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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.
Development of Hydrophobic Non-Fluorine Sol-Gel Coatings on Aluminum Using Long Chain Alkyl
Silane Precursor
225
226
Development of Hydrophobic Non-Fluorine Sol-Gel Coatings on Aluminum Using Long Chain Alkyl
Silane Precursor
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.
GPTMS (ml)
HDTMS (ml)
TEOS (ml)
Sol A
0.5
1.5
Sol B
Sol C
Sol D
Sol E
12
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
decreases
drastically
after
substantial
amount
of
HDTMS
was
required
for
Development of Hydrophobic Non-Fluorine Sol-Gel Coatings on Aluminum Using Long Chain Alkyl
Silane Precursor
227
(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
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
228
Development of Hydrophobic Non-Fluorine Sol-Gel Coatings on Aluminum Using Long Chain Alkyl
Silane Precursor
(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 .
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
226
Development of Hydrophobic Non-Fluorine Sol-Gel Coatings on Aluminum Using Long Chain Alkyl
Silane Precursor
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
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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