International Journal of Advanced Research in ISSN: 2278-6252

Engineering and Applied Sciences Impact Factor: 4.817

SUPER-HYDROPHOBICITY ON TEXTILES A REVIEW

Chinchwade S.S.*
Landage S.M.**
Bonsule S.***

Abstract: Engineering interfaces with unique chemical, physical and mechanical properties
has become a major branch of material science. Surfaces that combine a low surface energy
with a high surface roughness, so called superhydrophobic surfaces, are ascribed the
greatest potential in terms of their exceptional water repellent properties. Superhydrophobic
surfaces have developed great deal of interest among researchers because of their unique
ability to shed water off the surface. The two key elements that determine
superhydrophobicity are surface energy and surface roughness. Superhydrophobicity is
somewhat ambiguously applied to surfaces exhibiting a water contact angle of more than
150. Surfaces with water and oil repellency have attracted increasing interest for their
applications in diverse fields such as self-cleaning paint, sports and outdoor clothing,
biomedical layers, integrated sensors, micro-fluidic channels. Such surfaces are usually
achieved by the combination of surface geometrical structure and low surface energy
chemical compositions.
Key words: superhydrophobicity, self-cleaning, nanoparticles, surface energy etc.

*Prof., Dept. of Textiles, D.K.T.Es Textile & Egg. Institute, Ichalkaranji, India
**Asstt. Prof., Dept. of Textiles, D.K.T.Es Textile & Egg. Institute, Ichalkaranji, India
***M.Text. (Tech.Text.) candidate, D.K.T.Es Textile & Egg. Institute, Ichalkaranji, India

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 International Journal of Advanced Research in ISSN: 2278-6252
Engineering and Applied Sciences Impact Factor: 4.817

1. INTRODUCTION
Wettability is one of the most important properties of a solid surface and the contact angle
has been commonly used to characterize the surface wettability. Superhydrophobic surfaces
have attracted much interest because of their potential practical applications such as anti-
sticking, anti-contamination, and self-cleaning coating. Attracted by their potential industrial
applications, numerous attempts to preparing artificial superhydrophobic surfaces have
been done by mimicking the lotus leaf structure. Porous structures, nano-fibers and carbon
nanotubes have also been used to develop superhydrophobic surfaces.
1.1. Superhydrophobicity
For many years, people have been attracted by the self-cleaning property of the lotus leaf,
and dream to develop man-made superhydrophobic surfaces. Superhydrophobic and self-
cleaning surfaces exist widely in nature. Butterfly wings, legs of a water strider and leaves of
some plants are good examples. Thanks to the innovation of scanning electron microscopy,
today, scientists know the plants ability to repel water and dirt results from the
superhydrophobicity, due to the combination of micrometer-scale hills and valleys and
nanometer-scale waxy bumps, in combination with the reduced adhesion between surfaces
and particles. A surface with water contact angle large than 150 and a low sliding angle (the
critical angle where a water droplet with a certain weight begins to slide down the inclined
plate) is usually called a superhydrophobic surface. A combination of low surface energy and
adequate surface roughness is necessary to obtain superhydrophobic and superoleophobic
surface. High contact angles are achieved by reducing the surface energy of the solid surface
and increasing its roughness in an appropriate manner, thus reducing wetting. Techniques
involved in developing such surfaces include plasma treatment, chemical etching, chemical
vapor deposition, lithography, and so forth.

1.2. Nanomaterials and Nanotechnology

Nanos (Greek) means dwarf and nano-materials are measured in units of nanometer which
is 1 billionth of a meter i.e.110-9 m and involves developing materials or devices within that

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 International Journal of Advanced Research in ISSN: 2278-6252
Engineering and Applied Sciences Impact Factor: 4.817

size. Nanotechnology is defined as the precise manipulation of individual atoms and

molecules to create layered structures. Nano size particles can exhibit unexpected
properties different from those of the bulk material. Small size of nanoparticles leads to
particle particle aggregation here by making physical handling of nanoparticles difficult in
liquid and dry powder forms. The basic premise is that properties can dramatically change
when a substances size is reduced to the nanometer range.
The nano-technological approach starts from producing nanobers or nanocomposite bers
to nanostructure formation and nano-electronics embedded garments to produce a wide
range of smart and intelligent textiles.
Therefore, real applications of such super-hydrophobic surfaces have been very limited so
far. Currently, many researches are focusing on super-hydrophobic surfaces. However, oil
repellency is also a very important property for the super-hydrophobic surface to maintain
its self-cleaning property. If a self-cleaning surface is not oil repellent, when it is in a dirty
environment, oily materials can accumulate on the surface, eventually fill the textures,
leading to the loss of the super-hydrophobic and self-cleaning properties
2. PRINCIPLE OF SUPERHYDROPHOBICITY
Wetting of a solid surface is dominated by three interfacial tensions and can simply
be evaluated by the spreading parameters(S).
S = ( + ) (1)
If the spreading parameter S>0, the liquid tends to spread completely on the solid.
While for S<0, the liquid partially wets the solid and forms a spherical cap with a
contact angle C, which is usually used for quantitative characterization of the wetting
phenomena (Fig.a).

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 International Journal of Advanced Research in ISSN: 2278-6252
Engineering and Applied Sciences Impact Factor: 4.817

The value of the angle is determined by three surface tensions where the chemical
potential in the three phases should be at equilibrium. Therefore, the contact angle
relationship C derived by balancing the three tension forces onto the solid surface
sv sl
Cos c = lv
(2)

This is Youngs equation for the determination of contact angles.

The case we are specifically interested in is how liquid droplets act on solid surfaces.
Hydrophobicity or wettability of a surface is often characterized by the static and
apparent contact angle measurement of water. If the value of the static contact angle
is 00 C 900, the liquid tends to spread on the surface. It is usually referred to as
hydrophilic or oleophilic surface in terms of aqueous or oily liquid, respectively. If the
value of the contact angle is 900 < C 1800, the wetting area tends to shrink. It is
then referred to as a hydrophobic or oleophobic surface in terms of aqueous or oily

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 International Journal of Advanced Research in ISSN: 2278-6252
Engineering and Applied Sciences Impact Factor: 4.817

liquid, respectively. Surfaces with the water contact angle between 1500 and 1800 are
usually referred to as super-hydrophobic.
2.1. Classical models for contact angles on rough surfaces
Homogeneous solidliquid interface: Wenzel model Youngs equation is an
oversimplified expression, and is only valid for ideally flat surfaces that are atomically
smooth and chemically homogeneous. Conversely, very few solids are atomically flat.
Wetting on rough surfaces was first considered by Wenzel In the Wenzel state,
where the roughness grooves are completely filled with liquid (Fig. 2b), the contact
angle (W) can be described by.
Cos (w) = Rf [SV SL / LV]. (3)
where R is the surface roughness factor, which is defined as
Rf = actual area/projected area.. (4)
Combining Eq. (4) with Youngs equation yields
cos (w) = Rf. cos (c)................... (5)
Since the roughness factor is always larger than unity in practical situations, it is
obvious that the apparent angle on a roughened surface will become smaller if its
intrinsic contact angle on a smooth surface is less than 900. Similarly, the apparent
contact angle will be larger, if its intrinsic contact angle is larger than 900.
2.2. Heterogeneous solidliquid interface: CassieBaxter model:
The Wenzel regime is usually recognized as homogeneous wetting, since the liquid
completely penetrates into the grooves. Under some circumstances, especially with high
surface rough-ness, vapor pockets may become trapped underneath the liquid yielding a
composite interface (Fig.2c). This heterogeneous wetting phenomenon is usually described
by CassieBaxter (CB) theory, from which the apparent contact angle (CB) is given by Eq.
(6):
cos (CB) = fs. cos (c) + fv. cos (v) (6)
where C is the intrinsic contact angle on the original smooth surface, and fS and fv are
the area fractions of the solid and vapor on the surface, respectively. Since fs+ fv= 1,
and V = 1800 (implying that a suspended liquid droplet in air is a perfect sphere.),
Eq. (7) can be rewritten as follows:
cos (CB) = fs. (cos (C) +1) 1 .. (7)

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 International Journal of Advanced Research in ISSN: 2278-6252
Engineering and Applied Sciences Impact Factor: 4.817

From Eq. (7), it can be found that droplets will have a higher apparent contact angle
if less area is in contact with the solid substrate. The CB equation simply indicates the
contact angle can be increased even when the intrinsic contact angle of a liquid on
the original smooth surface is less than 900.
3. APPLICATION TECHNIQUES
Numerous techniques were employed to obtain super-hydrophobic and super-oleophobic
surfaces:
Covalent layer by layer assembly.
Polymer film roughening.
Chemical vapour deposition.
Sol-gel process
3.1. Covalent Layer by layer assembly
Ming, Wu, van Bentham and De With (2005) developed a procedure for preparing Super-
hydrophobic films with a dual-size hierarchical structure composed of raspberry-like
particles. These particles were silica based with amine-functionalized surface and were
chemically deposited on the epoxy films. Another layer of poly (dimethylsiloxane) was
grafted on the raspberry-like particles, thus hydrophobic characteristics were achieved.
Manca et al (2009) adopted a sol - gel process to produce a double-layer coating consisting
of silica nanoparticles with a trimethoxysiloxane-functionalized surface which were partially
embedded into an organosilica binder matrix. A glass substrate was used and the treated
surface showed super-hydrophobic contact angles.
3.2 Polymer film roughening
This process uses phase separation of a multicomponent mixture as a means to super-
hydrophobic polymer films. Franco, Kentish, Perera and Stevens (2008) designed a super-
hydrophobic polypropylene membrane by a solvent casting of polypropylene and utilizing
the surface roughness and porosity developed with a nonsolvent. Levkin, Svec and Frechet
(2009) used the phase dispersion technique where, in situ polymerization of common
monomers such as butylmethacrylate, ethylene dimethacrylate in the presence of a
pathogenic solvent such as 1-decanol, cyclohexanol and/or tetrahydrofuran resulted in
superhydrophobic surfaces with micro- and nanoscale roughness. Yuan, Chen, Tan and Zhao
(2009) prepared a stable super-hydrophobic high-density polyethylene (HDPE) surface using

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 International Journal of Advanced Research in ISSN: 2278-6252
Engineering and Applied Sciences Impact Factor: 4.817

ethanol in a humid atmosphere at 5 C. Zhang et al (2008) created an emulsion

copolymerization of acrylates with silicone oligomers. Wool fabric was treated with this
emulsion and it exhibited excellent water repellency. Cao et al (2009) fabricated
superhydrophobic surfaces with anti-icing properties using a combination of organosilane-
modified silica nanoparticles and an acrylic polymer binder. Steele, Bayer and Loth (2008)
described a technique of spraying a super-oleophobic coating of ZnO nanoparticles blended
with water borne per fluoro acrylic polymer emulsion on practically any surface.
3.3. Chemical vapor deposition
In this method gaseous reactants can be deposited onto a substrate to form a nonvolatile
solid film. Zimmerman et al (2008) used one-step gas phase coating a layer of poly-methyl-
silses-quioxane nano-filaments onto individual textile fibres. Li, Xie, Zhang and Wang (2007)
used a sealed chamber with a saturated atmosphere of trichloro-methyl-silane to deposit on
a hydrophilic cotton fabric. Polymerization of SiOH groups resulted in nanoscale silicone
coating rendering superhydrophobicity.
3.4. Sol-gel process
This method synthesizes gels and nanoparticles. Sol-gel method can be easily tuned by
varying the method and composition of the reaction mixture. Gan Zhu, Guo and Yang (2009)
created hydrophobic cotton and polyester fabrics using sol-gel coating and treatment with
hydrolyzed hexadecyltrimethoxysilane. Daoud, Xin and Tao (2004) prepared transparent
durable knit/woven cotton substrates using a modified silica sol formed by co-hydrolysed
and polycondensed mixture of hexa-decyl-trimethoxysilane, tetra-ethoxy-orthosilicate and 3
glycid-oxypropyl-trimethoxysilane.
They showed this treatment was persistent even after 10 cycles of washing. Yu, Gu, Meng
and Qing (2007) used a combination of silica-sol and perfluorooctylated quaternary
ammonium silane coupling agent and were applied to cotton fabrics using a conventional
pad-dry-cure process. The fabrics were super-hydrophobic after treatment.
4. MATERIALS
Super-hydrophobic coatings can be made from many different materials. The following are
known possible bases for the coating:
Manganese Oxide Polystyrene (MnO2/PS) nano-composite
Zinc Oxide Polystyrene (ZnO/PS) nano-composite

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 International Journal of Advanced Research in ISSN: 2278-6252
Engineering and Applied Sciences Impact Factor: 4.817

Precipitated Calcium Carbonate

Carbon nano-tube structures
Silica nano-coating
5. TECHNICAL APPLICATIONS
Since the Lotus-effect is solely based physico-chemically and is not bound to a living system,
a self-cleaning surface can be technically manufactured. The materials for such new coatings
are available. Until today, however, the contradictory demand for rough surfaces as a basis
for clean surfaces was ignored. Still scientific investigation and industry have made intensive
efforts to develop dirt-repellent or self-cleaning surfaces. Some materials allow the
production of coatings with hydrophobic and oleo phobic properties. They are thus neither
wettable nor can they get oil-slicked, and can be called ultra phobic. Possible fields for
application are facade paints, roof tiles, textiles and the rich field of coatings. If application is
successfully managed, the Lotus-effect surely is one of the most impressing examples of
biomimicy of the last years.
6. CONCLUSION
Nanotechnology holds an enormously promising future for textiles. The development in
functional finishes based on nanotechnology has endless possibilities and at present the
application of nanotechnology merely reached the straight line. The new concepts exploited
for the development of nano-finishes have opened up exciting opportunities for the further
research and development. Nanotechnology does not affect other properties of the fabric
which gets affected in other types of finishes. Nanotechnology involves a three-dimensional
surface structure on the textile surfaces which is very beneficial and does not affect the
properties of the substrate like the handle and breathability and does not add more extra
weight to the treated textile. When nanosols technology is used for water repellency then
finish involves a three-dimensional surface structure with gel-forming additives which repel
water and prevent dirt particles from attaching themselves. The mechanism is similar to the
lotus effect occurring in nature. With this technology we can achieve super hydrophobic
surfaces which are rough and textured.

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 International Journal of Advanced Research in ISSN: 2278-6252
Engineering and Applied Sciences Impact Factor: 4.817

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