Note
DOI: 10.1002/bkcs.10025 J. Hwang and Y. Ahn
Fabrication of Superhydrophobic Silica Nanoparticles and
Nanocomposite Coating on Glass Surfaces
Jisu Hwang and Yonghyun Ahn*
Department of Chemistry, GRRC, Dankook University, Yongin 448-701, Korea.
*E-mail: yhahn@dankook.ac.kr
Received August 25, 2014, Accepted September 19, 2014, Published online January 5, 2015
Keywords: Silica nanoparticles, Superhydrophobicity, Nanocomposite solution, Dip-coating, Lotus effect
The discovery of the self-cleaning property of the lotus leaf has
spurred the interest on superhydrophobic surfaces, which has
been growing over recent decades.1–3 The self-cleaning effect
is a wonderful natural phenomenon resulting from the low sur-
face energy of the material coated on the nano/micro-rough
surface. Impurities are easily washed away by water droplets
owing to their weak interaction in the superhydrophobic sur-
face; therefore, the surface of the lotus leaf is always clean. It is
composed of nano/microscale protrusions, and its surface is
covered with wax. Moreover, it has a high water contact angle
(WCA >150
) and low sliding angle (<10
). The surface is
hydrophilic if WCA <90
and hydrophobic if WCA >90
;
moreover, if WCA is higher than 150
, the surface is sometimes
considered superhydrophobic. A water droplet on a superhy-
drophobic surface does not penetrate the cavities of the nano/
micro-rough surface because of the air inside the cavities.
The generation of rough surfaces and subsequent coating
with a material having a low surface energy is a common
process for fabricating artificial superhydrophobic surfaces.
Various techniques have been recently used to generate
such surfaces, with the common ones being lithography,4–6
plasma treatment,7,8 electrospinning,9,10 chemical vapor
deposition,11,12 sol–gel process,13,14 and chemical etching.15,16
Silica nanoparticles are one of the most popular nanomaterials
and produced by numerous companies. Mass-produced silica
nanoparticles are available in the nanoscale and microscale at
a very low cost. Silica nanoparticles are commonly used in
the fields of biomedicine and material science; for instance, it
is used as a composite coating material to harden polymers.
Although silica nanoparticles are hydrophilic, their surface
can be modified with a material having low surface energy;
thus, these are popularly used to fabricate materials with a super-
hydrophobic surface. This method has been applied, for exam-
ple, in the formation of alkyl silane self-assembled monolayers
(SAMs),17 layer-by-layer assembly of multilayer films,18 and
chemical vapor deposition of thin films on a surface.19
In this work, we report the fabrication of a superhydrophobic
surface using silica nanoparticles. The initial step is the chem-
ical reaction of the hydroxyl groups on the silica surface with 3-
aminopropyl triethoxysilane (APTES),20–23 followed by the
condensation of palmitoyl chloride with the modified nanopar-
ticles (Scheme 1). To enhance the superhydrophobicity of the
Bull. Korean Chem. Soc. 2015, Vol. 36, 391–394 © 2015 Korean Chemical Society, Seoul & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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surface of silica nanoparticles, polystyrene (PS) was selected
as a raw material. It has low surface energy and is a popular
material for the fabrication of a superhydrophobic sur-
faces.24–28 A nanocomposite coating solution is prepared
by combining modified silica nanoparticles and PS in tetrahy-
drofuran (THF), which is then used to fabricate the superhy-
drophobic glass.
Experimental
Materials. Tetraethoxysilane (TEOS, 99.0%), ethanol, poly-
styrene (MW = 192 000), APTES, palmitoyl chloride, and
ammonium hydroxide (28% NH3 in H2O) were purchased
from Sigma-Aldrich Korea (Yongin, Korea). Glass was pur-
chased from Paul Marienfeld GmbH & Co. KG (Lauda-
Königshofen, Germany). All chemicals were used as-received
without further purification.
Synthesis of Silica Nanoparticles. Silica nanoparticles were
prepared using the Stöber method.20,29 First, TEOS (25 g,
118 mmol) was added to a solution of methanol (300 mL),
deionized H2O (3 mL), and NH4OH (30 mL), and the resulting
mixture was stirred vigorously at 50
C for 3 h. The prepared
silica nanoparticles were collected by centrifugation (4000
rpm, 20 min) at room temperature and subsequently cleaned
three times by centrifugation with ethanol (300 mL). The silica
nanoparticles were dried overnight at 40
C.
Modification of Silica Nanoparticles
Preparation of 3-Aminopropylsilylated Silica Nanoparticles
(ASNPs). ASNPs were prepared following the Lu method.20
A solution of APTES (4.7 mL, 20.2 mmol), NH4OH (0.6 mL),
and deionized H2O (14.6 mL) was added to the suspension of
silica nanoparticles (8.1 g) in ethanol (250 mL). The mixture
was heated at 70
C for 3 h. The precipitate was collected by
centrifugation (4000 rpm, 20 min) at room temperature. The
precipitate was washed twice by sonication with ethanol
(300 mL), followed by centrifugation (4000 rpm, 20 min).
Preparation of 3-Palmitoylamido-propylsilylated Silica
Nanoparticles (PASNPs). Triethylamine (TEA, 5.6 mL,
40 mmol) and palmitoyl chloride (12.1 mL, 40 mmol) were
added consecutively to the suspension of ASNPs (8 g) in
dimethylformamide (200 mL), and the resulting mixture
was heated at 80
C overnight. The precipitate was collected
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Scheme 1. Modification of the surface of silica nanoparticles.
by centrifugation (4000 rpm, 20 min) at room temperature. It
was then sonicated in a mixture of CH2Cl2 (160 mL) and dis-
tilled H2O (160 mL) for 20 min and collected by centrifugation
(4000 rpm, 20 min). The washing step was repeated to obtain
clean PASNPs.
Preparation of Composite Solution. PASNPs (0.3 g) were
dispersed in THF (10 mL), to which PS (0.2 g) was added. The
mixture was stirred at room temperature for 1 h, sonicated for 1
h, and then used for dip coating.
Fabrication of Glass Plate
Dip-coating Procedure. Following the typical method, a glass
plate was cleaned by sonication in ethanol for 10 min and dried
at 40
C overnight. The clean glass plate was immersed in the
coating solution for 30 s, and consistently withdrawn at a rate
of 1 cm/s. The plate was dried for 30 min at 40
C.
Characterization. The surface morphology of the modified
silica nanoparticles was observed using field-emission scan-
ning electron microscopy (FE-SEM, Hitachi S4300, Hitachi
Inc., Tokyo, Japan). Fourier transform infrared spectroscopy
(FTIR, Spectrum 100, PerkinElmer, Santa Clara, CA, USA)
was used to identify the chemical functional groups in the
coated material. The WCA with a droplet of purified water
(5 μL) was measured at room temperature using an optical con-
tact angle meter (Phoenix 300, Surface Electro Optics, Suwon,
Gyunggido, Korea). X-ray photoelectron spectroscopy (XPS,
Theta Probe AR-XPS System, Thermo Fisher Scientific,
Loughborough, UK) was used to determine the chemical com-
position of the coated material.
Results and Discussion
Polystyrene has recently become a popular plastic in the indus-
try. It dissolves well in THF and was therefore selected to bind
modified silica nanoparticles for fabricating a superhydropho-
bic surface.
Modified silica nanoparticles were obtained through treat-
ment with APTES and subsequent condensation with palmi-
toyl chloride (Scheme 1). The ethoxy groups of APTES
were hydrolyzed and the resulting product was condensed
with the hydroxyl groups on the surface of silica nanoparticles.
As a result, silica nanoparticles were covered with APTES
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molecules. The amino groups of ASNPs condensed with pal-
mitoyl chloride in the presence of TEA at 80
C. After the reac-
tion, the diameter of the spherical silica nanoparticles was
68 nm, as determined from the SEM image (Figure 1).
PASNPs were used to form liquid marbles. A water droplet
(30 μL) was dropped on the PASNP powder and rolled slowly
back and forth. The formation of liquid marble indicates that the
surface of the modified silica nanoparticles was superhydropho-
bic. The liquid marbles were very stable even after transfer onto
a different Petri dish. Particle deformation occurred after 2 h at
room temperature because of water evaporation (Figure 2). The
liquid marbles were covered with a multilayer of superhydro-
phobic silica nanoparticles and showed significant roughness.
In addition to liquid marble formation, the buoyancy of silica
nanoparticles in water was also tested. Unmodified silica nano-
particles sank to the bottom (Figure 3(a)), while the modified
ones floated on water. A glass tube was slowly dipped into
the water containing the modified silica nanoparticles and
became covered with the nanoparticles. The surface of the test
tube was mirror-like, and bubbles were evident (Figure 3(b)).
This was attributed to the layer of trapped air that formed
between the superhydrophobic surface and water.30
Surface roughness on a solid plate is one of the key
factors to generate a superhydrophobic surface. Functionalized
Figure 1. SEM images of (a) unmodified silica nanoparticles, (b)
ASNPs, and (c) PASNPs.
Figure 2. Evolution of a 30-μL water marble with time: (a) 0, (b) 40,
(c) 80, and (d) 120 min.
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PASNPs were mixed with PS in THF to produce a composite
solution, which was used to coat the glass plate by dip coating.
Figure 4 shows the WCAs of the coated glass plates with differ-
ent silica nanoparticles. The surface coated with silica nanopar-
ticles/PS was found to be moderately hydrophobic (WCA =
100
). Therefore, the modified silica nanoparticles were used
to provide roughness to the surface. SEM images showed the
difference in roughness between silica/PS and PASNPs/PS
(Figure 4(c)and (d)). The surface roughness of the glass plate
coated with PASNPs/PS was greater than that of the plate coated
with silica/PS, resulting in a superhydrophobic surface (WCA
= 159.5
).
The surface-functionalized silica nanoparticles were charac-
terized by FTIR analysis. ASNPs had a very strong NH2 peak at
3323 cm−1, which decreased after reaction with palmitoyl chlo-
ride. The band at 1655 cm−1 of PASNPs was assigned to the
C O stretching vibration of the amide group. Asymmetric
and symmetric stretching of the aliphatic CH2 group appeared
at 2923 and 2853 cm−1, respectively, and the very strong band at
1038 cm−1 was assigned to the Si O Si group. The results
indicate that the surface of the silica nanoparticle was success-
fully modified with APTES and palmitoyl chloride.
In the Cassie–Baxter model, water does not penetrate the
valley between protrusions because air is trapped in the valley.
Figure 3. Images of (a) sunken unmodified silica nanoparticles and
(b) PASNPs covering the immersed test tube.
Figure 4. SEM images of glass plates coated with a solution of (a)
untreated glass plate, (b) PS, (c) untreated silica nanoparticles/PS,
and (d) PASNPs/PS.
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Therefore, the contact area between the water droplet and
rough surface is minimized, resulting in superhydrophobicity.
The Cassie–Baxter equation2 can be used to describe the wet-
ting property of the glass surface.
cos θ∗ = Φs ð1 + cos θÞ− 1
In this equation, θ∗ and θ are the WCAs of the surface mod-
ified with PASNP/PS and PS, respectively. Φs is the fraction of
the base of the water droplet in contact with the hierarchical
modified surface. The WCA of the glass plate surface coated
with PASNP/PS was θ∗ = 159.5
, while that of the plate coated
with PS was 93
. The calculated value for Φs was 0.066, indi-
cating that only 6.6% of the water droplet was in contact with
superhydrophobic surface while the rest was in contact with
air. The air trapped in the interspaces and the low surface
energy of the material coating the silica nanoparticles contrib-
uted to the superhydrophobicity of the glass surface.
The composition of the coated plate was determined by energy
dispersive spectroscopy (EDX) analysis. C, O, N, and Si peaks
were observed in the EDX spectrum. This result confirms that the
surface was coated with the PASNPs/PS (Figure 5).
XPS was used to determine the chemical composition of the
modified surface. The spectra showed that the PASNP/PS
glass coating was composed of C, O, Si, and N. The peaks
of C, O, and Si were found on the SiO2/PS coating surface.
The ratios of C, O, and Si changed depending on the modifi-
cation of the silica nanoparticles. It was found that the C/O
ratios are 0.20 and 0.77 for the unmodified silica nanoparti-
cle/PS and PASNP/PS composite glass coating, respectively.
Thus, the carbon atom concentration increased threefold with
the modification. In addition, a nitrogen peak at 399 eV was
found for the modified silica nanoparticles used to coat the
glass surface (Figure 6). The C 1s peak can be resolved into
two peaks (Figure 7). The first peak at 285.7 eV can be
assigned to the C N group in PASNP, while the second peak
at 284.6 eV may originate from the C C and C H groups.
In summary, we demonstrated that a simple dip-coating
method enabled the fabrication of a superhydrophobic glass
coated with a composite solution of PASNP/PS in THF.
Superhydrophobic PASNPs were successfully prepared by
treatment with APTES and subsequent condensation with
Figure 5. EDX spectrum of the glass plate coated with PASNPs/PS.
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Figure 6. XPS spectra of untreated glass and glass coated with unmo-
dified silica nanoparticles/PS and PASNP/PS.
Figure 7. High-resolution C 1s XPS spectra of glass coated with the
PASNPs/PS.
palmitoyl chloride. PASNPs formed stable liquid marbles
with water, which indicated that ASNPs successfully reacted
with palmitoyl chloride. The chemical composition of
PASNPs was determined by XPS and FTIR analyses. The
composite solution of PASNP/PS was used to fabricate a sta-
ble superhydrophobic surface on a glass plate. This solution
endowed the surface of the dip-coated glass with nano/micro-
scale roughness, which resulted in superhydrophobicity
(WCA = 159.5
). PASNPs can be used in academic or indus-
trial applications, such as catalysis and design of sensors.
Acknowledgment. This work was supported by the GRRC
program of Gyeonggi Province (GRRC Dankook 2014-B04,
“Development of advanced hard coating materials and proces-
sing methods”).
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