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D

Journal of Materials Science and Engineering A 3 (4) (2013) 224-231

DAVID

PUBLISHING

Development of Hydrophobic Non-Fluorine Sol-Gel


Coatings on Aluminium Using Long Chain Alkyl Silane
Precursor
Ruchi Grover Wankhede1, Shantaram2, Karan Thanawala1, Anand Khanna3 and Nick Birbillis4
1. Department of Metallurgical Engineering and Materials Science IITB-Monash Research Academy, Mumbai 400076, India
2. Dow Chemicals, Pune, India
3. Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai 400076, India
4. Department of Materials Engineering, Monash University, Victoria 3800, Australia
Received: April 17, 2012 / Accepted: May 21, 2012 / Published: April 10, 2013.
Abstract: Hydrophobic surface can be achieved by synergistic effect of lowering of surface energy and increase in surface roughness.
Present work emphasizes on the development of thin hydrophobic sol-gel coatings on aluminium substrate using a long chain C-16
silane precursor i.e., Hexadecyltrimethoxysilane (HDTMS) crosslinked with Glycidoxypropyltrimethoxysilane (GPTMS) and
Tetraethoxyorthosilcate (TEOS), in varying concentrations. Condensation and hydrolysis reactions of all three silane precursors
resulted in hydrophobic sol-gel coating with a contact angle greater than 90. This can be attributed to the self assembled, low energy
HDTMS groups on the surface. By further, enhancing the surface roughness of the aluminium substrate, before coating application,
using various etching solutions, it was possible to achieve enhanced hydrophobicity with contact angle of about 130 and sliding
angle of 20. Surface morphology, surface roughness and hydrophobicity of the coating were characterized using SEM, AFM and
water contact angle analysis, respectively.
Key words: Hydrophobicity, etching, non-fluoro, surface roughness, contact angle.

1. Introduction
It is generally recognized that the wet ability of a
solid surface depends on both of its chemical
composition and its geometrical structure. In order to
create a super hydrophobic surface, two factors are
important. First, the surface should have low energy
and second it should have an optimum roughness,
preferably in nano range. Roughness, combined with
hydrophobicity, often results in air pockets, being
trapped between the solid and liquid (the composite
solid-liquid-air interface), thus leading to a significant
decrease in the solid-liquid adhesion and hence an
increase in the contact angle [1]. This minimizes the
Corresponding author: Ruchi Grover Wankhede, Ph.D.,
research field: metallurgical and materials engineering. E-mail:
123.ruchi@gmail.com.

attractive forces between the water molecules and the


atoms of the surface and thus allows the water to
bead up and roll off, which leads to a number of
potential industrial applications like water repellent
coatings on the satellite dishes, solar energy panels,
exterior architectural glass, pipelines, antifouling on
boats and antisticking of snow for antennas and
windows, biomaterials etc. [1-6]. There are many ways
to create a hydrophobic surface, by modifying the
surface with a reactive chemical group that reduces the
surface energy. Surface energy for some commonly
used groups, for example fluoro groups, varies in the
order of -CF3 < -CF2 < -CH3 < -CH2, indicating that use
of fluorinated compounds is beneficial for the
enhancement of water-repellency [7-10]. Since,
fluoroalkyl compounds have potential risk for human

Development of Hydrophobic Non-Fluorine Sol-Gel Coatings on Aluminum Using Long Chain Alkyl
Silane Precursor

health and environment, development of eco-friendly


non-fluoroalkyl based sol gel coating was the main
objective of this work. One of the effective methods of
lowering surface energy without using fluorine
compounds is to use long chain hydrophobic silanes
like hexadecyltrimethoxy silane (HDTMS) and
octadecyl trichlorosilane (ODTCS). There is some
evidence in reported literature on the use of long chain
silanes. Kulinich, et al. [11] developed self-assembled
organic monolayers (SAMs) on solid substrates based
on octadecyltrichlorosilane precursor having low
surface energy. Daoud, et al. [12], Latthe, et al. [13]
and Gao, et al. [14] successfully prepared transparent
and durable superhydrophobic silica-coating films on
cotton substrates at low temperatures via
co-hydrolysis
and
polycondensation
of
hexadecyltrimethoxysilane (HDTMS) and various
other silane precursors with contact angle ranging
from 125 to 150. Similar work is also reported by
Textor, et al. [15] according to which, hydrophobic
sol-gel based coatings can be prepared by combining
simple TEOS-based sols with minor amounts of
hydrophobic additives like alkyltrialkoxy silanes, as
methyltrimethoxysilane (C1), butyltrimethoxysilane
(C4),
octyltrimethoxysilane
(C8),
dodecyltrimethoxysilane (C12), hexadecyltrimethoxy
-silane (C16) and octadecyltrimethoxysilane (C18).
Present work aims at the development of such
coatings on aluminium by roughening the metal
surface prior to application of sol-gel coatings.
According to Youngs equation when surface
roughness increases, the contact angle needs to
increase accordingly to balance the enlarged surface
energy between the solid substrate and liquid droplet.
Wenzel and Cassie-Baxter proposed that by
microscopically increasing the surface roughness of a
substrate, it is possible to increase its hydrophobicity
because water droplets lie in a suspended state resting
on the top of the surface textures instead of dropping
between each texture. It has also been established that
the height and width of the textures, as well as the

225

distance between textures, are determining factors to


achieve a Cassie-Baxter state [16]. There are many
techniques to create roughness patterns on metal like
chemical etching, mechanical roughening, anodic
oxidation, laser lithography, plasma treatment,
chemical vapor deposition and so on. However, in the
present work, etching of aluminium using different
etchants was used to create roughness grooves by
revealing the grain boundaries. Many such etchants
have already been tried by several workers. Qu, et al.
[17] and Fu, et al. [18] etched aluminium specimens
by immersing in a Becks dislocation etchant, Cu
(NO3)2 and HNO3 solution respectively. The etched
metallic surface when hydrophobized with
fluoroalkylsilane
exhibited
superhydrophobic
properties. Qian, et al. [19] used nitric acid and
hydrogen peroxide mixed-solution system as the
etching reagent on the engineering materials to obtain
the rough surfaces.
Hence synergistic effect of HDTMS, GPTMS and
TEOS based hybrid sol-gel and chemical etching of
aluminium with various etchants was explored to
develop a hydrophobic non-fluoro coating system.

2. Materials and Methods


Hexadecyltrimethoxysilane
(HDTMS),
Glycidoxypropyltrimethoxysilane (GPTMS) and
Tetraethoxyorthosilicate (TEOS) (Sigma Aldrich,
make) were procured, while other standard chemicals
such as, ethanol, glacial acetic acid, hydrochloric acid,
sodium hydroxide, hydrogen peroxide, nitric acid and
hydrogen fluoride were procured from E-Merk. The
hydrophobicity of the films was tested by measuring
the contact angle (C.A.) of a water droplet of volume
5 L placed on coated surface using the contact angle
meter equipped with CCD camera (Model OCA15EC,
make: Dataphysics) at room temperature. The C.A.
was measured at 4 different spots on each sample and
the average value is reported as contact angle. The
microstructure of the film was observed by scanning
electron microscopy (Model No. S3400, Hitachi) and

226

Development of Hydrophobic Non-Fluorine Sol-Gel Coatings on Aluminum Using Long Chain Alkyl
Silane Precursor

the surface topography along with surface roughness


was examined using atomic force microscopy (Model
Smart SPM 1000, make: AIST-NT) in tapping mode.

3. Experiments
The Various formulations of sol-gel coatings were
made with different concentrations of GPTMS,
HDTMS and TEOS. These were represented as Sol A,
B, C, D and E as given in Table 1 which also lists
various concentrations of HDTMS, GPTMS and
TEOS. Ethanol was added to this mixture and
allowed to stir for 10 minutes at speed of 400 rpm.
After 10 minutes 18ml of 50% acetic acid was added
drop wise to adjust the pH up to 3 and stirring was
continued for 8 h till a slight hazy solution was
obtained. All these preparation were carried out at
room temperature. Aluminium panels, with smooth
finish were used and were etched using various
chemical etchants to create surface roughness. This
was followed by the application of HDTMS modified
sol-gel coatings using brush, followed by baking at
120 C for one h. Details of various etchants used are
as follows:
(1) 10% NaOH solution: Aluminium panels were first
prepared by polishing with emery papers of 400 and 600
grades, cleaned, dried and then etched in 10% NaOH
solution for 5 to 10 minutes. Etched samples were
washed with running tap water and acetone, dried and
then brush coated with as prepared sol-gel coatings.
(2) Krolls reagent: Krolles reagent was prepared by
mixing 40 ml of water, 5 ml nitric acid, 3 ml
hydrochloric acid and 2 ml hydrogen fluoride. Bare
aluminium panels were dipped in the as prepared
Krolls reagent for 1 min. Etched samples were washed
with water and acetone and brush coated with various
HDTMS sols.
(3) Becks reagent: Becks reagent was prepared by
mixing 40 ml hydrochloric acid, 12.5 ml water and 2.5
ml hydrogen fluoride. Bare aluminium panels were
etched for 5 s and brush coated with various HDTMS
sol.

Table 1 Various formulations of HDTMS, GPTMS and


TEOS based sol-gel coatings.
Formulations

GPTMS (ml)

HDTMS (ml)

TEOS (ml)

Sol A

0.5

1.5

Sol B

Sol C

Sol D

Sol E

12

Table 2 Gel-time and contact angle of various sols coated


on un-etched aluminium substrate.
Formulation

Gel Time

Contact angle on
un-etched flat substrate

Sol A

1 month

95

Sol B

7 days

97

Sol C

1 day

100

Sol D

15 days

95

Sol E

15 days

98

4. Results and Discussion


4.1 Contact Angle Analysis
Sol-gel coated aluminium substrates, without any
modification were found to be hydrophilic with
contact angle of around 65-70. After modifying the
same with various HDTMS formulations, the surface
turned hydrophobic with contact angle ranging from
95 to 100. It was found that the hydrophobicity
increases with increase in concentration of HDTMS.
Since, HDTMS is long chain alkyl precursor,
responsible for lowering the surface energy, contact
angle increases with increase in its amount, but
gelling time is another important factor, which
actually

decreases

drastically

after

substantial

increase in HDTMS concentration. Hence, only


small

amount

of

HDTMS

was

required

for

introducing hydrophobicity and for longer pot life.


Sol D with GPTMS: HDTMS: TEOS volume ratio of
2:2:6 was found to be the optimum formulation to
achieve a reasonable contact angle of about 95 with
a long gel time of 15 days. Table 2 lists gel-time and
contact angle of various sols coated on un-etched
aluminium substrate.

Development of Hydrophobic Non-Fluorine Sol-Gel Coatings on Aluminum Using Long Chain Alkyl
Silane Precursor

In order to achieve higher value of water contact


angle, aluminium substrates were further etched using
various chemical etchants. Fig. 1 and Table 3 shows
the variation of contact angle achieved on aluminium
samples, etched with various etchants, followed by
coating with various sols. It was found that no matter
what kind of roughening method was used,
hydrophobicity on etched surfaces increases when
compared to un-etched surface. All hydrophobic
formulations showed similar trend for a particular
surface roughness. The surface of bare specimens
etched with Krolles reagent, 10% NaOH and Becks
regent, showed hydrophillic behavior with contact
angles of about 45, 65 and 55, respectively.
However, after coating with various HDTMS sols the
average contact angle increased to 105o for Krolles

227

etching, 115o for 10% NaOH etching and about 130o


for becks etching.

Fig. 1 Variation of contact angle of different formulations


of HDTMS coated aluminium samples etched with various
reagents.

(a)
(b)
(c)
Fig. 2 (a) SEM image, (b) EDAX Spectra and (c) AFM image of flat aluminium substrate coated with sol-gel formulation
having GPTMS: HDTMS: TEOS ratio 2:2:6.
Table 3 Water contact angle of various formulations of sol-gel coatings developed on differentially etched aluminium
specimens.
Formulation
Uncoated
Sol A
Sol B
Sol C
Sol D
Sol E

C.A on Krolles reagent etched


specimen
45
105
105
107
107
102

C.A on NaOH reagent etched


specimen
65
110
110
115
115
110

C.A on Becks reagent etched


specimen
55
120
125
135
130
128

Table 4 Variation of sliding angle with different kind of etching on aluminium after coating with various hydrophobic
sol-gel formulations.
Etched surface coated by various formulations
Flat Surface
Krolles reagent
NaOH reagent
Becks reagent

Sliding Angles of 10 L water droplet


> 90
75-65
55-45
15-25

228

Development of Hydrophobic Non-Fluorine Sol-Gel Coatings on Aluminum Using Long Chain Alkyl
Silane Precursor

coated sample. This shows that both long chain


hydrophobic HDTMS sol-gel coating and roughening
due to etching were synergistically responsible for
achieving hydrophobic aluminium surface.
4.2 SEM Analysis
(a)

(b)

(d)

(e)
(f)
Fig. 3 SEM images of specimens coated with sol-gel
formulation having GPTMS:HDTMS:TEOS ratio of 2:2:6
after (a) Krolles etching at magnification of 1,000 ; (b)
5,000 ; (c) 10% NaOH etching at magnification of 1,000 ;
(d) 5,000 and (e) Becks etching at magnification of 1,000
and (f) 5,000 .

Fig. 4 FE-SEM image of thickness of sol-gel coated


(GPTMS:HDTMS:TEOS ratio 2:2:6) becks reagent etched
aluminium sample.

Table 4 shows the sliding angle behavior of


optimized sol D formulation, coated various etched
surfaces. It was found that sliding angle decreases
with increase in severe nature of etchant with
minimum value of about 15 to 25 for becks etched

Fig. 2a shows scanning electron microscopic (SEM)


image along with energy dispersive X-ray analysis
(EDAX) spectra of un-etched flat aluminium substrate,
followed by application of sol D, according to which
the surface is covered by large number of silica
particles also confirmed from EDAX responsible for
initial hydrophobic behavior with C.A. >90 due to
lower
energy
HDTMS
components.
The
microstructures formed on the substrates after etching
of aluminium surface by various methods followed by
application of formulation sol D using SEM are
shown in Fig. 3. These images clearly indicate that the
formation of micro-scale hillocks on the surface due to
etching of grain boundaries enhance surface roughness.
Extent of roughness increases with the severity of the
etchant, with maximum roughness achieved after
etching with becks etchant. According to Quin, et al
[19], one of the major constituent of Becks reagent is
HCl which helps in revealing grain boundaries and
polycrystalline microstructure of aluminium substrate,
resulting in wider and deeper pits as compared to
other etchants. Further, hydrophobization with
HDTMS based sol-gel coatings resulted in
superhydrophobicity with contact angles of about 130o.
Also average coating thickness was measured using
field emission scanning electron microscope (FE-SEM)
and found to be about 2 m. Hence, chemical etching
is one of the effective methods for introducing desired
amount of surface roughness which is the key factor
combined with low surface energy responsible for
developing superhydrophobic coatings.
4.3 AFM Analysis
Atomic force microscopic (AFM) analysis was
carried on sol-gel coated un-etched and various etched

Development of Hydrophobic Non-Fluorine Sol-Gel Coatings on Aluminum Using Long Chain Alkyl
Silane Precursor

(a)

(b)

225

(c)

(d)
(e)
(f)
Fig. 5 AFM images and RMS values of aluminium samples etched with (a), (d) Krolls reagent, (b), (e) 10% NaOH and (c),
(d) Becks reagent followed by coating with sol-gel formulation having GPTMS:HDTMS:TEOS ratio 2:2:6 and ratio 1:3:6,
respectively.

Fig. 6

Probable mechanism of reaction of GPTMS, TEOS and HDTMS.

specimens in the tapping mode to evaluate surface


morphology of various specimens. Fig. 2c shows the
AFM topography of un-etched aluminium substrate
followed by coating with sol D having small
protruding nubs due to long chains of HDTMS on
surface with root mean square roughness (RMS) value

of about 5 nm. The AFM images and RMS values of


aluminium specimens, etched with various etchants,
followed by application of formulation C and D are
shown in Fig. 4. The average RMS values of Krolls,
10% NaOH and Becks etched sol-gel coated samples
were found to be 30 nm, 60 nm and 120 nm,

226

Development of Hydrophobic Non-Fluorine Sol-Gel Coatings on Aluminum Using Long Chain Alkyl
Silane Precursor

respectively for all the five formulations which is


significantly high as compared to coated un-etched
substrate. The surface of the films showed many
dispersed islands that were distributed on the film
surface with Becks etched sample, having maximum
height of the protruding islands which supports high
value of contact angle of 130 the low value of sliding
angle of about 25 attributed to increased fraction of
air entrapped below the roughness grooves leading to
lowering of friction between the surface and water
droplet. Hence the similar trend was observed from
AFM analysis as from SEM studies, thereby
indicating that chemical etching along with HDTMS
modification is one of the effective approaches to
obtain hydrophobic surface.

5. General Discussion
Hydrophobic thin films were developed using long
chain HDTMS, GPTMS and TEOS as silane
precursors over chemically etched aluminium surface.
Presence of large number of polar Si-OH groups on
the surface imparts hydrophilicity. Replacement of
the Hs from the Si-OH groups by the hydrolytically
stable non hydrolysable Si-R (were, R = alkyl or aryl)
groups, prevent the adsorption of water, resulting in
the dehydroxylation of the film surface, leading to
hydrophobicity [10]. Hence condensation reactions of
TEOS and GPTMS followed by hydrophobization
with HDTMS layers of long chain alkyl groups
imparting both hydrophobicity and roughness could
be a possible sol-gel mechanism. In a similar work
reported by Mahadik et al. [20], trimethylchlorosilane
(TMCS) was used in the sol-gel processing to replace
the -OH group by hydrolytically stable -O-S-(CH3)3
groups, producing superhydrophobic films. Fig. 5
shows the probable reaction of GPTMS, TEOS and
HDTMS that may result in grafting of surface Si-OH
groups with non polar Si-(C16H32) groups of HDTMS
forming a non-hydrolysable and hence hydrophobic
layer on the surface with C.A. > 90 [10]. Sol D with
GPTMS:HDTMS:TEOS ratio of 2:2:6 was found to

have optimum hydrophobicity with C.A. of 95 on


un-etched aluminium sample with gel time of 15 d.
At higher concentrations, long chain structure of
HDTMS may contribute to the decrease in the
reaction rate due to steric hindrance, leading to poor
adhesion and other mechanical properties [15].
Further, the extent of hydrophobicity was found to
increase with enhanced surface roughness. It is well
known that contact angles of long chain hydrocarbon
and fluorocarbon self-assembled monolayers generally
do not exceed 112 and 115, respectively on smooth
hydrophobic surface. However, the situation is quite
different when the surface is rough [21]. The effect of
chemical etching with various etchants prior to
coating application, resulted in enhanced roughness. It
was observed that surface roughness increases with
severity of the etchant with maximum contact angle
achieved for Becks reagent of about 130 and RMS of
about 100 nm. According to Qu, et al. [17], etching of
aluminium revealed grain boundaries, cavities and
island structures. Such a rough surface plays an
essential role in trapping air between the substrate
surface and the liquid droplets, leading to lowering of
forces of friction and hence enhancing the
hydrophobic and sliding behavior of the water
droplets.

6. Conclusions
(1) Eco-friendly hydrophobic sol-gel coatings were
synthesized for aluminium substrates by non-fluoro
approach, using long chain alkyl HDTMS, GPTMS
and TEOS precursors. Application of these coatings
on smooth and clean aluminium substrates resulted in
hydrophobic surface with contact angle of about 95.
(2) Further pre-treating the aluminium substrate,
using various etchants, helped in enhancing the
hydrophobicity substantially by creating suitable
roughness of about 120 nm. This resulted in contact
angle of about 130. Hence, chemical etching,
combined with HDTMS modification, resulted in an
effective water repellent surface.

Development of Hydrophobic Non-Fluorine Sol-Gel Coatings on Aluminum Using Long Chain Alkyl
Silane Precursor

Acknowledgements
The authors acknowledge the financial support from
DOW Chemicals. They also sincerely thank Arun
Basrur, and Vijay Ramakrishnan for their useful
suggestions and critical comment to complete this
work.

[10]

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