Preparation of Silane-Functionalized...

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Applied Surface Science 317 (2014) 147–153

Contents lists available at ScienceDirect

Applied Surface Science


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

Preparation of silane-functionalized silica films via two-step dip


coating sol–gel and evaluation of their superhydrophobic properties
Maedeh Ramezani a,∗ , Mohammad Reza Vaezi a , Asghar Kazemzadeh b
a
Division of Nanotechnology and Advanced Materials, Materials and Energy Research Center, P.O. Box 31787-316, Karaj, Iran
b
Division of Semiconductors, Materials and Energy Research Center, P.O. Box 31787-316, Karaj, Iran

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

Article history: In this paper, we study the two-step dip coating via a sol–gel process to prepare superhydrophobic silica
Received 15 April 2014 films on the glass substrate. The water repellency of the silica films was controlled by surface silyla-
Received in revised form 17 August 2014 tion method using isooctyltrimethoxysilane (iso-OTMS) as a surface modifying agent. Silica alcosol was
Accepted 18 August 2014
synthesized by keeping the molar ratio of ethyltriethoxysilane (ETES) precursor, ethanol (EtOH) solvent,
Available online 23 August 2014
water (H2 O) was kept constant at 1:36:6.6 respectively, with 6 M NH4 OH throughout the experiment and
the percentages of hydrophobic agent in hexane bath was varied from 0 to 15 vol.%. The static water con-
Keywords:
tact angle values of the silica films increased from 108◦ to 160◦ with an increase in the vol.% of iso-OTMS.
Superhydrophobic surfaces
Silica film
At 15 vol%. of iso-OTMS, the silica film shows static water contact angle as high as 160◦ . The superhy-
Sol–gel process drophobic silica films are thermally stable up to 440 ◦ C and above this temperature, the silica films lose
Contact angle superhydrophobicity. By controlling the primer particle size of SiO2 about 26 nm, leading to decrease the
final size of silica nanoparticles after modification of nanoparticles by isooctyltrimethoxysilane about
42 nm. The films are transparent and have uniform size on the surface. The silica films have been charac-
terized by atomic force microscopy (AFM), fourier transform infrared spectroscopy (FT-IR), transparency,
contact angle measurement (CA), Zeta-potential, Thermal stability by TG–DTA analysis.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction typical size of roughness detail in superhydrophobic surface is


micro and nano scales. Various materials are used to make super-
Self-cleaning surfaces are capable of repelling contaminants, hydrophobic coatings and can be divided into two series: causing a
including solid particles, organic liquids. The most common prin- rough surface with a low surface energy material and modifying a
ciple of a superhydrophobic self-cleaning surface is Lotus effect, rough surface by a material which have a low surface energy [9–15].
induced by surface roughness. Surfaces with a water contact angle Organosilanes are used as efficient coupling agents extensively
greater than 150◦ are called “superhydrophobic” are of interest used in composites and improving the adhesion of various coat-
for numerous applications, including self-cleaning coating, anti- ings. Functional trialkoxysilanes, Rı́Si(OR)3 , are common graffiting
corrosion, biotechnology, low friction coatings. Many biological agents, used in numerous industrial application in order to increase
structures in nature are highly hydrophobic including the bird adhesion between organic and inorganic substrate. The organosi-
feathers, rice leaves, mosquito eyes, gecko feet and plants leave lane molecule has two key elements; a non-hydrolyzable organic
such as cabbage. Among the natural surfaces, which are super- moiety (Rı́). This moiety can be reactive toward another chemical
hydrophobic self-cleaning are the leaves of the water repellent or nonreactive and a hydrolyzable group (OR) [16,17].
plants such as Nelumbo nucifera (lotus). Electron microscopy of Superhydrophobic surface can be prepared from a variety of
lotus leaves shows bumps which protruding nubs about 20–40 ␮m. methods [18]. However, sol–gel process has been used to fabri-
In turn; they are covered by an additional layer which is smaller cate superhydrophobic surfaces [19]. Sol–gel techniques for a long
scale rough surface of epicuticular waxes [1–8]. time have been used for preparing a range of materials which
To achieve superhydrophobicity, a surface must have two phys- have a wide range of physicochemical properties. There are many
ical properties: a surface roughness and a low surface energy. The reports available for the preparation of superhydrophobic silica
films by sol–gel process [20–23]. But till date, there is not any
report on the preparation of superhydrophobic silica film using
∗ Corresponding author. Tel.: +98 9112146943; fax: +98 26 36280030. isooctyltrimethoxysilane as a silylating agent. The surface chemi-
E-mail address: [email protected] (M. Ramezani). cal modification of the silica film using octyltriethoxysilane (OTES)

http://dx.doi.org/10.1016/j.apsusc.2014.08.095
0169-4332/© 2014 Elsevier B.V. All rights reserved.
148 M. Ramezani et al. / Applied Surface Science 317 (2014) 147–153

as a hydrophobic agent has been reported [24,25]. The OTES mod- hydroxide (6 M) was added to alcosol. Silica sol was stirred at 55 ◦ C
ified films exhibited water contact angles (107◦ and 125◦ ). In the for 4 h and was kept to stir for 18 h before the dip coating to com-
present research work, the preparation of the silica films on the plete hydrolysis and condensation reactions. The substrates were
glass samples was carried out by ethyltriethoxysilane (ETES) as a dipped vertically in transparent silica sol and withdrawn with the
precursor and isooctyltrimethoxysilane (iso-OTMS) as a modifying speed of 5 mm/s. After coating, the films were dried at room tem-
agent via two-step dip-coating method. Wetting behavior of sil- perature for 2 h to form chemical bonding between deposition sol
ica films was tested by measuring water contact angle. The water and hydroxyl groups on the surface of substrate. Then, the trans-
contact angle before and after modifying with iso-OTMS increased parent coatings were heated at 120 ◦ C for 2 h to covalent linkage
from 108◦ to 160◦ and is quite better than silica films modified is formed in the substrate with losing of residual solvent. After the
by OTES. Scanning electron microscope studies revealed that the deposition of transparent films, they were put into the modifying
superhydrophobic the silica film modified with 15 vol.% of iso- solution consist of iso-OTMS in hexane bath for 6 h at 60 ◦ C. The
OTMS is related to its nanostructure which size about 42 nm. In this percentage of silylation agent was varied from 2.5 to 15%. The sam-
research work by controlling the gelation time of alcosol containing ples were washed with hexane to remove the excess hydrophobic
of ethyltriethoxysilane as precursor, we could decrease the primer agent from the surface. The films were dried at 150 ◦ C for 1 h and a
particle size of SiO2 ranging about 26 nm, which was not achieved half.
by dip-coating method in the previous research works. This leads
to decrease the final size of silica nanoparticles after modifica- 2.3. Sample characterization
tion of nanoparticles by isooctyltrimethoxysilane about 42 nm in
comparison of previous works that agglomeration of nanoparticles The size and morphologies of the nanoparticles on the sub-
occurred and led to increase in particle size. In other words, con- strates coated with gold were studied by field emission scanning
trol of hydrolysis and condensation reaction of sol–gel process and electron microscopy (FE-SEM: Hitachi-S4160, Hitachi City, Japan).
gelation time is one of the best ways to decrease the size of nanopar- The surface topography of the silica films was analyzed by atomic
ticles and improve the hydrophobicity and transparency. Another force microscopy (CP, Park Scientific Instrument, USA) in contact
factor that is improved by decreasing the size of the nanoparticles mode. The root-mean-square (RMS) roughness value of the sam-
is surface roughness. The iso-OTMS modified silica film showed a ples was calculated by nano scope software. Organic and inorganic
root-mean-square (RMS) roughness value of 9.172 nm. Whereas, in bands such as Si C, Si OH, C H and Si O Si in modified surfaces
the other research works, the superhydrophobic silica films were were studied by fourier transform infrared spectroscopy (Spectrum
prepared in dip-coating method showed higher roughness values RXI, Perkin Elmer, USA). Contact angle analysis was carried out
[6,23,27,34,36,39]. to provide information on the hydrophobicity and the degree of
modification of substrates by measuring the static contact angle of
4 ␮L DI water droplet on the three different areas of each sample
2. Experimental using a contact angle analyzer equipped with a CCD camera (Dat-
aphysics Instrument, Model OCA 15 plus) at room temperature.
2.1. Materials Percentage of optical transmission of the coated glass substrate
was measured in the visible range by UV-V–vis spectrophotome-
All chemicals were used as received: ethanol and hexane (99%, ter (Lambda 25 Spectrometer, Perkin Elmer, USA). Blank glass was
Merck, Germany), ethyltriethoxysilane (97%, Sigma–Aldrich, used as a reference. Termogravimetric measurement was carried
Germany), isooctyltrimethoxysilane (97%, Sigma–Aldrich, out with TGA-DTA (BAHR-STA-503, Germany). Thermal stability
Germany), ammonia (28%, Merck, Germany). Deionized water of the coating was determined by putting the silica nanoparticles
was used for preparation of the catalyst. in furnace (Exction, EX 1200-4L) and was heated to 600 ◦ C with
speed of 10 ◦ C/min. The zeta potential of the silica suspensions was
calculated using an electrophoretic light scattering spectrometer
2.2. Sample preparation (Zeta Sizer, Model 3000HS, Molvern instrument Ltd.). The pH of
each suspension was adjusted with hydrochloric acid or sodium
In order to obtain transparent silica film, alcosol was syn- hydroxide.
thesized under basic condition from ethanol (EtOH) as solvent,
ethyltriethoxysilane (ETES) as a precursor, in the presence of the 3. Result and discussion
ammonium hydroxide (NH4 OH) as a catalyst. Before treatment, all
the glass substrates of 15 × 10 × 1 mm were washed with a deter- 3.1. Reaction mechanism
gent solution and were ultrasonicated for 15 min with H2 SO4 10%,
deionized water and ethanol respectively. Then all of them were For enhancing the adhesive force between hydrophobic agent
dried in an oven for 1 h and a half at 70 ◦ C. The molar ratio of and substrates, ethyltriethoxysilane group can be introduced on
ETES:EtOH:H2 O was kept constant at 1:36:6.6 respectively, with the surface via sol–gel method [26]. Initially, hydrolysis of the tri-
6 M NH4 OH concentration. In the first step, ETES was diluted in ethoxysilane groups of ETES occurred to afford Si OH groups. Then,
the ethanol and stirred for 40 min. Deionized water was dropped condensed with silanol groups to produce Si O Si linkage and cat-
into the mixture, while stirring (15 min). After that, ammonium alyzed by ammonium hydroxide [27], as shown in the Eqs. (1)–(3):
Hydrolysis
M. Ramezani et al. / Applied Surface Science 317 (2014) 147–153 149

Water condensation

Alcohol condensation

Then, the glass substrates were dipped in transparent alcosol.


The nano particles then can form hydrogen bonds with OH groups
of the substrate. Finally, the nanoparticle surface was functional- surface with large roughness and the apparent contact angle,  c can
ized with different concentration of isooctyltrimethoxysilane as a be expressed as
hydrophobic agent (Fig. 1).
The superhydrophobicity of the silica film is due to displace- cos  c = f1 cos 1 + f2 cos 2 (5)
ment of non-polar organic substitution of the Si (C8 H17 ) groups Where f 1 and f 2 are fraction of different surface (f 1 + f 2 = 1),  1 and
to hydroxyl groups on the silica nanoparticles and the surface is  2 are Young’s contact with the homogeneous surface, respectively.
effectively shielded [28]. In this study, the increase of water con- When a unit area of the surface has a wetted solid surface area
tact angle was observed when the silylation agent concentration fraction f with a water contact angle  0 , Eq. (5) can be expressed as
was increased. the following equation, assuming 180◦ water contact angle for air:

3.2. Effect of percentage of the hydrophobic agent on water cos  c = f cos 0 + (1 − f ) cos 180◦ = f (cos 0 + 1) − 1 (6)
contact angle Where f is the fraction of liquid–solid contact with the pro-
jected surface area. In the ideal situation of a perfectly smooth
The wetting properties of a surface are dependent on the sur- and homogeneous surface, the static contact angle a single num-
face chemistry and morphology. The effect of roughness on wetting ber which corresponds to the unique equilibrium position of the
was investigated to describe superhydrophobic surfaces by “Wen- solid–liquid–air contact line [10,26].
zel” and “Cassie–Baxter” [10]. The Wenzel equation for the contact Hydrophobic properties of the coated glasses were calculated
angle  w with a rough surface: by measuring the static contact angle values on the silica films pre-
r (SV − SL ) pared with different concentrations (2.5, 5, 7.5, 10, 12.5, 15 vol.%)
cos  w = = rf cos 0 (4) of iso-OTMS-coated surfaces. Fig. 2 shows images of water droplet
LV
on the silica film with different percentage of iso-OTMS. A drop of
Where  SL ,  SV , and  LV , are interfacial free energies per unit water on the surface without iso-OTMS shows a water contact angle
area of solid–liquid, solid–gas, and liquid–gas interfaces, respec- which is about 108◦ . A large number of hydroxyl groups on the sur-
tively [29]. In addition,  0 is the equilibrium contact angle on the face of the silica film, which can form hydrogen bond with water
smooth surface or the Young’s [30] contact angle. In this equa- molecules are responsible for the low hydrophobicity [32,33]. How-
tion, rf is the roughness factor defines as the ratio of the rough ever, the ethyl groups present in the ETES lead to the hydrophobic
interfacial area over the apparent surface area. A rough solid sur- character and the water repellency of the unmodified surface up to
face with the roughness factor rf > 1, rises hydrophobicity of the 108◦ . After silylation by iso-OTMS, an unmodified silica film, which
hydrophobic surface. When the substrate is hydrophilic ( 0 < 90◦ ), showed hydrophobic behavior changed to the superhydrophobic.
solid–liquid interaction is favored;  w will be decreased by rough- As expected, with the increase in percentage of iso-OTMS in hex-
ness, resulting in spontaneous spreading on the rough surface. If ane bath, the hydrogen of the hydroxyl groups on the silica films is
some air trapped between the rough solid surface, only the frac- replaced by the non-polar and hydrolytically stable of Si (C8 H17 )
tion 0 < f SL < 1 is constituted to be a composite surface of solid and groups and leads to the further surface coverage and the increase
air [31]. Cassie–Baxter proposed an equation for a hydrophobic in contact angle from 108◦ to 160◦ (Fig. 3). As the trend shows, with

Fig. 1. Schematic illustration of the surface modification of the silica nanoparticle by iso-OTMS on the glass substrate.
150 M. Ramezani et al. / Applied Surface Science 317 (2014) 147–153

Fig. 2. Contact angle images on the silica films prepared with (a) 0 vol.%, (b) 7.5 vol.%, and (c) 15 vol.% of iso-OTMS.

further increase in vol.% of iso-OTMS the films will show the same
contact angle about 160◦ or slight increase in degree of superhy-
drophobicity. Because in higher than 15 vol.%, replacement of polar
OH groups by non-polar groups of iso-OTMS on the silica film is
almost completed and further silylation cannot proceed. Also, the
influence of the steric hindrance in branched alkyl groups prevents
from further replacement of Si (C8 H17 ) groups on the silica surface
[34].

3.3. Surface morphological study

Two dimensional FE-SEM images of the superhydrophobic silica Fig. 3. Variation of contact angle with vol.% of iso-OTMS.
film, before (0 vol.%) and after modification with (15 vol.% of iso-
OTMS) revealed, with an increase in iso-OTMS concentration 0 vol.%
to 15 vol.%, silica film covered on top of the layers and silica film has 3.4. Atomic force microscopy
much more functionalized nanoparticles. Fig. 4 shows the unmodi-
fied and modified silica films. The size of unmodified and modified The surface topography of the dip-coated silica films was
nanoparticles on the substrate is 26 and 42 nm respectively. When recorded by AFM. Fig. 5 shows the surface morphology of the
the silica film was dipped into the hydrophobic agent’s solution, unmodified silica nanoparticles (0 vol.%) and iso-OTMS modified
the alkyl groups will condense onto the hydroxyl surface of the sil- (15 vol.%) respectively. AFM images showed the root-mean-square
ica core particles and form an outer coating. In other words, after (RMS) roughness values increased from 1.815 nm (0 vol.%) to
functionalization with iso-OTMS, the nanoparticles of SiO2 increase 9.172 nm (15 vol.%) with increasing the percentage of iso-OTMS.
about 42 nm in particle size. This indicates the growth of ∼16 nm AFM images suggest that the surface roughness value, contributes
of functionalized shell thickness. to higher contact angle [35].
M. Ramezani et al. / Applied Surface Science 317 (2014) 147–153 151

Fig. 5. AFM images of dip-coated silica films treated at different concentration of


iso-OTMS. (a) 0 vol.%, and (b) 15 vol.%.

Fig. 4. FE-SEM images (a) 0 vol.% and after (b) 15 vol.% of iso-OTMS.

3.5. FT-IR analysis

Infrared spectroscopic measurements were carried out by FT-IR


spectrophotometer at room temperature (25 ◦ C) using the KBr pel-
let method. The sol–gel reaction was confirmed via FT-IR is shown
in Fig. 6. The strong absorption peak at around 1089 cm−1 , which
represents the information of the Si O Si asymmetric stretching
vibration [36]. The broad absorption band at around 3417 cm−1 and
sharp band at 1631 cm−1 were respectively corresponded to the
O H stretching and bending absorption. The absorption peaks at
around 2980 cm−1 and 1400 cm−1 corresponded to the stretching
Fig. 6. FT-IR spectra of (a) 0 vol.%, (b) 5 vol.% and (c) 15 vol.% of iso-OTMS.
and bending of C H bonds. However, with increasing concentration
of hydrophobic agent, the intensity of O H bands at 3417 cm−1 and
1631 cm−1 decreased and the absorption bonds relating to methyl
groups (C H), at 2980 cm−1 and 1400 cm−1 increased in inten-
sity. This confirms the modification of the silica nanoparticles by
displacing the polar and hydrophilic groups’ OH with non-polar
bonds like Si C and C H leads to increase in the hydrophobicity of
the silica films [37].
Fig. 7 is the FT-IR spectra of the functionalized silica nanoparti-
cles by 15 vol.% of iso-OTMS was heated to 400 ◦ C. During annealing,
the siloxane (Si O Si) bonds at around 1136 cm−1 and 812 cm−1
grew and shifted to the higher wave number and the O H bands
at 3433 cm−1 and 1627 cm−1 with curing increased in intensity.
The methyl groups (C H) regions at 2980 cm−1 and 1400 cm−1
declined. This is due to organic group getting oxidized into the
hydrophilic Si OH groups and the chemical nature of the silica film
changed on annealing [38]. Fig. 7. FT-IR spectra of iso-OTMS (15 vol.%) cured at 400 ◦ C.
152 M. Ramezani et al. / Applied Surface Science 317 (2014) 147–153

Fig. 9. Optical transmittance spectra of the coating with (a) 0 vol.% and (b) 15 vol.%
of iso-OTMS.

Fig. 8. STA curve of the silica film prepared with (a) 0 vol.%, (b) 15 vol.% of iso-OTMS.

3.6. Termogravimetric and differential analysis

The thermal durability of nanoparticles of silica functionalized


in the air was tested by STA (TG–DTA) analysis (Fig. 8). STA curves Fig. 10. ␨-potential of ETES () and iso-OTMS () silica suspensions at different pH.
were recorded in the air at a heating rate of 10 ◦ C/min from room
temperature to 600 ◦ C. The endothermic peak at 30–100 ◦ C for both
the 0 vol.% and 15 vol.% of iso-OTMS is the result of desorption of
water and liberation of the byproduct of the modification of silica
surface by ethyltriethoxysilane and isooctyltrimethoxysilane like
ethanol and methanol, respectively [39]. There is an exothermic
peak at 300 ◦ C and 440 ◦ C for 0 vol.% and 15 vol.% of iso-OTMS corre-
sponding to the oxidation and thermal decomposition of ethyl and
isooctyle surface organic groups respectively [40]. This consider-
able difference in the decomposition temperature (140 ◦ C) is due to
differences in the organic substituent of the surface silica particles
covered by a larger alkyl group of isooctyle which provided better
surface treatment and thermally stable than the ethyl group [41].
This is obvious; the hydrophobic silica films are thermally stable up
Fig. 11. Representation of electrostatic repulsion with barrier steric of iso-OTMS.
to 300 ◦ C and 440 ◦ C respectively. However, above these tempera-
tures, the silica films lose hydrophobicity due to oxidation of alkyl
groups and the hydrophobic character becomes hydrophilic.
iso-TMS suspensions. The magnitude of the zeta-potential of the
3.7. Optical transmission studies ETES and iso-OTMS particles increased as the pH was increased.
Both of them have a negative charge. pH = 2 appears as bound-
Transparency and surface roughness are generally competitive ary, since the point of zero charge (PZC), where the surface charge
properties. To get high transparency in the visible light, the size is zero. For pH < PZC and pH > PZC, the surface is positively and
of roughness should be lower than 100 nm [42]. The percentage negatively charged, respectively. The ETES and iso-OTMS silica
of the optical transmission of the unmodified and modified silica nanoparticles have silanol groups on their surface, which above
films with 15 vol.% of iso-OTMS in the UV–visible range has been pH ≥ 3 where the silica particles ionized and produced a negative
shown in Fig. 9. Both of the silica coatings are transparent. The sil- charge. Thus, as the pH increased, the most acidic silanol likely to
ica film with 0 vol.% and 15 vol.% of iso-OTMS showed an optical be deprotonated which produced a negative zeta potential. But, in
transmission of up to 96% and 92%, respectively. the iso-OTMS the steric hindrance of the organic moiety (isooctyle)
of the particles prevents from approaching each other reducing the
3.8. Analysis of dispersion property role of the van der Waals forces and permitted the greatest separa-
tion of charge between the deprotonated sites and produced more
The zeta-potential of the ETES and iso-OTMS were calculated highly negative zeta-potential [43,44]. In the other hand, electro-
to determine the surface charge and evaluate the effect of pH on static stabilization is combined with steric effect and nanoparticles
the surface charge. Fig. 10 shows the zeta-potential of the ETES and are completely stabilized (Fig. 11).
M. Ramezani et al. / Applied Surface Science 317 (2014) 147–153 153

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