J Sol-Gel Sci Technol

DOI 10.1007/s10971-012-2798-3

BRIEF COMMUNICATION

Thermally stable and transparent superhydrophobic solgel

coatings by spray method
Satish A. Mahadik D. B. Mahadik M. S. Kavale
V. G. Parale P. B. Wagh Harish C. Barshilia
Satish C. Gupta N. D. Hegde A. V. Rao

Received: 26 February 2012 / Accepted: 9 May 2012

Springer Science+Business Media, LLC 2012

Abstract A facile method was developed for the fabrication of the methyltriethoxysilane based transparent and superhydrophobic coating on glass substrates. The transparent
and hydrophobic coatings were deposited on the glass substrates, using spray deposition method followed by surface
modification process. A spray deposition method generates
hierarchical morphology and post surface modification
with monofunctional trimethylchlorosilane decreases the
surface free energy of coating. These combined effects of
synthesis produces bio-inspired superhydrophobic surface.
The deposited coating surface shows high optical transparency, micro-nano scale hierarchical structures, improved
hydrophobic thermal stability, static water contact angle of
about 167 1, low sliding angle about 2 1 and stable
superhydrophobic nature. This paper provides the very
simple solgel approach to the fabrication of optically
transparent, thermally stable superhydrophobic coating on
glass substrates. This fabrication strategy may easily extend
to the industrial scale up and high-technology fields.
S. A. Mahadik
D. B. Mahadik
M. S. Kavale

V. G. Parale
A. V. Rao (&)
Air Glass Laboratory, Department of Physics, Shivaji University,
Kolhapur 416004, Maharashtra, India
e-mail: avrao2012@gmail.com
D. B. Mahadik
e-mail: superhydrophobicmaterial2100@gmail.com
P. B. Wagh
S. C. Gupta
Applied Physics Division, Bhabha Atomic Research Centre
(BARC), Trombay, Mumbai 400085, Maharashtra, India
H. C. Barshilia
Surface Engineering Division, CSIR-National Aerospace
Laboratories, Bangalore 560017, India
N. D. Hegde
G. S. Science College, Belgaum, Karnataka, India

Keywords Spray coating
Superhydrophobic
Solgel

process
Contact angle
TMCS

1 Introduction
The nature impels us that living organisms and plants have
the capability of self-cleaning character owing to the superhydrophobic surface. The most emblematic illustration
is the so-called lotus-effect [13]. The wettability of the
surface not only affects the fundamental movement of the
living organisms in nature but also has a deep influence on
our daily life and in manufacturing, such as self-cleaning
materials, micro-fluid chips and micro-reactors. Recent
discoveries have linked the self-cleaning mechanism of a
lotus plant to a microscopic morphology leading to superhydrophobic surfaces [49]. This finding has been
sparked the interest of numerous researchers to develop a
bio-mimetic approach to produce the same effect [1012].
The vision of production of superhydrophobic surfaces has
huge potential applications in the area of corrosion inhibition for metal components, chemical and biological agent
protection for clothing, and many other industrial and
commercial applications. A variety of surface modification
approaches have been used successfully for achieving the
superhydrophobic character.
The dual scale morphology and chemical composition of
surface plays the crucial role in all domestic and technical
applications to provide anticorrosive coatings, self-cleaning surfaces, paints, and textiles to low-friction surfaces for
fluid flow. Many simulated strategies and materials have
been reported for obtaining superhydrophobicity with
outstanding performance, including solgel processing and
solution casting, casting and molding, chemical vapor
deposition, laser/plasma/chemical etching, lithography,

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electrical/chemical reaction and deposition, layer-by-layer,

electrodeposition/electropolymerisation and self-assembly
and electrospinning [13]. Except for the sol gel spray
coating and surface modification with mono-functional
trimethylchlorosilane (TMCS), all of these methods are
complicated and require special equipment, high temperature or vacuum conditions, involving multiple steps, which
makes it difficult for understand their chemistry behind it
and practical applications in large scale coatings. To get the
superhydrophobicity by surface chemical modification
methods, there are many reports are available in the literature, viz. Hikita et al. [14] and Shang et al. [15], created
superhydrophobic surface using colloidal silica particles
and fluoroalkylsilane as a silyalating precursor through sol
gel process. These studies address the critical issue of
surface introducing poisonous fluorine molecules, which
highly hazardous to human health. Another demonstration
of the concept was presented by Xiu et al. [16], who prepared two-tier roughness on silicon, followed by a fluorination treatment to render the hydrophilic silicon surface
hydrophobic. Kang et al. [17], reporting time consuming
method to produce superhydrophobicity with high-water
adhesion properties by surface modification with dopamine. Similarly, Junqi et al. [18], reported plasma etching
process for fabricating superhydrophobic surface have a
complex and multiple steps.
Many superhydrophobic coating materials suffer from
thermal degradation problem at low temperature
300350 C. Also superhydrophobic coating film shows
the low transmittance due to high roughness [19, 20], and
high cost and complex procedure for the coatings preparation. It was because that the coating surface morphology
or composition degraded at low temperature and in some
process has poor control on their thickness and porosity
which was greatly affected on the transmittance such issue
reduces their application field. However, the superhydrophobic of coating procedure have been prepared by combining, simple and low cost strategy from spray coating and
surface modification with TMCS through the solgel process gives the best solution for obtaining transparent superhydrophobic coating with enhanced thermal stability of
superhydrophobicity hydrophobic.

2 Experimental
2.1 Materials
Chemicals used for synthesis superhydrophobic coating are
methyltriethoxysilane (MTES) (Fluka Chemie, Switzerland), trimethylchlorosilane (TMCS) (SigmaAldrich
Chemie, Germany), methanol, hexane (S.D. fine Chem.
Ltd., Mumbai) and liquor ammonia (NH3, Sp.Gr.0.91

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Qualigens Fine Chemicals, Mumbai), and glass substrates

(Blue star, Mumbai).
2.2 Sample preparation
The organically modified silica (ORMOSIL) superhydrophobic coatings was prepared in the following three steps:
(1) hydrophobic alcosol preparation, (2) spraying alcosol
on hot glass substrates at 100 C and (3) surface modification by TMCS. In the first step, the alcosol was prepared
at an optimized molar ratio of MTES (1): CH3OH (35.22):
ammonium hydroxide (NH4OH) (2.01). Initially, methyltriethoxysilane diluted in methanol and NH4OH (13.6 M)
was added drop wise into the solution with the constant
stirring. The whole solution was stirred for 1 h at room
temperature to complete hydrolysis of MTES precursor.
The hydrolyzed alcosol was kept as it is for 12 h. In the
second step, 20 ml transparent alcosol with fine droplets
was sprayed on glass substrates placed on the iron hot plate
held at 100 C constant temperature for 3 min through fine
nozzle (bore size 0.5 mm, the RPM of nozzle 25). The
deposition was taken using a spray coating system with
optimized parameters like spray pressure kept constant
90 Psi and distance between substrates and nozzle kept
around 30 cm. Initially, substrate temperature kept constant at 100 C, and then alcosol was spray on glass substrates through a spray nozzle. Due to temperature gradient
developed in the path of the droplets, before reaching the
fine droplets of alcosol on the substrates, droplets convert
into fine particles of silica material by partial evaporation
of alcohol from droplets. The remaining residue of alcohol
from coatings was completely removed in next steps; most
of the alcohol evaporates during deposition of silica particles on hot glass substrates and annealing process in the
oven after deposition. The uniform spray of alcosol on
glass substrate at constant temperature forms uniform
coating of silica particles. The as-deposited silica films
were annealed at 150 C for 2 h in the oven in order to
improve adherence of coating material to the substrate. In
the final stage of preparation, as deposited coatings kept in
a furnace at 550 C for 1 h in order completely thermally
unstable ethoxy groups from coating material and final
coating effectively modified using mono-functional 10 %
TMCS in the hexane bath for 5 h at room temperature. In
order to improve the SiC bonds induced from silylation on
coating surface, the films were annealed in an oven at
100 C for 1 h after washing with methanol and hexane to
remove un-reacted residue from surfaces.
2.3 Sample characterization
The surface morphology of the ORMOSIL films was
observed using scanning electron microscopy (SEM,

J Sol-Gel Sci Technol

Fig. 1 SEM image of a TMCS modified silica film at different magnifications a 10,000; b 20,000

JEOL, JSM-6360, Japan), and 3-D morphological image

was obtained using an atomic force microscope (AFM,
Nano scope E, Digital Instruments, USA) operated in
contact mode. The optical transmission of the superhydrophobic coating and glass substrate were determined by
UVVIS spectrophotometer (Systronics 119, USA) with
reference to air. Surface chemical modification of the silica
coatings was studied by using FT-IR (PerkinElmer,
Model no. 783, USA). The degradation of organic groups
of coatings at various temperatures was studied from the
TGADTA (TA Instrument, Q600, USA). Contact angle
measurements were carried out by the sessile drop method
with a droplet volume of 5 ll to minimize the gravitational
effects using a goniometer (Rame hart Instrument Co.,
Model 501F1, USA). The static contact angle values are
measured five times and average contact angle value is
reported. The sliding angle measured by the tilting plate
method, to measure at which angle water droplet falls from
the substrate. The hydrophobic thermal stability of coatings
was confirmed by placing samples in the furnace (Neytech,
VULCAN Model 3-550, USA) at different temperatures in
ascending order (50600 C) with 50 C differences. After
reaching the set temperature at furnace, sample was
exposed to set temperature for 1 h and finally, substrates
were cooled to room temperature. Again, the water contact
angle was measured using goniometer.

3 Result and discussions

3.1 Surface morphological studies
The surface morphologies of ORMOSIL coatings were
investigated by scanning electron microscope (SEM) analysis given in Fig. 1. The surface morphology of surface
modified with TMCS silica coating at different magnifications is shown in Fig. 1a and b. The figure shows the rough
surface morphology of TMCS modified silica coatings. As
shown in Fig. 1a SEM images at 10,000 magnifications, the

Fig. 2 AFM image of the TMCS modified silica coating

surface morphology of ORMOSIL coating reveals the

uniform distribution of dual scale silica particle over the
film. From SEM image Fig. 1b at higher magnification
(20,000), reveal a uniform distribution of modified silica
particles having size ranging from 100 to 300 nm provides a
rough surface with a surface covered by the low surface free
energy of methyl groups (confirmed by FTIR study) which
is the basic need of the superhydrophobicity.
3-D topography of modified silica coating was observed
using an AFM operated in contact mode and shown in
Fig. 2. The AFM image of superhydrophobic coating
synthesized from simple spray coating method reveals the
rough surface. AFM image revealed that the micronized
grains shown in Fig. 1b of SEM, have grown perpendicular
to the surface with hill-like microstructure. Figure 2 shows
the topography of the TMSCS modified silica film which
support to SEM results. The AFM images were recorded at
2 9 2 lm2 in contact mode. The root-mean-square (RMS)
roughness value analyzed from AFM comes out to be
137 nm.

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3.2 Thermal stability of superhydrophobic coatings

Hydrophobic thermal stability is very important physical
property of coating materials in application point of view.
Thermal deterioration and thermal instability of material
exerts a bad influence in the application of superhydrophobic coating at high temperature. Here we have
improved thermal stability of hydrophobicity of silica
coatings by post surface treatment on spray deposited
coatings with monofunctional TMCS. To improve superhydrophobicity of any surface one has to decrease surface
free energy of surface by modifying the surface chemical
composition with non-polar groups like CH or SiC.
Monofunctional (TMCS) surface silylation process effectively enhances the number density of thermally stable
SiC bonds on surface of coatings and this existence of a
SiC bond confirmed from FT-IR study. In the TGA and
DTA analysis carried out at a heating rate of 10 C/min in
the air atmosphere. Figure 3a shows TGA curve for both
surfaces modified by TMCS silica coating material and asdeposited coating material. From TGA studies, it is clearly
observed that both materials are thermally stable up to
200 C after that coating material gradually starts to
decompose up to 600 C. Finally, after total degradation of
organic groups, a weight loss curve becomes flat for
modified and unmodified silica coating material. For
unmodified material, TGA curve shows total weight loss
near about 35 %. However in case of surface modified
coating material weight loss reduces up to 16 % over the
temperature up to 1,200 C.
Figure. 3b shows the DTA thermograms for unmodified
and TMCS modified silica coating materials. In case of
unmodified silica coating material shows two exothermic
peaks. First broad exothermic peak corresponding to formation of CO2 with 8 % weight loss and second sharp
exothermic peak corresponding to the oxidation of surface
organic [O(C2H5)]3 groups present in ORMOSIL material with 25 % sudden weight loss [21]. But in case of
surface modified superhydrophobic coating material, the
broad exothermic peak at temperature shifted from 284 to
355 C as compared to the DTA curve of the unmodified
coating material. Second sharp peaks also shifted from 515
to 547 C due to higher thermal stability of grafted highly
thermally stable methoxy groups on coating surface with
weight loss significantly reduces up to (19 %) in TGA
curve. This exothermic peak appeared might be due to the
decomposition of methyl groups and the SiC bonds in the
coating material. This might be leads to enhance the thermal stability of superhydrophobic material up to 547 C,
after degradation of organic groups coating material
becomes superhydrophilic [22]. Surface modification cant
show any significant change on a glass transition temperature of both materials which remains the same as 290 C.

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Fig. 3 a TGA curves for surface modified and unmodified coating

materials. b DTA curves for surface modified and unmodified coating
materials

However decomposition rate and decomposition temperature of alkyl group shift from 515 to 547 C.
The hydrophobic thermal stability of coatings was
confirmed by placing samples in the furnace at different
temperatures and confirmed by water contact angle measurement. A study reveals that hydrophobicity retains up to
500 C in case of unmodified (as deposited) coating but we
get different results in the case of modified coating superhydrophobicity extend up to 550 C becomes superhydrophilic at 600 C as shown in Fig. 4. The coating
exposed to 600 C shows superhydrophilic nature and
confirms the total decomposition of non-polar groups from
the coating material. The TGA-DTA analysis reveals that
the surface modification of as-deposited films with 10 %
TMCS in hexane bath enhances thermal stability due to
effective replacement of Si(OC2H3)3 groups with nonhydrolysable, thermally stable Si(CH3)3.

J Sol-Gel Sci Technol

Fig. 4 Thermal stability of wettability

found to be drastically reduced after the effective surface

modification. Simultaneously intensity of CH and SiC
peaks is enhanced for the TMCS modified film. We get
interesting results about thermally degraded material
(Fig. 5b) all peak related to CH and OH bonds completely
removed from coating material but still remaining SiO
Si bonds indicating existence of silica network. In order to
effectively surface modification, firstly coating annealed at
550 C with slow rate heating (5 C/min) for 1 h sufficient
for completely degraded on ethoxy groups from coating
surface. During the surface modification of the silica film,
effectively mono layer of non-hydroxyls Si(CH3)3
groups deposited on the surface results to produce low free
energy surface area, which leads to excellent superhydrophobicity [27]. Form FT-IR analysis confirms that surface chemical modification with 10 % TMCS, effectively
reduces wettability and enhancement of thermal stability of
coating mainly due to non-polar and low energy methyl
groups deposited on the surface surface.
The optical transmission of such superhydrophobic
coatings was measured using UVVIS spectrophotometer.
Figure 6 shows, the transmission spectra of modified silica
coating with respect to air. To increase the optical transmission, we have tuned the thickness of films by regulating
the spray timing and sol conditions for optical visible
transmittance. The best performances were obtained when
silica particles were distributed uniformly on the surface
without any precipitation of silica particles at optimized
spray conditions. A highest absolute transmittance of
coating raised up to 82 % at 600 nm was observed from
spectra. Inset of Fig. 6 shows the photograph of water
droplet on the optically transparent silica coating on glass
substrate.

Fig. 5 Comparative FT-IR Spectra of coating material (A) As

deposited (B) After surface modification (C) After annealing at
550 C.

3.3 FT-IR analysis and optical transmittance

Comparative FT-IR study of as deposited coating material,
thermally degraded material, and TMCS modified coating
materials as shown in Fig. 5. The absorption bands
observed at near around 2,950 and 1,400 cm-1 are due to
the CH stretching vibration of CH3 groups and the peaks
observed at 780 cm-1 present stretching vibration SiC
and rocking vibration of CH3. Absorption bonds observed
at 1,275 and 1,412 cm-1 are due to the CH3 symmetric
and anti-symmetric deformation of SiCH3 bonds [23].
The peak at around the 905, 1,641 cm-1 and the broad
absorption band at around 3,400 cm-1 are due to the OH
group. [2429]. Comparative FTIR study reveals that, OH
peaks are quite visible for as-deposited silica film, which

Fig. 6 Optical properties of TMCS modified silica coating (A) transmission spectra (B) water drop on visible transparent coating

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3.4 Effect of surface modification on wettability

The water contact angle on the unmodified and TMCS
modified silica coatings was measured by using a static
drop method with drop size 5 ll. Inset of Fig. 5A shows a
photograph of water drop on unmodified silica film having
a contact angle equal to 94 3. The water drops stick to
the surface of the unmodified silica film and dislodges after
tilting the film up to 39 4. This is due to the presence
of a surface hydroxyl OH groups. Thermally degraded
coating surface easily absorb within fraction seconds as
shown in inset of fig. 5C, but after effective surface modification of the silica film with 10 % TMCS in hexane bath,
the surface chemical configuration recovers with enhanced
hydrophobicity up to superhydrophobicity. Inset Fig. 5B
shows the spherical water droplet on TMCS modified silica
coating surface. The water drops on modified silica film
rolls off easily without any adhesion. After surface modification with TMCS, the water contact angle enhances
drastically from 94 3 to 167 1 and simultaneously
the tilt angle of water is decreased drastically from
39 4 to 3 1. This change in surface wettability is
due to methyl groups grafted after surface modification
using TMCS.

4 Conclusions
We have successfully fabricated a kind of hierarchical
structures of silica particles with low free energy surface on
glass substrates. After surface modification with TMCS,
the as-prepared surfaces successfully attained thermally
stable superhydrophobic surface. A solgel combined
strategy of spray coating and surface modification process
was carried out to fabricate the superhydrophobic coating.
By using this simple method, we demonstrated that the
prepared surface structures could preserve a transparent
superhydrophobicity with thermal. Our work suggests a
new protocol to enhance surface superhydrophobicity with
thermal stability.
Acknowledgments It is a great pleasure to thank The Department
of Atomic Energy (DAE), Board of Research in Atomic Energy
(DAE) Board of Research in Nuclear Science (BRNS) Mumbai,
Government of India, for financial support for this Work No. 2008/37/
47/BRNS). Mr. Satish A. Mahadik also thank to the University Grant
Commission (UGC), New Delhi, Government of India, for providing
UGC Research Fellowship in Sciences for Meritorious Students.

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