Journal of Colloid and Interface Science 337 (2009) 170–175

Contents lists available at ScienceDirect

Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

Superhydrophobicity of cotton fabrics treated with silica nanoparticles

and water-repellent agent
Geun Yeol Bae, Byung Gil Min *, Young Gyu Jeong, Sang Cheol Lee, Jin Ho Jang, Gwang Hoe Koo
School of Advanced Materials and Systems Engineering, Kumoh National Institute of Technology, Gumi 730-701, Republic of Korea

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

Article history: To obtain the superhydrophobic water-repellent cotton fabrics, cotton fabrics were treated with silica
Received 16 February 2009 nanoparticles and/or a cost-effective water-repellent agent (WR agent). Two different silica nanoparticles
Accepted 22 April 2009 were synthesized via a sol–gel process and their shapes, sizes, and compositions were characterized. It
Available online 3 May 2009
was found that silica particles are spherical and have diameters of 143 and 378 nm. For the cotton fabrics
treated with the WR agent alone, the water contact angles on the fabric surface remained lower than 20°
Keywords: at the WR agent concentration of 0.3 wt% or less. Silica nanoparticle treatment itself did not change the
Superhydrophobicity
hydrophilic surface of cotton fabric, indicating that water drops were adsorbed into fabrics due to the
Cotton fabric
Silica nanoparticle
hydroxyl groups on both cotton and silica nanoparticle surfaces. However, for the cotton fabrics treated
Water-repellent agent with both silica nanoparticles and the WR agent, a contact angle above 130° can be obtained even at the
Sol–gel process very low WR agent concentration of 0.1 wt%. Therefore, superhydrophobic cotton fabrics could be
obtained via the combined treatment of silica nanoparticle and WR agent, which is cost effective com-
pared with fluorinate silane treatment.
Ó 2009 Elsevier Inc. All rights reserved.

1. Introduction For practical applications of superhydrophobic surfaces, eco-

Since the discovery of the self-cleaning effect of such things as
lotus leaves [1–3] and insect wings found in nature [4], superhy-
drophobic surfaces have received great attention because of their
wide range of applications such as frictionless flow water pipes
[5], hydrophobic treatment on vehicle windshields [6], and super-
hydrophobic fabrics [7], etc.
It is well-known that superhydrophobic surfaces with self-
cleaning properties are caused by the water-repellent double
structures of the surfaces [2]. These hierarchical double structures
are achieved by the two physical characteristics: surface roughness
due to the micro- or nano-structures and hydrophobicity because
of waxy materials on top of the rough structures. Thus, to attain
superhydrophobic surfaces, modification of surface chemistry is al-
ways needed [8,9] in conjunction with the surface roughness.
Recently, roughened surfaces have been commonly obtained by
introducing nano-size particles onto the surface. The nano-size
particles can be synthesized easily via the sol–gel method
[10,11]. There are several kinds of inorganic nano-size particles
such as SiO2, TiO2, and ZnO [12–14]. Surface-modifying chemicals
of fluorinated silanes [15–19] or alkylated silanes [20–24] have
been used to transform the hydrophilic surface of the particles into
hydrophobic ones.
* Corresponding author. Fax: +82 54 478 7710.
E-mail address: bgmin@kumoh.ac.kr (B.G. Min).
nomical and environmental aspects in treatments of nano-size
materials and hydrophobic chemicals have become important
parameters. For instance, fluorinated silane used to create a
hydrophobic surface of the nano-size particles is too expensive
to be applied in general purpose. Furthermore, most fluorinated
materials may often cause serious risks for the human health in
case of skin contact and for the environment in case of emissions
of fluorine during and after the treatment process [25–27]. There-
fore, it is necessary to minimize the usage of fluorinated
materials.
Recently, as markets in leisure and outdoor sporting textiles
have been expanded, the needs for superhydrophobic fabrics have
increased. There have been some reports on the improvement of
hydrophobic properties of several kinds of fabrics using nano-
structures achieved by nanotechnology [7,14,28,29]. Cotton has
always been the principal clothing fabric due to its attractive
characteristics such as softness, comfort, warmness, biodegrada-
tion, and low cost. However the abundant water-absorbing hy-
droxyl groups on cotton surfaces make the fabrics absorbent
and easily stained by liquids. Therefore, additional finishes are re-
quired to impart superhydrophobicity and self-cleaning proper-
ties on cotton fabrics [14].
In the present study, we have introduced superhydrophobicity
to the hydrophilic cotton fabric by the combined treatment of silica
nanoparticles and a cost-effective commercial WR agent. Two dif-
ferent silica nanoparticles were prepared via the typical sol–gel
process and treated onto the cotton fabrics with/without the WR

0021-9797/$ - see front matter Ó 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2009.04.066
 G.Y. Bae et al. / Journal of Colloid and Interface Science 337 (2009) 170–175
agent. Surface structures and compositions of the cotton fabrics
treated with silica nanoparticles and/or the WR agent were charac-
terized by using scanning electron microscopy, particle size ana-
lyzer, energy dispersive spectroscopy, X-ray photoelectron
spectroscopy, and scanning prove microscopy. The hydrophobicity
of cotton fabrics was evaluated by measuring the contact angles of
sessile water drops on the fabrics.
2. Experimental
2.1. Materials
Tetraethyl orthosilicate [(C2H5O)4Si, TEOS], ammonium hydroxide
(NH4OH, 28 wt%), and ethanol (C2H5OH, 94 wt%) were obtained
from Samchun Chemicals (Korea), Junsei (Japan) and SK Chemicals
(Korea), respectively. All the chemicals were used as received with-
out further purification. The water used for the nanoparticle prep-
aration was purified by both ion-exchange and distillation. The
plain cotton fabric used in this work was desized and bleached.
The commercial WR agent, KF255, was supplied by Nicca Korea
and it was an emulsion consisting of perfluoroacrylate, benzyl
metharcylate, water, etc. where the solid amount of perfluoroacry-
late and benzyl metharcylate was 22.1 wt%.
2.2. Synthesis of silica nanoparticles
The spherical silica nanoparticles were prepared by the modi-
fied Stober method [30] of hydrolysis, dehydration and condensa-
tion of TEOS as a precursor. Firstly, a mixture of 0.39 mol TEOS and
2.35 mol ethanol was prepared, then it was mixed with another
mixture of 2.94 mol distilled water, 2.35 mol ethanol, and NH4OH.
Here NH4OH was used as a catalyst to control the particle size and
distribution (Table 1). The synthesis was carried out by vigorously
stirring the mixtures at 30 °C for 24 h.
2.3. Treatment of cotton fabrics with silica nanoparticles and the WR
agent
The cotton fabrics were immersed in a sol of silica nanoparticles
at 30 °C for 5 min while stirring. The wet fabrics were squeezed
using a laboratory mangle (DL-2005H, Daelim Starlet, Korea) with
a pressure 3.5 kgf/cm2 and a rate of 10 rpm, resulting in a wet-
pick-up of ca. 70%. The fabrics were then dried at 80 °C for 3 min
and cured at 160 °C for 3 min with a preheated laboratory tenter
(DL-2016, Daelim Engineering, Korea) to immobilize silica nano-
particles on the cotton fabric. A laboratory laundering machine
(DL-2002, Daelim Engineering, Korea) was used to remove the
residual silica particles not immobilized on the fabric. A standard
laundering condition, 2 g of detergents in 400 ml of distilled water
while stirring at 40 °C for 30 min, was applied (ISO 105-A01). For
the impartment of hydrophobic property to the hydrophilic cotton
fabrics previously applied with silica nanoparticles, they were im-
mersed in an aqueous solution at the WR agent concentration of
0.1–1.0 wt% at 30 °C for 5 min while stirring and then squeezed.
Subsequently the fabrics were dried and cured simultaneously at
180 °C for 3 min using a laboratory tenter. Table 2 summarizes
the fabrics treated with various conditions.
Table 1
Components and compositions for preparing silica nanoparticles.
Silica sample code TEOS (mol) NH4OH (mol) H2O (mol)
Sol 1 0.39 0.05 2.94
Sol 2 0.39 0.18 2.94
171
Table 2
Cotton fabrics treated with silica nanoparticle and/or WR agent.
Fabric sample code Silica nanoparticle WR agent
a
F(x) -COT No Yes
S1-COT Sol 1 No
S1-F(x)-COT Sol 1 Yes
S2-COT Sol 2 No
S2-F(x)-COT Sol 2 Yes
a
x denotes the concentration (wt%) of WR agent solution.
2.4. Characterization
The size and distribution of silica nanoparticles were measured
by a Zeta Potential and Particle Size Analyzer (ELS-Z2, OTSUKA) in
an ethanol solution (volume fraction of silica nanoparticles was
10%) after ultrasonication for 15 min to minimize the presence of
silica aggregates. The shape and immobilization state of silica
nanoparticles applied to cotton fabric were observed using field
emission scanning electron microscopy (FE-SEM, JEOL 6500F). A
thin platinum layer was sputtered onto the pristine and treated
cottons to improve conductivity before observation. Energy disper-
sive spectroscopy (EDS) was also used for the identification of silica
particles on the fabrics. Surface topology of silica–cotton fabric
after treatment with the WR agent was observed using a scanning
probe microscope (SPM, XE-100, Park System Co). Chemical com-
position of the fabrics before and after the treatment of the WR
agent was analyzed using X-ray photoelectron spectroscopy (XPS,
K-ALPHA, Thermo Fisher). Hydrophobic properties of the cotton
fabric surfaces were estimated by measuring contact angles using
a contact angle goniometer (DM 700, Kyowa). The measurement
of the contact angle was carried out using the sessile drop method.
The contact angle value and image were acquired 30 s after the
dropping of a distilled water drop (about 3.3 lL) on the fabrics.
More than ten readings were averaged to obtain one representative
contact angle for each sample. All the measurements were carried
out at 24 °C.
3. Results and discussion
3.1. Synthesis of silica nanoparticles
Silica nanoparticles were prepared through a typical sol–gel
process including the hydrolysis of TEOS and the condensation of
the hydrolyzed silica species in the presence of an ammonia cata-
lyst. The sol–gel reactions were as follows
(1) Hydrolysis
SiA½OC2 H5 4 þ 4H2 O ! SiAðOHÞ4 þ 4C2 H5 OH
(2) Alcohol condensation
SiAðOHÞ4 þ SiA½OC2 H5 4 ! BSiAOASiB þ 4C2 H5 OH
(3) Water condensation
SiAðOHÞ4 þ SiAðOHÞ4 ! BSiAOASiB þ 4H2 O
The synthesized silica sols exhibited slightly viscous state due
to the high concentration of nanoparticles. The reaction yield
reached >99% in both cases (Table 1). The silica nanoparticles have
partially spherical shape, as can be seen in Fig. 1. It has been known
that the size and distribution of silica nanoparticles are very
important factors in the Lotus effect. In this study, two kinds of sil-
ica sols with different particle size were prepared by changing the
EtOH (mol)
amount of NH4OH catalyst, as shown in Fig. 2. The average diame-
4.70
ters and standard deviations of the silica nanoparticles (Sol 1 and
4.70
Sol 2) were measured to be 142.5 ± 9.6 nm and 377.7 ± 16.5 nm,
172 G.Y. Bae et al. / Journal of Colloid and Interface Science 337 (2009) 170–175
Fig. 1. SEM image of the silica nanoparticles (Sol 2) synthesized via the sol–gel
process.
Fig. 2. Average size and size distribution of the silica nanoparticles: (A) Sol 1; (B)
Sol 2.
respectively. This reveals that the average diameters of the silica
nanoparticles increased with increasing amounts of NH4OH and
the silica nanoparticles have relatively narrow size distribution.
This result is consistent with the previous reports [13,30,31].
Fig. 3. SEM images of the neat and silica nanoparticle-treated cotton fabrics: (A)
neat cotton fabric; (B) S1-COT; (C) S2-COT. All the cotton fabrics treated with silica
nanoparticles were cured at 160 °C for 3 min and washed before observation.
3.2. Immobilization of silica nanoparticles on cotton fabric
It is known that immobilization of the nanoparticles on a target
surface is the major factor in obtaining the Lotus effect, which is
particularly important in textile application where laundering
durability is required. Xu and Cai [14] reported that silica can be
adhered onto cotton fiber by heat treatment, resulting in forming
the chemical bond between hydroxyl groups of cellulose and silica
 G.Y. Bae et al. / Journal of Colloid and Interface Science 337 (2009) 170–175
Fig. 4. EDS spectrum of the cotton fabric (S2-COT) treated with the silica nanoparticle of Sol 2.
nanoparticles. In the study, for the cotton fabrics immersed in the
silica nanoparticles sols and then squeezed between rollers to
maintain the constant pickup of 70% based on the fabric weight,
stable adhesion of the silica nanoparticles can be obtained by heat
treatment at 160 °C. The SEM images of the heat-treated and
washed cotton fabrics are displayed in Fig. 3. It is notable that
the uniformity and bumps of cotton fabrics treated with Sol 2 are
better and bigger than those by Sol 1. EDS and XPS spectra in Figs.
4 and 5 also support that the bumps on the cotton fabrics were
identified as silica nanoparticles.
3.3. Hydrophobicity of cotton fabrics treated by silica nanoparticle and
WR agent
It is well-known that Lotus effect requires micro- or nano-
bumps covered with hydrophobic materials. As silica is not hydro-
phobic due to abundant hydroxyl groups on its surface, it is needed
to treat the silica surface with a hydrophobic material. As men-
tioned above, there have been many reports on using alkylated
or fluorinated silanes for hydrophobication of silica [15–24]. How-
ever, the hydrophobic silane compounds have been limited in prac-
tical applications due to their high cost. Hence, instead of silanes, a
cost-effective commercial WR agent was selected as a material to
Fig. 5. XPS spectrum of the cotton fabric (S2-COT) treated with the silica
nanoparticle of Sol 2.
173
make the silica-treated cotton fabric hydrophobic. It is a hydropho-
bic agent commercialized for textiles, which has perfluoro-chemi-
cals as a main ingredient. Fig. 6 shows the SEM images of the
treated cotton fabrics. When SEM images in Figs. 3 and 6 were
compared, it is clear that the silica nanoparticles are covered with
the WR agent. The existence of WR agent on cotton fabrics was
proven by the appearance of Fluorine (F1s) peaks in XPS spectra
(Fig. 7). As expected, it was found that fluorine content of the cot-
ton fabric surfaces increased with the increment of the WR agent.
Water-repellent ability of the fabrics was analyzed by measuring
contact angles of water drops on the fabrics treated with silica
nanoparticles and/or WR agent. The contact angles were measured
in 30 s after placing the water drop on the fabrics. Fig. 8 exhibits
the changes in contact angles as a function of aqueous WR agent
concentration. Before finishing with the WR agent, the contact
angles of water sessile drops on the neat and silica-treated cotton
fabrics are almost zero, indicating that the cotton fabrics untreated
with WR agent absorbed water drops without showing any hydro-
phobicity. This result stems from the hydrophilic hydroxyl groups
on both surfaces of cotton fabric and silica nanoparticle. For the
neat cotton fabric, no significant change in contact angle was de-
tected at lower WR agent concentration of WR agent up to
0.3 wt%. It means that at those low concentrations the hydropho-
bicity of the fabric is not enough to prevent water drop from wick-
ing into the fabric by capillary force. On the contrary, the contact
angle of 130° was achieved for the silica-treated fabric (S2-COT)
at a very low WR agent concentration of 0.1 wt%. This high water
contact angle (Lotus effect) can be attributed to the synergistic ef-
fect of nano-sized bumps of silica particles and hydrophobicity of
the WR agent. As expected, the hydrophobicity increased with
increasing concentrations of the WR agent. On the other hand, it
should be noted that the increase in contact angles with the WR
agent concentration is much higher for S2-COT than S1-COT and
S2-COT with bumpier surfaces shows higher contact angles than
S1-COT, as can be seen in Fig. 8. This result is consistent with the
Cassie–Boxter theory on Lotus effect which describes that the
rougher the surface the more air-trap on the contact area between
surface and water [32]. In this study, two different SiO2 nanoparti-
cles (Sol 1 and Sol 2) were prepared by changing the amount of
NH4OH at the same concentration of other components of TEOS,
H2O and EtOH, as listed in Table 1. The size ratio and volume ratio
between Sol 1 and Sol 2 are evaluated to be 1:2.65 and 1:18.6,
respectively, from the SEM data that the average diameters of Sol
1 and Sol 2 nanoparticles were142.5 and 377.7 nm, respectively.
It means that the number of Sol 1 nanoparticle is much larger than
174 G.Y. Bae et al. / Journal of Colloid and Interface Science 337 (2009) 170–175

Fig. 7. XPS spectrum of the cotton fabric treated with the silica nanoparticle of Sol 2
followed by the WR agent: (A) S2-F(0.1)-COT; (B) S2-F(0.5)-COT.

180

160

140
Contact angle (degree)

120

100

80

60

40
Neat cotton
20
S1-COT
S2-COT
0
Fig. 6. SEM images of the cotton fabrics treated with the silica nanoparticles and/or
WR agent, as listed in Table 2: (A) F(0.1)-COT: (B) S2-F(0.1)-COT: (C) S2-F(0.5)-COT.
All samples were washed before observation. 0.0 0.2 0.4 0.6 0.8 1.0
Concentration of water-repellent agent (wt%)

that of Sol 2 by 18.6 times. Therefore, S1-COT, which is the cotton
fabric treated with much higher number of smaller Sol 1 nanopar-
ticles, exhibited less surface roughness than S1-COT, as can be seen
in Fig. 3. Ling et al. [33] reported that a close-packed silica layer is
not good to obtain that superhydrophobic surface than a moder-
ately dense silica layer. Therefore, it is valid to conclude that the
higher water contact angles of S2-COT stem from the higher sur-
Fig. 8. Effects of the silica nanoparticles and the WR agent on the contact angles of
water drops on the cotton fabrics.
face roughness, compared with the close-packed and less rough
surface structure of S1-COT.
In the case of S2-COT, the contact angle did not increase signif-
icantly as the concentration of the hydrophobic agent increased
 G.Y. Bae et al. / Journal of Colloid and Interface Science 337 (2009) 170–175 175

NH4OH catalyst. For the cotton fabrics treated with silica nanopar-
ticles of average diameter 378 nm, water contact angles above
130° could be easily obtained even with a very low WR agent con-
centration of 0.1 wt% at which no hydrophobicity was exhibited for
the neat cotton fabric treated with the WR agent only. Overall, it is
considered that the combined treatment of silica nanoparticles and
cost-effective WR agent can be a practical process to obtain cotton
fabrics with superhydrophobicity.

Acknowledgments

This research was financially supported by the Ministry of Com-

merce, Industry and Energy (MOCIE) and Korea Industrial Technol-
ogy Foundation (KOTEF) through the Human Resource Training
Project for Regional Innovation.

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