Applied Surface Science 257 (2010) 333–339

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Transparent Superhydrophobic silica coatings on glass by sol–gel method

Satish A. Mahadik a , Mahendra S. Kavale a , S.K. Mukherjee b , A. Venkateswara Rao a,∗
a
Air Glass Laboratory, Department of Physics, Shivaji University, Vidyanagar, Kolhapur 416 004, Maharashtra, India
b
Fuel Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, Maharashtra, India

a r t i c l e i n f o a b s t r a c t

Article history: Wetting behavior of solid surfaces is a key concern in our daily life as well as in engineering and science. In
Received 30 December 2009 the present study, we demonstrate a simple dip coating method for the preparation of Thermally stable,
Received in revised form 22 June 2010 transparent superhydrophobic silica films on glass substrates at room temperature by sol–gel process.
Accepted 22 June 2010
The coating alcosol was prepared by keeping the molar ratio of methyltriethoxysilane (MTES), trimethyl-
Available online 30 June 2010
methoxysilane (TMMS), methanol (MeOH), water (H2 O) constant at 1:0.09:12.71:3.58, respectively with
13 M NH4 OH throughout the experiments and the films were prepared with different deposition time
Keywords:
varied from 5 to 25 h. In order to improve the hydrophobicity of as deposited silica films, the films
Superhydrophobic
Transparent
were derivatized with 10% trimethylchlorosilane (TMCS) as a silylating agent in hexane solvent for 24 h.
Wetting Enhancement in wetting behavior was observed for surface derivatized silica films which showed a max-
Sliding angle imum static water contact angle (172◦ ) and minimum sliding angle (2◦ ) for 25 h of deposition time. The
Coating superhydrophobic silica films retained their superhydrophobicity up to a temperature of 550 ◦ C. The silica
films were characterized by field emission scanning electron microscopy (FE-SEM), surface profilometer,
Fourier transform infrared (FT-IR) spectroscopy, thermo-gravimetric and differential thermal analysis
(TG–DTA), percentage of optical transmission, water contact angle measurements. The imperviousness
behavior of the films was tested with various acids.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction method was applied to the fabrication of water repellent surfaces

The nature of interactions between water and superhy-
drophobic surfaces has been a subject of enormous interest.
Superhydrophobic surfaces provide an ideal model interface to
study behavior of the water droplets. Surface energy and surface
roughness are the dominant factors for wettability of the surface.
Various methods have been employed to generate the surfaces that
can mimic the structure and chemistry of natural superhydropho-
bic surfaces like lotus leaves [1]. Several studies have reported that
by finely controlling the micro/nanostructure or chemical compo-
sition of a surface, the adhesion between the superhydrophobic
surface and water can be changed. Such superhydrophobic sur-
faces show potential in a variety of applications from antisticking,
anticontamination and self-cleaning to anti-corrosion and low fric-
tion coatings [2–10]. Beyond the existence of large water contact
angles, very low adhesion, characterized by a small sliding angle is
a requirement for many applications.
Sol–gel technology makes it promising to produce silicate mate-
rials with properties that cannot be achieved by other methods and
to improve the properties of conventional materials. The sol–gel
∗ Corresponding author. Tel.: +91 231 2609228; fax: +91 231 2609233.
E-mail address: avrao2012@gmail.com (A.V. Rao).
by several groups [11–20]. The water uptake of silica films is due to
the presence of Si–OH groups on the surface. Substitution of the Hs
from the Si–OH groups by the hydrolytically stable Si–O–R (where,
R = alkyl or aryl) groups through the oxygen bonds prevents the
adsorption of water and hence results in the hydrophobic silica
surfaces [21,22]. Gellermann et al. [23] modified surfaces of silica
spheres by using different silane coupling agents. Orozco-Teran et
al. [24] modified triethoxyfluorosilane (TEFS) films by silylation for
the enhancement of hydrophobicity. In the present research work,
we report an easy and efficient method to synthesize superhy-
drophobic surface by simple dip coating sol–gel method exhibiting
a self-cleaning behavior.
2. Experimental
2.1. Materials
The superhydrophobic silica films have been prepared by
sol–gel process using a simple dip coating method. Chemicals used
were methyltriethoxysilane (MTES) (Sigma–Aldrich Chemie, Ger-
many), methoxytrimethylsilane (TMMS) (Fluka Chemie, Switzer-
land), trimethylchlorosilane (TMCS) (Sigma–Aldrich Chemie, Ger-
many), methanol, hexane (S. D. Fine-Chem Ltd., Mumbai) and
Ammonia (NH3 , Sp.Gr.0.91 Qualigens Fine Chemicals, Mumbai).

0169-4332/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2010.06.062
334 S.A. Mahadik et al. / Applied Surface Science 257 (2010) 333–339
2.2. Sample preparation
The superhydrophobic silica coating was synthesized by fol-
lowing four main steps: (1) alcosol preparation, (2) dipping and
withdrawing the substrates from the alcosol, (3) annealing of the
as deposited silica films and (4) surface derivatization. To get uni-
form coating, the glass microslide substrates were cleaned by the
procedure described earlier [25]. The coating alcosol was pre-
pared at optimized molar ratio of MTES:TMMS:CH3 OH:H2 O at
1:0.09:12.71:3.58, respectively with 13 M NH4 OH at room tem-
perature (27 ◦ C). A single step base catalyzed sol–gel process was
followed to prepare the coating alcosol. In the first step, MTES and
TMMS were diluted in methanol solvent at given molar ratio. Then
basic water (ammonium hydroxide, 13 M) was added drop-by-drop
to the solution and stirred for 15 min to get homogeneous alcosol.
The alcosol cannot turns to gel within depositions time due to their
higher gelation time. So efforts were made to deposit the films prior
to gel formation. All the films were prepared at room temperature
and deposition time was varied from 5 to 25 h. The prepared alcosol
was taken in test tubes and the substrates were dipped vertically.
The substrates were withdrawn from the bath containing alcosol
at a speed of 5 mm/s. The withdrawn films were dried for 24 h at
room temperature (27 ◦ C) to get good chemical bonding between
the coating sol and the substrate. Finally, these films were kept in
the oven for annealing at 100 ◦ C for 5 h and soaked in the mixture
containing 10% TMCS in hexane for 24 h at room temperature. The
derivatized silica films were annealed at 100 ◦ C for 1 h and taken
out from the oven after cooling at ambient temperature.
The surface morphology of the silica films was examined using
Field Emission Scanning Electron Microscope (JEOL, JSM 7001F,
Japan). The roughness of the films was determined by using
a surface profilometer (Ambios XP-1 Model, India). The surface
roughness was measured ten times at the same location and an
average of the 5 measurements was taken for each sample. The sur-
face chemical modification of the films was studied using infrared
spectroscopy (Perkin-Elmer, Model No. 783, USA). The samples for
FT-IR characterization are prepared by removing film from the sub-
strate by using stainless steel knife. Sample powder was mixed with
KBr and a homogeneous mixture formed with a mortar and pestle.
This mixture was placed in a cylindrical die of 13 mm diameter
and pressed for about 5 min at 200 kg/cm2 to form a pellet and
then scanned in frequency range from 450 to 4000 cm−1 . The ther-
mal stability of coating was studied by TGA-DTA (TA Instrument
Q600 USA), thermal stability in terms of retention of hydropho-
bicity confirmed by putting sample in Furnaces (Neytech. VULCAN
Benchtop Model 3-550 USA) at different temperatures. Percentage
of optical transmission of the films was measured in the visible
range using UV-VIS spectrophotometer (Systronic 119, USA). Wet-
ting properties of the films was tested by measuring the static and
dynamic water contact angles using computer interfaced contact
angle meter equipped with a CCD camera (Ramehart Instrument
Co., advanced goniometer model no. 500 F1 USA) at room temper-
ature (∼27 ◦ C). Contact angles were measured at six different spots
for each sample and the average value was adopted as the contact
angle.
Table 1
Wetting properties of coating after derivatization.
Deposition time (hours) Roughness (nm) Contact angle () after derivatization
◦
5 10 161
10 11 164◦
15 18 167◦
20 887 168◦
25 1129 172◦
3. Results and discussions
3.1. Static and dynamic water contact angle measurements
Young [26] had described the forces acting on a liquid droplet
spreading on a surface. The contact angle () of the drop is related
to the interfacial energies acting between the solid–liquid ( SL ),
solid–vapor ( SV ) and liquid–vapor ( LV ) interfaces given by rela-
tion:
SV − SL
cos  = (1)
LV
The expression given by Eq. (1) is strictly valid only for surfaces that
are atomically smooth, chemically homogeneous, and those that
do not change their characteristics due to interactions of the prob-
ing liquid with the substratum, or any other outside force. In the
Wenzel regime [27], the liquid wets the surface, but the measured
contact angle (*) differs from the “true” contact angle ():
cos  ∗ = r cos  (2)
where r is the ratio between the true surface area and its horizon-
tal projection. According to the Cassie and Baxter [28] model, the
surface traps air in the hollow spaces of the rough surface, so that
the droplet essentially rests on a layer of air. The contact angle ( CB )
governed by the Cassie–Baxter model is expressed as follows:
cos CB = rf (cos FLAT ) + f − 1 (3)
where f is the fraction of surface area that supports the liquid
droplet, and  FLAT is the contact angle on a flat surface.
The tilt angle refers to the critical angle between the substrate
and the horizontal plane, below which the water droplet begins
to move upon elevating one end of the substrate. The maximum
frictional force (fmax ) required to dislodge a liquid from a surface
can be calculated by,
fmax = mg sin  (4)
where m is the mass of the water droplet and g is the accelera-
tion due to gravity, respectively. Where,  represents the minimal
sliding angle of the water droplet on the surface. The effect of
deposition time on static water contact angle, sliding angle and
maximum frictional force to slide is given in Table 1. To evaluate
the wetting behavior of the coating, the images of the contact angle
() of the water droplet on the coatings synthesized before and
after derivatization and at different deposition time values have
been measured using contact angle meter, as shown in Fig. 1. The
sliding angle was measured on derivatized silica films. The water
droplets roll off from the silica film prepared at 5 h of deposition
time, having a water contact angle of 161◦ and maximum frictional
force required to slide the water droplet on film surface is 56 ␮N
at sliding angle of 9◦ . Whereas the water droplet rolls off quickly
from the silica film prepared at 25 h of deposition time having a
water contact angle of 172◦ and maximum frictional force required
to slide the water droplet on film surface is 18 ␮N at sliding angle of
2◦ . The as prepared silica films contain a large number of hydroxyl
and alkoxy groups which are responsible for the hydrophilic char-
Sliding angle () Maximum friction force (fmax ) (␮N)
9 56
8 50
7 43
4 25
2 18
 S.A. Mahadik et al. / Applied Surface Science 257 (2010) 333–339 335

Fig. 1. The effect of surface modification on the hydrophobicity.

acter of the film surface. However, using TMCS in the sol–gel
processing stage the –OH groups are replaced by hydrolytically
stable –O–Si–(CH3 )3 groups. The coatings surface becomes super-
hydrophobic because of the hydrolytic stability of Si–C bonds. At
lower deposition time, the silica film surface introduces roughness
required to superhydrophobicity with surface covered by silicon
trimethyl groups. However, as the deposition time increases; sur-
face roughness increases resulting large water contact angle and
low sliding angle. Although, the maximum frictional force required
to slide water droplet on a film surface is decreased with increas-
ing the deposition time. This strongly suggests that the contact
model of a water droplet on the film prepared from T = 25 h is the
Cassie–Baxter’s model. The effect of different organic liquids and
acids on the contact angles of superhydrophobic surface are shown
in Table 2. As regards close approach of applications and stability of
a superhydrophic coating, their hydrophobicity against the organic
liquids and strong acids was checked. It is clear that the coatings
show superhydrophobic nature against the double distilled water,
glycerin and HCL, but hydrophobic nature against the H2 SO4 and
HNO3 . It shows the superhydrophilic nature with hexane. Accord-
336 S.A. Mahadik et al. / Applied Surface Science 257 (2010) 333–339

Table 2 superhydrophobic behavior of the silica film. The higher magni-

Hydrophobicity of coating against different organic liquid and strong acids.
fied image (5500×) of the silica film (Fig. 2(f)) shows the surface
Liquids Contact angle () having microsized particles with inhomogeneous size distribution.
Double distilled water 172◦ According to the Cassie–Baxter model air trapped within micro-
Glycerine 170◦ scale particles reduces contact surface area between liquid drop
Pure HCl 157◦ and coating surface.
H2 SO4 125◦
HNO3 90◦
Ethanol 15◦
3.4. Imperviousness against strong acids
Hexane 0◦
It was observed that the contact angle on a coating changes
due to the effect of the nitric acid (HNO3 ), sulphuric acid (H2 SO4 )
Table 3
and hydrochloric acid (HCl) in water [29]. Fig. 3 shows the contact
Table shows effect of surface roughness and transparency on superhydrophobicity
of films. angle variations for different concentrations of nitric acid (HNO3 ),
sulphuric acid (H2 SO4 ) and hydrochloric acid (HCl) in water. From
Deposition time Roughness (nm) Transparency (%) Hydrophobicity ()
Fig. 3, it is clear that the coatings show hydrophophobic nature and
in hours
does not allow to wet strong acids completely on the surface of coat-
5 10 90.45 161◦ ings even though at 100% concentration (pure acid). Such hybrid
10 11.2 90.33 164◦
15 18.4 90.30 167◦
coatings show the contact angles 157◦ , 125◦ and 90◦ at 100% con-
20 887.2 90.25 168◦ centration of hydrochloric acid (HCl), sulphuric acid (H2 SO4 ) and
25 1129.7 90.22 172◦ nitric acid (HNO3 ) respectively.
According to the Zisman’s rule [30], each coating surface having
a critical surface tension,  C such that there is a partial wetting if
ing to this result it is clear that this type of coating is effective  >  C , and total wetting if  <  C , where  is the surface tension of
against strong acids, and it opens a variety of potential applica- the liquid. From this, it follows that the critical surface tension,  C
tions such as transparent coating on a marble sculptures to avoid of the hydrophobic surface is sufficiently less so that pure water or
acidic effect. pure acids with higher surface tension values do not wet the surface
completely. But, when an organic liquid such as alcohol is mixed in
3.2. Effect of deposition time and surface modification on water, the surface tension of water ( W ) is lowered. Considerable
wettability of the films lowering of the surface tension is caused at low concentrations; but
at intermediate and high concentrations, the surface tension of the
The water repellent coatings were deposited on glass substrate solution,  A , changes comparatively little and mostly tends towards
for various time intervals varying from 5 to 25 h. We found that, the value possessed by the organic liquid. The effect of concentra-
the water contact angle increases with increase in deposition time tion of acid on wettability of coating is described by Szyszkowski
and surface modification of the films with 10% TMCS in hexane for formula [31]:
24 h as shown in Table 1. The static water contact angle increases
W − A C
 
from 161◦ to 172◦ with increase in deposition time from 5 to 25 h = log +1 (5)
after derivatization. This is due to the fact that, surface rough- W k
ness increases with deposition time which favors to increase in where C is the concentration of the organic acid in water, and b
the water contact angle. The roughness increases from 10 nm to and k are the constants. From Eq. (5), it is clear that the surface
1129 nm with increase in deposition time from 5 to 25 h after tension of the acid in water does not affect surface tension of the
derivatization. The coating shows water contact angle of 161◦ at solution considerably as the concentrations of these acids increase
deposition time of 5 h and shows improvement in its water contact in water. As a result, hydrophobicity of the coatings remains up
angle with increase in deposition time. After derivatization maxi- to higher concentration of acid in water even as an impurity. The
mum number of polar (–OH) groups are replaced by non-polar and MTES and TMMS based surface modified coatings shows hydropho-
thermally stable –(CH3 )3 groups and we get resultant low energy bicity even at 100% concentration (pure acid) of H2 SO4 , HNO3 and
surface required for the superhydrophobic surface. The substrates HCl because of the surface roughness and low surface energy of the
deposited before 5 h of deposition time shows non-uniform coating coating. Thus, the coatings are more resistant to hydrochloric acid
due to incomplete hydrolysis and condensation reactions. How- (HCl), sulphuric acid (H2 SO4 ) and nitric acid (HNO3 ) hence, they are
ever, at higher deposition time, the optical transmission of the films most suitable for anti-rusting and anti-corrosive coatings on met-
was decreased due to the increase in surface roughness as shown als, alloys and avoid the effect of acid rain and acidic environments
in Table 3. on sculptures.

3.3. Surface morphological studies 3.5. FT-IR analysis and thermal stability coating

The FE-SEM observation showed the microstructure of the
MTMS/TMMS based superhydrophobic coating. Fig. 2(a)–(f) shows
the SEM images of the derivatized silica films prepared at differ-
ent deposition time from 5 to 25 h, respectively. Fig. 2(a) and (b)
shows the non-uniform deposition over the substrate at deposi-
tion time of 5 and 10 h, respectively. At 15 and 20 h of deposition
time, uniform deposition occurs on the substrate with microsized
particles as shown in Fig. 2(c) and (d). Fig. 2(e) shows the film pre-
pared at 25 h of deposition time having micro level size spherical
particles (typically ranges from 1 to 10 ␮m in diameter) uniformly
deposited on the substrate surface. These microsized particles pro-
vide an appropriate surface roughness which may responsible for
Fig. 4 shows FT-IR spectra of unmodified and TMCS modified
silica films deposited at 25 h. The absorption band of the –OH
around 3422 cm−1 and that of water adsorbed around 1600 cm−1
are decreased after modifying the surface with TMCS [32]. The FT-
IR spectra of unmodified and TMCS modified silica films shows a
very strong absorption band at 1096 cm−1 is due to the stretch-
ing vibration of Si–O–Si bridges [33] and the peaks splits into
bonds separated at 1021 and 1096 cm−1 in a hybrid coating struc-
ture. Olejniczak et al. have shown that in the hybrid gel structure,
asymmetric stretching vibration of Si–O–Si splits separate into two
bands due to functionalization of silanols [34]. The presence of C–H
stretching vibration is supported by two peaks around 3000 and
 S.A. Mahadik et al. / Applied Surface Science 257 (2010) 333–339 337

Fig. 2. FE-SEM images of superhydrophobic film derivatized with 10% TMCS at deposition time: (A) 5 h; (B) 10 h; (C) 15 h; (D) 20 h; (E) 25 h; (F) 25 h (5500×).

765 cm−1 . The intensity of the bands related to the C–H groups
slightly increased by the TMCS modification.
The thermal stability of superhydrophobic coating in air was
checked by TG–DTA analysis as shown in Fig. 5. It is clear that
superhydrophobic coating is thermally stable up to 300 ◦ C. The two
exothermic peaks, one is broad exothermic peak at temperature
353 ◦ C corresponds to the formation of CO2 with 6% weight loss
and other small exothermic peak at temperature of 544 ◦ C, causes
sudden weight loss up to 36% corresponding to the oxidation of sur-
face organic (–CH3 )3 groups present in the material with oxygen in
the air [35]. The superhydrophobic coating was thermally stable
up to 550 ◦ C and above this temperature they lose their hydropho-
bicity and become superhydrophilic at 600 ◦ C as shown in Fig. 6.
This thermal stability is due to the surface silica particles covered
by thermally stable and non-hydrolysable silicon trimethyl groups.
The coating starts to lose the superhydrophobicity above 550 ◦ C
and becomes superhydrophilic at 600 ◦ C due to oxidation of methyl
groups and other organic groups [36]. The thermal stability studies
revealed that the superhydrophobic coating retain their superhy-
drophobicity up to 550 ◦ C was confirmed by putting the films in
furnace (Neytech. VULCAN Benchtop Model 3-550, USA) at different
temperatures and measured contact angle on the sample after cool-
ing at room temperature until the superhydrophic coating turned
to super hydrophilic as shown in Fig. 6.
3.6. Optical transparency and surface roughness
The hydrophobicity and transparency are competitive proper-
ties from viewpoint of surface roughness. The roughness induces
scattering of light and decreases intensity of transmitted light. In
338 S.A. Mahadik et al. / Applied Surface Science 257 (2010) 333–339

Fig. 6. Thermal stability of the derivatized silica film prepared at deposition time of
25 h.
Fig. 3. Imperviousness against strong acids.

Fig. 7. Transmittance of prepared superhydrophic films at different deposition

times in the visible wavelength range.
Fig. 4. FT-IR spectra of the unmodified and TMCS modified silica film.

order to achieve higher transparency of the coatings in the visible

range (380–760 nm), the surface roughness should be controlled
below 100 nm [37] or much higher than the certain range (more
than few micrometers). Fig. 7 shows the percentage of the opti-
cal transmission of the films in the visible range (380–760 nm).
From Fig. 7, it is clear that transmittance of coating decreases with
increasing in deposition time and surface roughness. As shown in
Table 3, the surface roughness of the film increases with an increase
in deposition time. With increase in the deposition time from 5 to
25 h, the surface roughness increased from 10 to 1129 nm, respec-
tively. It is clear that hydrophobicity of the film increases with
increasing surface roughness and with decrease in optical trans-
mission.

4. Conclusions

Simple dip coating method with single step sol–gel processing

was used to prepare Thermally stable, transparent superhydrophic
hybrid coating on a glass. By controlling surface roughness of
resultant coatings, it is possible to achieve transparent superhy-
Fig. 5. TG–DTA of the derivatized silica film prepared at deposition time of 25 h. drophobic coating having excellent wetting behavior properties
 S.A. Mahadik et al. / Applied Surface Science 257 (2010) 333–339
with high optical transmission, thermal stability and impervious-
ness against strong acids. Such non fluorinated Thermally stable
transparent superhydrophobic coating potentially suitable for var-
ious industrial applications such as a lens, goggle, biker helmet,
wind shield, solar panels and sculptures (made from metals, marble
stones etc.) to avoid the effect of acid rain on them.
Acknowledgements
The authors are grateful to the Board of Research in Nuclear
Sciences (BRNS), Department of Atomic Energy (DAE), Mumbai,
Government of India, for the financial support for this work
through a major research project on “Aerogels and coatings” (No.
2007/37/18/BRNS). Mr. Satish A. Mahadik also thank to Univer-
sity Grant Commission (UGC), New Delhi, Government of India, for
providing “UGC Research Fellowship in Sciences for Meritorious
Students”. Authors also thankful to Miss. Jyoti L. Gurav for providing
FE-SEM facility.
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