that dissolves the dislocation
sites in the grain. The etched surfaces (Fig. 23) after treating with
fluoroalkylsilane exhibited superhydrophobic properties. The
WCA obtained by this process is about 153 .
Chemical vapour deposition (CVD) is a competent technique
to produce micro and nano surface topographies on a macroscopic substrate.9294 Yan et al.92 produced pyramid like micro
structures through capillary driven self-assembly during the
evaporation of water from aligned CNTs wrapped by poly
(sodium 4-styrenesulfonate). The surface exhibited good superhydrophobicity. Ci et al.93 constructed an array of vertically
aligned large diameter double walled carbon nanotubes by
a water assisted chemical vapor deposition process. The prepared
surface exhibited a WCA of about 170 .
3.2.2.7. Solgel method and polymerization reaction. The sol
gel method can be employed in the fabrication of superhydrophobic surfaces in all kinds of solid substrates.95102 Huang
et al.101 fabricated biomimetic superhydrophobic surfaces on
alloys of copper using hexamethylenetetramine and ethylene
glycol (Fig. 24a), a strong bidentate chelating agent to Cu2+ and
Fe2+ ions with a high stability constant, as the capping reagent.
Duan et al.102 produced ordered pore indium oxide array films
bya sol-dipping method using polystyrene colloidal monolayers
(Fig. 24b). It is found that the superhydrophobic properties
exhibited by the film can be controlled by increasing the pore size
on the film. Shirtcliffe et al.103 used different proportions of
(organo-triethoxysilane) methyltriethoxysilane (MTEOS) to
Fig. 24 The biomimetic superhydrophobic surfaces constructed by sol

gel methods. (a) A SEM image of a nanorod film of Cuferrite formed by
a solgel process;101 (b) a SEM image of indium oxide pore array films
after removal of the PS sphere and annealing at 400 C, based on the
colloidal monolayer templates by the sol-dipping method.102
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Fig. 25 Superhydrophobic surfaces produced by the solgel method.

Top, phenolphthalein in water on MTEOS solgel foams heated to 390

C (left) and 400 C (right). Centre, a SEM image of an unheated solgel
foam. Bottom, foam films on glass cover slips with (left) drop of water
with brilliant blue G and (right) imbibed.103
Fig. 27 The superhydrophobic surfaces created by polymerization

reactions. (a) A SEM image of the nanoporous anodic aluminium oxide
substrate fabricated by anodizing for 30 min at 155 V and wet-chemical
etching at 45 C for 30 min, the surface shows superhydrophobic after
chemical modification with the pSAMs of poly(TMSMA-rfluoroMA),
and the scale bar is 1 mm;108 (b) an AFM image of the hybrid film surface
and water CA on it.109
produced film exhibited very high superhydrophobicity. Choi

et al.108 used a new random copolymer, poly(TMSMA-r-fluoroMA) [3-(trimethoxysilyl)propylmethacrylate] (TMSMA),
methacrylate (MA)] on oxide-based substrates. The WCA
obtained was about 163 (Fig. 27a). A water repellent surface
instigated from quincunx-shaped composite particles was constructed by utilizing the encapsulation and graft of silica particles
to control the surface tomography (Fig. 27b).109
3.2.2.8. Other techniques. Besides the techniques cited above,
researchers around the world are working on several other
methods like texturing,110,111 electrospraying,112,113 and sandblasting,114 which were employed to fabricate superhydrophobic
surfaces in recent times. In year 2009, Zhang et al.110 fabricated
superhydrophobic surfaces by surface texturing the porous
silicon films with capillary stress (Fig. 28). Chien et al.111
synthesized stable superhydrophobic surface of a three tier
Fig. 26 A superhydrophobic surface produced by a solgel method. The

image in the left shows the transparency of the coating. The image on the
right is the AFM image of a solgel film containing 30 wt% colloidal
silica.104
produce solgel foams. These foams, when exposed to different

temperatures, exhibited binary switching between superhydrophilicity and superhydrophobicity (Fig. 25). Hikita et al.104
prepared solgel films by hydrolysis and condensation of
alkoxysilane compounds. Colloidal silica and fluoroalkylsilane
were used to control the surface energy and roughness of the film.
By optimizing the amount of colloidal silica and fluoroalkylsilane in the film, superhydrophobicity was created in it
(Fig. 26). Shang et al.105 described an easy method to fabricate
a transparent superhydrophobic film by modification of silicabased gel films with a fluorinated silane.
Polymerization is another efficient method to tailor different
surface topographies for the fabrication of superhydrophobic
surfaces.106109 Tiemblo et al.106 synthesized superhydrophobic
aerosol 200 using methoxysilanes in toluene reflux with p-toluenesulfonic acid as a catalyst. Zhong et al.107 fabricated a polypropylene film with a nanoribbon polyaniline structure. The
16314 | J. Mater. Chem., 2011, 21, 1630416322
Fig. 28 Surface morphologies and wettability of alkene-modified PSi

films with different etching times: (ac) 120 min, with multiscale structures and (d) 10 min, with a smooth porous surface. The inset of (b) is the
magnification of a papillary tip; the inset of (c) and (d) show water drops
on the corresponding surfaces.110

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roughened texture of microscale carbon fabrics decorated with

submicroscale silica (SiO2) spheres and carbon nanotubes with
low contact angle hysteresis. They found that the produced
surface exhibited superhydrophobicity without any surface
treatment. Burkarter et al.112 used an electrospray technique to
deposit polytetrafluoroethylene (PTFE) films on fluorine-doped
tin oxide coated glass slides. Liu et al.113 demonstrated an inexpensive technique for the fabrication of superhydrophobic
surfaces with a crater-like structure on Ti6Al4V alloy substrate by
means of sandblasting with SiO2 microparticles, which is a pure
physical process, and the surface compositions remain
unchanged. It is believed that this method should be easily
applied to other metals and their alloys.
4. Functions of hydrophobic surfaces

Though lots of research works are centred around fabrication
techniques for superhydrophobic surfaces, in recent years,
researchers started focusing on various functions and applications of these surfaces (Fig. 29). This review article will explain
only the primary functions of superhydrophobic surfaces, such
as anti-icing, oil repellency, and electrowetting and elucidate
different research works carried out in these areas.
4.1.
understanding of the various factors affecting frost nucleation,

particularly the surface energy of the base surface. The experimental results showed that air at the cold surface should be
supersaturated to ensure frost nucleation. But the supersaturation degree is mainly dependent on the surface energy, which will
in turn affect the initial frost nucleation. They concluded that
cold substrates of lower surface energy require a higher supersaturation degree for nucleation than higher energy surfaces, and
surface roughness will also reduce the required supersaturation
degree. As the extreme of low energy surfaces, superhydrophobic
films are also considered as promising materials for alleviating
frost growth on cold substrates. Gao et al.121 used nanoparticle
polymer composites to fabricate anti-icing superhydrophobic
coatings that can prevent the formation of ice upon the impact of
supercooled water. The experimental results showed that the
anti-icing capability of these composites depends on the superhydrophobicity and also on the size of the particles exposed on
the surface.
Icing of water on superhydrophobic surfaces is a complicated
phenomenon and there are lots of factors like temperature,
contact area, surface roughness and surface thermodynamics, all
of which play a vital role in the occurrence of this phenomenon.
Further research is needed to get a clear understanding on the
effect of these factors on icing.
Anti-icing
4.2.
In cold regions, layers of ice gets deposited on solid materials,

particularly on overhead transmission lines, which results in the
mechanical failure of the system. Recent research works orbits
around the fabrication of superhydrophobic surfaces to reduce
the accumulation of snow and to even eliminate the formation of
ice on solid surfaces.115120
Kulinich et al.117119 investigated the adhesion strength of
artificially created glaze ice (similar to that accreted in nature) on
rough fluoropolymer-based superhydrophobic coatings with
similar self-assembled monolayers. Glaze ice is prepared by
spraying supercooled water microdroplets on the target
substrates at a sub-zero temperature. Ice adhesion is evaluated by
spinning the samples at constantly increasing speed until ice
delamination occurred. Na et al.120 gave a fundamental
Fig. 29 Functions of superhydrophobic surfaces.
Electrowetting and other functions
Electrowetting on superhydrophobic surfaces122135 is an interesting phenomenon that has attracted much attention in recent
years. In the year 2004, for the first time Krupenkin et al.127
demonstrated a technique for dynamic electric control over the
wetting behaviour of the liquid droplets on a superhydrophobic
surface by etching an array of microscopic cylindrical nanoposts
into the surface of a silicon wafer. He found that the wetting
properties of the surface can be tuned from superhydrophobic
behaviour to nearly complete wetting as a function of applied
voltage and liquid surface tension (Fig. 30a). McHale et al.128
investigated the electrowetting on a patterned layer of SU-8
photo-resist with amorphous Teflon coating, finding that contact
angle decreased from 152 to 114 after a cycle from 0 to 130 V
and back to 0 V (Fig. 30b).
Fig. 30 Optical images of the electrowetting of liquid droplets on

superhydrophobic surfaces with no reversible effect. (a) Four images
demonstrating electrically induced transitions between different wetting
states of a liquid droplet on the nanostructured substrate;127 (b) images of
a water droplet on a SU-8 patterned surface with a Teflon-AF under
various applied voltage.128
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Besides the works mentioned above, lots of research work has

been carried out in this area, which may lead the way to the
designing of electrowetting systems at very low voltages with
potential applications in the field of lab-on-a-chip and also in
developing functional microfluidic devices.
Evaporation and condensation of water droplets on a solid
substrate was first explained in the year 1977. Picknett et al.136
proposed two kinds of models to explain the phenomenon of
evaporation of water droplets on the solid surface. The first
model is constant contact angle with diminishing contact area
and the second is constant area with diminishing contact angle.
Birdi et al.137 found that there are two possibilities for a volatile
liquid drop on low surface energy substrates: (1) the rate of
evaporation is linear and follows the constant contact area mode
for the initial CA < 90 . (2) The rate of evaporation is non linear
and follows the constant CA mode for CA > 90 . Inspired by this
work, research138143 has been carried out in investigating the
evaporation and condensation phenomenon of water droplets on
superhydrophobic surfaces.
Sticky and magnetic properties of the water droplets,144146
interaction between a water droplet and solid surfaces,147,148 the
Leidenfrost droplets149151 and oil-repellency are the other functions that are the areas of attention for researchers in recent
times.
5. Hydrophilic photocatalytic coatings

Unlike hydrophobic/superhydrophobic surfaces that rely solely
on the flow of water to clean the surface, hydrophilic coatings
chemically break down dirt and other impurities when exposed
to sunlight. This process is called photocatalysis. The technique is basically inspired from the photosynthesis process of the
green leaves, which uses sunlight to drive the chemistry.
Although a few products that work on the principle of hydrophilicity are commercialized, this field is far from attaining
maturity. Research works are under way in developing hydrophilic self-cleaning coatings and there are regular publications in
this field.
5.1.
Fig. 31 Upon irradiation of TiO2 by ultra band gap light, the semiconductor undergoes photo-excitation. The electron and the hole that
result can follow one of several pathways: (a) electronhole recombination on the surface; (b) electronhole recombination in the bulk reaction
of the semiconductor; (c) electron acceptor A is reduced by photogenerated electrons; and (d) electron donor D is oxidized by photogenerated holes.
surface. On the surface, holes oxidise the organic molecules while

electrons combine with atmospheric oxygen to give superoxide
radicals, which in turn attack nearby organic molecules. This
results in the cleaning of surfaces by conversion of organic
molecules into carbon dioxide and water at ambient temperature.
This process is called cold combustion. An example is the total
decomposition of stearic acid [CH3(CH2)16CO2H] in the presence
of atmospheric oxygen to CO2 and H2O on TiO2 surfaces
(Fig. 32).152 A large number of organic pollutants can be broken
down by this technique, which includes aromatics, polymers,
dyes and surfactants. Superhydrophilicity in TiO2 is also
a light induced property in which the holes produced by the
Materials and mechanism to produce hydrophilic coatings
5.1.1. Titanium dioxide (TiO2). In the year 2001, Pilkington

Glass commercialised the first self-cleaning coating for glass
windows that was made of a thin transparent layer of TiO2. The
TiO2 cleans the window in sunlight through two distinct properties. (1) photocatalysis (2) hydrophilicity. During photocatalysis, organic dirt and other impurities present on the
coatings are chemically broken down by absorption of sunlight.
Hydrophilicity causes water to form sheets by reducing the
contact angle and washes away the dirt. TiO2 is highly efficient at
photocatalyzing dirt in sunlight. It is non toxic, cheap, easy to
deposit in the form of a thin film, chemically inert in the absence
of light and can easily reach the state of superhydrophilicity. All
these properties made TiO2 a highly suitable material to produce
hydrophilic surfaces. In normal conditions, TiO2 absorbs light
with energy equal to or greater than its band-gap energy,
producing excited charge carriers: positively charged holes (h+)
and negatively charged electrons (e) (Fig. 31). Though most of
these charges undergo recombination, few of them migrate to the
16316 | J. Mater. Chem., 2011, 21, 1630416322
Fig. 32 Photocatalytic decomposition of stearic acid is monitored by

infrared spectroscopy. The two CH stretching bands decrease in area
with irradiation, indicating that the surface is self-cleaning. The photocatalysis takes place on a nanocrystalline TiO2 film under 365 nm
irradiation.152
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photo-excitation process oxidize the lattice oxygen at the surface

of the material.
This results in oxygen vacancies that can be filled by adsorbed
water, resulting in surface hydroxide groups that make the
wetted surface more suitable than the dry surface, lowering the
static contact angle152 to almost 0 after irradiation. The selfcleaning properties of TiO2 are basically governed by the
absorption of ultra band-gap light and electronhole pair
generation. The band gap of bulk anatase TiO2 is 3.2 eV, corresponding to light of wavelength of 390 nm (near UV range).
5.1.2. Improving TiO2. TiO2 has become the most significant
material for photocatalytic hydrophilic coatings. The photocatalytic activity of TiO2 decreases by a considerable amount
when it is deposited as a smooth, nanocrystalline film. But most
of the requirements in the optical and glazing industries involve
the use of a robust, nanocrystalline film. Therefore, a lot of
research effort is going into improving the self-cleaning properties of these nanocrystalline films. Recent research work proved
that the photocatalytic activity of thick films is higher than thin
TiO2 films. TiO2 coatings of 3 mm thickness produced by spin
coating and annealing TiO2 paste was tested for photocatalysis
against a 25 nm coating. The thicker coatings absorb near-UV
light more strongly and the photocatalytic activity was very high,
exhibiting quantum yields of around 0.15% while it was only
0.04% for the thin film. This indicated that the thicker films
absorb more light and thus generate more excited charge carriers,
which have a life time long enough to reach the surface to induce
chemical reaction in the surface. But there is a limit to increasing
the thickness of the film. When all available UV light is absorbed,
or the distance to the surface is very high so that the charge
carriers have very little chance of reaching it before they
recombine, a still thicker film will not increase the photocatalytic
activity. The properties like optical clarity and durability are very
poor for thicker films and these issues have to be addressed in
future research.
5.1.3. Improving TiO2 by doping. Doping of TiO2 is an
effective technique to improve the photocatalytic activity and it
can also be easily incorporated into CVD or solgel processes.153
Based on the methods that are employed to deposit coatings,
dopants can exist as a single phase, mixed oxide or a separate
phase. Recent research work in this direction mainly focus on the
transition metal dopants. These dopants, when present as a metal
oxide, can be divided into two, based on their effects: (1) lower
oxidation state ones and (2) higher oxidation state ones.153,154
Metals with higher oxidation states, like Mo5+, Nb5+ and W6+,
increase the photocatalytic activity whereas metals with lower
oxidation states (<+4) like Fe3+, Co2+ and Ni2+ slow it down.
Park et al.154 used differential scanning calorimetry (DSC) to
study the low oxidation state dopants. He found that lower
oxidation state dopants caused crystallization to occur at around
20 C higher than the higher oxidation state dopants when they
are in the form of mixed oxides. A study made using X-ray
photoelectron spectroscopy (XPS) explained that the higher
oxidation state metal-doped films had a higher concentration of
hydroxyl groups adsorbed onto the surface than undoped and
lower oxidation state metal-doped TiO2. Since hydroxyl groups
play a vital role in the process of photocatalysis, this could
explain the increase in the photocatalytic activity in the presence

of higher oxidation state dopants. Phase-separated dopants have
also been experimented to improve the self-cleaning property in
which a pure phase of TiO2 contains a pure phase of a second
material. Recent studies have centered around the use of nanoparticles (use of metallic gold or platinum nanoparticles that can
assist photocatalysis in TiO2) as a method of incorporating
a phase-separated dopant.155,156
5.1.4. Other materials. Though TiO2 has been the main focus
of study in self-cleaning applications, other materials like WO3,
ZrO2, ZnO, CdS and polyoxometallates have been investigated
in recent years. However, none of the materials could surpass
TiO2, which uses only light to activate the process.
5.2.
Mechanisms employed to produce hydrophilic coatings
Various mechanisms are employed to produce hydrophilic

surfaces using TiO2 and other inorganic metal oxides. In the year
1978, Harrop et al.157 reported the first hydrophilic protective
coatings on glass substrate. In this method, he used vinyl tricholosilane films on float glass that converts an olefinic bond into
other carbon functional groups resulting in hydrophilic properties. Though this work was not very effective, it paved the way for
the evolution of research work in superhydrophilic coatings.
Jiaguo Yu et al.158 employed a solgel technique using alkoxide
solutions containing polyethylene glycol (PEG) to fabricate
superhydrophilic TiO2 coatings. Ding et al. employed a solgel
technique to fabricate TiO2-based nanocomposite hydrophilic
coatings by mixing TiO2 nanoparticles with a solgel derived
silica sol and methoxysilane group-bearing styrene-co-acrylate
(SA) oligomer, and curing with aminopropyltriethoxysilane at
ambient temperature. The resulting surface exhibited excellent
self-cleaning properties.
Zhang et al.159 reported self-cleaning particle coatings by using
a LbL assembly technique. A sub-monolayer of SiO2 particles
was covered with TiO2 nanoparticles with the help of oppositely
charged polyelectrolytes to generate a low-refractive-index film
exhibiting superhydrophilicity. The same research group160
investigated further the possibility of creating the dual functions
of self-cleaning and antireflection in double-layered TiO2SiO2
films that consisted of a dense top layer of TiO2 and a porous
bottom layer of SiO2. The films were prepared by LbL assembly
of SiO2 nanoparticles and titanate nanosheets with polycations.
Yaghoubi et al.161 produced a self cleaning TiO2 coating on
a polycarbonate substrate by employing a chemical surface
Fig. 33 The surface topography of a substrate before (a) and after

chemical treatment (b).161
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treatment method to create hydrophilic groups on the polycarbonate substrate (Fig. 33).
Beobide et al.162 employed dip coating technique to produce
multi-functional coatings consisting of two-layer stacks with
a mesoporous SiO2 layer and a dense/mesoporous TiO2 layer.
This coating exhibited both anti-reflective and self-cleaning
properties (Fig. 34). Xu et al.163 employed a LbL dip coating
method using a TiO2 sol and a methanol solution of NH4F as
precursors to fabricate transparent, visible light activated CN
F co-doped TiO2 films exhibiting superhydrophilicity. The WCA
of these films were 2.33.1 (Fig. 35). Bhatia et al.164 employed
a nano surface texturing technique to induce superhydrophilicity
on a glass substrate. In this process a thin layer of nickel is
deposited on the glass substrates, followed by annealing to create
Ni (nickel) nanoparticles. These Ni nanoparticles were used as an
etch mask to pattern the glass substrates and removed after
etching by nitric acid rinse. The resulting glass surface exhibited
excellent self cleaning properties (Fig. 36).
Fujishimas group165170 and a few other groups171,172 did novel
works in the area of superhydrophilicity and photocatalysis.
Recently, Akira et al.158 developed hydrophobic/superhydrophilic patterns by a new fabrication technique consisting of
five steps: (1) photocatalytic reduction of Ag+ to Ag (nucleation),
(2) electroless Cu deposition, (3) oxidation of Cu to CuO, (4)
deposition of a self-assembled monolayer (SAM), and (5) photocatalytic decomposition of selected areas of the SAM. A
hydrophobic/superhydrophilic pattern with 500 mm2 hydrophilic
areas was obtained in this process. The same group also fabricated a SiO2/TiO2 bilayer film with self-cleaning and antireflection properties by employing solgel and dip coating techniques.
Gu et al.173 produced TiO2 nanofibers with diameters of 200
550 nm by high temperature calcinations of the as-electrospun
tetrabutyl titanate (Ti(OC4H9)4)/polystyrene (PS) composite
fibers prepared by solgel processing and electrospinning techniques. The fiber films exhibited extremely stable superamphiphilicity and self-cleaning properties.
Though many research works have been carried out; this
review article within its scope has highlighted only a few novel
and important works conducted in the area of hydrophilic
surface fabrication.
6. Characterization techniques
Several characterization techniques are employed to analyze the
surface morphology and to compute the water contact angle of
hydrophilic and hydrophobic surfaces. This paper also details
a few characterization techniques that are widely used in the
analysis of materials, contact angle and surface chemistry.
Contact angle measurements play a pivotal role in the characterization of hydrophilic and hydrophobic coatings. Dodiuk
et al. used this technique (contact angle Goniometer) to compute
the contact angle and sliding angle of hydrophobic surface made
of polycarbonate (PC) (Fig. 37).
Atomic force microscopy (AFM) topography is a technique
widely used in surface roughness measurements of the selfcleaning coatings. Teshima et al. used this technique to analyze
the roughness of the superhydrophobic surface produced by
etching using PET (Polyethylene terephthalate). Environmental
ellipsometric porosimetry (EEP), grazing incidence X-ray
analyzes at low and wide angles (GI-SAXS and GI-WAXS),
electronic and nearfield microcopies, field-emission scanning
electric microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR),
UV-visible transmittance, X-ray photoelectron spectroscopy
(XPS) and differential scanning calorimetry (DSC) are a few
other techniques that are widely used in characterizing hydrophilic and hydrophobic coatings.
7. Applications of self-cleaning coatings

Self-cleaning coatings find applications in diversified fields.
Potential application sectors include the textile industry (selfcleaning clothing), automobile industry (self-cleaning windshield
glass, car bodies and mirrors), optical industry (cameras, sensors,
lenses and telescopes), marine industry (anticorrosion protection) and aerospace industry (non sticky surfaces). Self-cleaning
coatings can also be used in windows (window coatings), solar
modules (self-cleaning coatings for solar modules) and in paints
(exterior paints with self-cleaning properties).
Because of the potential applications of self-cleaning coatings,
many companies have already been attracted to this technology
Fig. 34 (a) An AFM top view image of a mesoporous SiO2 coating. (b) An AFM top view image of a mesoporous TiO2 coating.162
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Fig. 35 AFM 3D images of the surface of (a) CTiO2 film; (b) CNFTiO2-0.5 film; (c) CNFTiO2-1 film; (d) CNFTiO2-2 film.163
Fig. 36 SEM images of nickel nanoparticles on glass substrates after

rapid thermal annealing for 5 min at (a) 600 C, and (b) 650 C
temperatures.164
and they have commercialized a few products. The Pilkington

group of companies commercialized the first self-cleaning coated
float glass product called Pilkington Activ (http://www.
pilkington.com/). Self-cleaning paints have been commercialized by a German-based company named Lotusan (http://www.
lotusan.de/) and they are now commonly available in Europe.
Cardinal Glass Industries (Neat Glass) (http://www.
cardinalcorp.com/), Saint-Gobain (SGG Aqua Clean) (http://
www.saint-gobain.com/en) and PPG Industries (http://www.
ppg.com/en/Pages/default.aspx) are a few other companies
working on this technology.
Fig. 37 Sessile drops for static contact angle measurements of: (a)
uncoated PC and PC coated with (b) 0.5 wt% silica 1.5 wt% FPOSS
(mixed) and (c) 0.5 wt% silica 1.5 wt% FPOSS (two-layer coating).
8. Other areas of focus

Though many research works have been successful in the
laboratory, they fail miserably when converted into real time
products due to many reasons. Peeling off of the coatings
from substrates is a major concern that has to be addressed
while developing self-cleaning membranes for windows. The
coating should not have any micro cracks/scratches on its
surface. The membrane should be deposited onto the substrate
without any air gaps. The behaviour of water droplets on the
surface of the coating is one other area that has to be focused as
J. Mater. Chem., 2011, 21, 1630416322 | 16319

View Article Online
Fig. 38 A flowchart explaining the summary of various materials and fabrication procedures.
well. The coating produced should not allow the water droplets
to penetrate through it. These are other factors that require
further research and development to make self-cleaning coatings
more viable for commercialization. The flowchart (Fig. 38)
below gives a brief summary of various materials and fabrication procedures involved in the synthesis of self-cleaning
coatings.
Acknowledgements
V.A.G and H.K.R. thank National University of Singapore for
graduate research fellowship. A.S.N and S.R. thank National
Research Foundation, Singapore for partially supporting the
program (Grant number: NRF 2007 EWT-CERP 01-0531).
References
9. Conclusion
All the research efforts, as we have seen here, are poised to
emulate the supreme strategies perfected by nature over billions
of years. The self cleaning surface on naturally occurring leaves
and wings of certain insects is multipurpose in achieving selfcleaning, anti-reflective, camouflage and various other functionalities which has got researchers across the globe take stock
and attempt to mimic. Though the self cleaning surfaces designed
by them are yet to match their naturally occurring counterparts,
the fabrication techniques have indeed evolved into more environmentally compatible and cost-effective. This review article
within its scope encompasses various research works conducted
in hydrophilic and hydrophobic surfaces within the last decade.
This article also highlights other challenges like the peeling-off
effect in developing competent self-cleaning surfaces. Selfcleaning surfaces can be used in several fields from glass industry
to textile industry and it is a promising field for exciting research
work.
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A Review On Self-Cleaning Coatings

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A review on self-cleaning coatings

Available from: Sreekumaran Nair

Dynamic Article Links <

A review on self-cleaning coatings

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Healthcare and Energy Materials Laboratories, National University of

Mr. Anand Ganesh Venkatesan

Mr. Hemant Kumar Raut is

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3. Hydrophobic and superhydrophobic coatings

Nature is the source of inspiration for many researchers around

This journal is The Royal Society of Chemistry 2011

Fig. 1 A schematic representation of hydrophilic, hydrophobic and

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paved way for the development of several synthetic methods to

16306 | J. Mater. Chem., 2011, 21, 1630416322

Fig. 3 The SEM images of biomimetic superhydrophobic surfaces made

nanopins on its surface along with the formed microstructure.

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3.2. Materials and mechanism to produce hydrophobic and

Fig. 4 SEM images of natural superhydrophobic surfaces with a unitary

Fig. 5 SEM images of biomimetic superhydrophobic surface with

the fluoroalkylsilane (FAS) modification, the cellulose acetate

3.2.1. Roughening the surface of low surface energy material

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Fig. 8 A SEM image of a PS-PDMS surface cast from a 5 mg mL1

Fig. 7 A SEM image of a PS-PDMS/PS electrospun fiber mat and the

16308 | J. Mater. Chem., 2011, 21, 1630416322

3.2.1.4. Inorganic materials. Superhydrophobic properties

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Fig. 11 A SEM image of the PS surface produced by electrostatic

Fig. 9 (a) A schematic illustration of honeycomb patterned21 film

Fig. 10 A SEM image of the flower-like crystal structure of PE.22

This journal is The Royal Society of Chemistry 2011

resulted in the production of films with reversibly switchable

Fig. 12 A SEM image of aligned ZnO nanorods prepared by a two-step

J. Mater. Chem., 2011, 21, 1630416322 | 16309

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3.2.2.1. Wet chemical reaction and hydrothermal reaction.

16310 | J. Mater. Chem., 2011, 21, 1630416322

oxidation pre-treatment and chemically modifying the surface

Fig. 14 The biomimetic superhydrophobic surfaces constructed by

This journal is The Royal Society of Chemistry 2011

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View Article Online

This journal is The Royal Society of Chemistry 2011

array of nanopits and nanopillars on the surface of the material.

J. Mater. Chem., 2011, 21, 1630416322 | 16311

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silicate multilayers on a silica-coated substrate (Fig. 19a). This

16312 | J. Mater. Chem., 2011, 21, 1630416322

3.2.2.5. Electrospinning technique. Electrospinning is

Fig. 20 A SEM image of electrospun nanofibers (a) before (b) after

This journal is The Royal Society of Chemistry 2011

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