Preparation of Silane-Functionalized...
Preparation of Silane-Functionalized...
Preparation of Silane-Functionalized...
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.
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
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].
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. 4. FE-SEM images (a) 0 vol.% and after (b) 15 vol.% of iso-OTMS.
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.
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