The 1st International Seminar on Fundamental and Application

of Chemical Engineering

ISFAChE 2010
November 3-4, 2010, Bali-Indonesia

Hydrophobic Glass Coated with Surface Modified-Silica Film Prepared

From Sodium Silicate
Heru Setyawan*, Vicky Samsiadi, and Ambarwati
Department of Chemical Engineering
Sepuluh Nopember Institute of Technology, Surabaya 60111 Indonesia
*

Corresponding Authors E-mail: sheru@chem-eng.its.ac.id

Keywords: Sodium silicate; sol-gel; hydrophobic silica film; surface modification.

Abstract
In this paper, we report on the hydrophobic coating of glass substrate with silica gel film based on
sodium silicate solution as the starting material. The silica gel film was formed by dip coating and
drying at room temperature. The silica gel film was made hydrophobic by surface modifying agent,
either using hexamethyldisiloxane (HMDS) or trimethylchlorosilane (TMCS), by solvent exchange
method. We found that the drawing speed during dip coating and the initial concentration of silica had
no significant effect on the hydrophobicity of the silica gel film. The hydrophobicity was measured by
measuring the contact angle of water on the film. However, the contact angle is greatly influenced by
the conditions during surface modification such as the concentration of surface modifying agent and
the contact time. A high contact angle of 142.5 can be obtained by modifying the silica gel film in
9.7 M TMCS solution at 50C for 7 hours. The transparency of the surface-modified silica gel film,
measured as the %transmittance using a spectrophotometer, slightly decreases compared to the glass
substrate. On average, they take the value of greater than 93.5% relative to that of the glass substrate.

1. Introduction
Hydrophobic surfaces have considerable technological potential for various applications due to
their excellent water-repellent properties. One of them is the self-cleaning application including selfcleaning windows, windshields, exterior paints for building, roof tiles, textiles, and drag reduction in
fluid flow. Hidrophobic surface are those on which the water contact angle is between 90-150 degrees.
Lotus leaf is a classical example of natural super-hydrophobic surface on which the contact angle of
water is larger than 150 degree. The super-hydrophobic and self-cleaning surface effects of lotus leaf
and other plant leaves such as rice and Indian cress is caused by the rough structure [1].
The increasing interest in studying and manufacturing hydrophobic surface results from their
possible practical applications. They find their primary use in corrosion, erosion or general
degradation protection applications on metallic, polymer and inorganic oxide (stone, glass, ceramic,
etc.) solid surfaces. In recent years, this field has evolved into a major industry trade which covers
modern applications from anti-fogging as well as water and snow repellent surfaces for construction
materials, glass, automotive and aerospace technology, all the way to reducing frictional drag on
airplane wings and ship hulls [2]. Glass coated with silica using tetraethylorthosilicate (TEOS) as the
silica source can make the glass surface hydrophobic and has a self-cleaning effect [3,4]. Self cleaning
is the key advantage which keeps the surface clean while rain water beads up and rolls over these
surface entrapping dirt and particulates. The use of an expensive material such as TEOS hinders their
practical applications.
In this work we report on a sol-gel derived method for coating glass substrate with a thin film of
silica by dip coating. The coating materials use sodium silicate as a silica precursor and
trimethylchlorosilane (TMCS) or hexamethyldisilazane (HMDS) as the surface modifying agent. The
use of cheap and non-toxic silicate precursor must be preferable than its counterpart alkoxide
compounds in the frame of environmentally friendly processes.

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The 1st International Seminar on Fundamental and Application

of Chemical Engineering

ISFAChE 2010
November 3-4, 2010, Bali-Indonesia

2. Experimental
Materials
The materials used for the preparation of hydrophobic glass coating were commercial microscope
glass slides of 25.4 76.2 1 mm as the substrate, sodium silicate solution (water glass, 28% SiO2,
SiO2:Na2O = 3.3) provided by PT. Ineos Silica Indonesia the silica as the precursor,
hexamethyldisilazane (Merck, p.a.) and trimethylchlorosilane (Merck, p.a.) as the surface modifying
agent, and methanol (Merck, p.a.) as the solvent exchange. All were used as supplied with no further
treatment except for the glass slides.
Method
The synthesis of silica films involves the following four key steps: (i) substrate pre-treatment for
good quality of films, (ii) preparation of silica sol from sodium silicate, (iii) dipping and drawing the
substrates in the silica sol, and (iv) surface modification of the silica film. Each step is described in
more detail below.
The pre-treatment of substrate was carried out by washing the glass slides with acetone for 15
min. The substrate was then dried in an oven at 105 oC. Silica sol was prepared from diluted sodium
silicate solution. The concentration of the dilute sodium silicate solution was ranging from 4.2 to 7.0
wt.%. The solution was then mixed with cation resin H+ with the volume ratio of 1:1 and stirred by
magnetic stirrer for 30 minutes to exchange Na+ ions in the sodium silicate solution with H+ ions. This
results silicic acid solution with a pH of about 2. This silicic acid solution was used as the precursor to
make silica film on the glass substrate.
Then, the pretreated substrate was coated with silica by dip coating method. In this case, the glass
substrate was dipped and then drawn at a speed of 7.5 cm/min unless otherwise stated. It was then
aged for 10 hours at room temperature in order to strengthen adhesion force between glass and silica
film. The modification of the silica surface was carried out by the solvent exchange method. This is
done by dipping the silica coated glass substrate into methanol for 1 h to exchange pore water with
methanol. This step is required because the surface modifying agents, i.e., TMCS and HMDS, are
immiscible with water. Then, the substrate was dipped in the TMCS or HMDS solution using
methanol solvent. The concentration of modifying agent was varied from 0.43 to 9.7 M, the dipping
time was from 1 to 9 hours and the temperature was at ambient temperature and 50 C. Finally, the
substrate was dried in an oven at 100 C for 2 hours.
Characterization
The hydrophobicity of the film was measured by measuring the contact angle of water dropped on
the film surface by a syringe. The contact angle measurement was done by photographing the water
drop using a camera (Sanyo, VPC-x1200) and measured the angle from the picture obtained. The
surface morphology of the films was observed by an optical USB Microscope (M-1 Scalar, ColePalmer) at 200x magnification. The transparency of the films was measured by measuring the
transmittance using UV-vis spectrophotometer (Genesys 10, Thermo Scientific).
3. Results and Discussion
Figure 1 shows the photographs of the water drop on the film prepared at various conditions and
an illustration on how to measure the contact angle from the images. The three photographs show the
films having contact angle greater than 90. It seems that a key factor to produce a hydrophobic film
is the successfulness to exchange silanol groups on the silica surface with alkyl groups. When we used
a lower concentration of HMDS or TMCS (< 1 M) to modify the silica surface, the contact angle is in
the range of about 80 to 87 degrees which indicates that the films are still hydrophilic. The low
concentration of the modifying agent makes the reaction to be in the regime of diffusion-limited. It
also happens for the case when the reaction time is too short to allow surface modification to occur.
With a reaction time of less than 3 hours, a contact angle greater than 90 could not be obtained.
Hence, in order to completely modify the silica surface, the concentration of modifying agent should
be high enough to overcome the diffusion limitation. In addition, the reaction time should be
sufficiently long to allow the reaction to be completed.

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The 1st International Seminar on Fundamental and Application

of Chemical Engineering

ISFAChE 2010
November 3-4, 2010, Bali-Indonesia

(d)
Figure 1. (a, b, c) Photographs of water drop on the surface of films at various preparation
conditions showing the films are hydrophobic; (d) Illustration of the contact angle
measurement using the photograph obtained.
Figure 2 shows the effect of silica precursor concentration on the contact angle for the films
prepared using TMCS as the surface modifying agent with a concentration of 9.5 M and a reaction
time of 7 h. We can see that the contact angle is greater than 90 which indicate that the film is
hydrophobic. It seems that the precursor concentration does not have significant effect on the contact
angle as it can be seen that by changing the silica precursor concentration, the contact angle remains
constant and it takes the value of about 110.
As explained before, in order to obtain hydrophobic coating, the silanol groups should be
exchanged completely with alkyl groups. It can be carried out by increasing the concentration of
modifying agent and/or lengthening the reaction time. Figure 3 shows the effect of reaction time on
the contact angle using TMCS as the surface modifying agent with a concentration of 9.7 M. It can be
seen that the contact angle increases significantly by the increase of reaction time. At a reaction time
of 3 h, the contact angle is still below 90 degree. It increases significantly to be 118 degree when the
reaction time is increased to 7 h and reaches 128 degree when the time is increased to 9 h. It confirms
that the completeness of groups exchange between silanol and alkyl is the key factor for the
successfulness to produce the hydrophobic coating.

150
140
Contact angle, degree

130
120
110
100
90
80
70
60

Silica concentration (wt.%)

Figure 2. Effect of silica concentration on the contact angle for the films prepared using
TMCS with a concentration of 9.7 M and reaction time of 7 h.
It was supposed that the reaction may be speed up by increasing the temperature as it is typically
the case for most reaction system. Hence, we tried to modify the silica film at a temperature of 50 C.
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The 1st International Seminar on Fundamental and Application

of Chemical Engineering

ISFAChE 2010
November 3-4, 2010, Bali-Indonesia

The contact angle of silica film prepared at silica concentration of 5.6 wt.% and TMCS concentration
of 9.7 M is 118 degree with reaction time 7 h. It increases significantly to be 142 degree when the
temperature is increased to 50 C while other conditions are kept the same.

150
140
Contact angle, degree

130
120
110
100
90
80
70
60

10

Reaction time, h

Figure 3. Effect of TMCS concentration on the contact angle for the films prepared
with a TMCS concentration of 9.7 M and a silica concentration of 5.6 wt.%.
It is sometimes desirable for some applications that the glass remains transparent after being
coated with hydrophobic silica. Figure 4 shows the effect of silica coating on the transmittance of
glass after being coated with hydrophobic silica in the visible range. The transmittance of the
uncoated glass substrate is also presented as comparison. It can be seen that comparing with the
uncoated glass, the transmittance of the coated glass only decreases slightly, i.e., the coating does not
influence the transparency significantly.

Figure 4. Effect of silica coating on the transpaency of the glass.

It has been demonstrated that the hydrophobicity of silica film is greatly dependent on the
amount of alkyl groups grafted on the silica surface. Comparing the two modifying agents, using the
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The 1st International Seminar on Fundamental and Application

of Chemical Engineering

ISFAChE 2010
November 3-4, 2010, Bali-Indonesia

same molar ratio of modifying agent and silicic acid, the contact angle of silica film modified with
HMDS is larger than that of TMCS. For example, the contact angle of silica film prepared using
silicic concentration of 5.6 wt.% modified with TMCS at a concentration of 0.43 M is only 39 degrees.
It increases significantly to be 80 degrees using HMDS. The reaction taking place for the two cases
can be written as
For HMDS:

For TMCS:

It clearly shows that if it requires one mole HMDS to modify one mole silicic acid. On the other hand,
it needs two moles TMCS for one mole silicic acid.
4. Conclusion
It has been demonstrated that hydrophobic glass can be produced by coating the glass with
alkyl-modified silica film. The hydrophobicity of the glass is greatly dependent on the successfulness
to exchange the silanol groups on the silica surface with alkyl groups. In order to enhance the
exchange reaction, a high concentration of modifying and/or a longer reaction time is required. The
transparency of the coated glass is not significantly influenced. The contact angle of the glass coating
with alkyl-modified silica is in the range of 118 to 142 degrees which indicate that the film is
hydrophobic.
Acknowledgements
This work has been partly supported by DGHE, The Ministry of National Education of Indonesia
through Research Grant of Strategis Nasional.
References
1. Cannavale, A., Fiorito, F., Manca, M., Tortorici, G., Cingolani, R., and Gigli, G. (2010)
Multifunctional bioinspired sol-gel coatings for architectural glasses. Building and Environment,
45:1233-1243.
2. Nadargia, D.Y., Guravb, J.L., El Hawia, N., Raoc, A.V., and Koebela, M. (2010) Synthesis and
characterization of transparent hydrophobic silica thin films by single step solgel process and dip
coating. Journal of Alloys and Compounds, 496:436441.
3. Yoneda, T., and Morimoto, T. (1999) Mechanical durability of water repellent Glass, Thin Solid
Films, 351: 279-283.
4. Radonjic, L., and Nikolic, L. (1998) Effect of The silica sol-gel coatings on the properties of glass
substrate, Ceramics International, 24:547-552.

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