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A facile method to fabricate superhydrophobic cotton fabrics

Article  in  Applied Surface Science · November 2012

DOI: 10.1016/j.apsusc.2012.08.055

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 Applied Surface Science 261 (2012) 561–566

Contents lists available at SciVerse ScienceDirect

Applied Surface Science

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

A facile method to fabricate superhydrophobic cotton fabrics

Ming Zhang, Shuliang Wang, Chengyu Wang ∗ , Jian Li
College of Materials Science and Engineering, Northeast Forestry University, 26 Hexing Road, Harbin 150040, China

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

Article history: A facile and novel method for fabricating superhydrophobic cotton fabrics is described in
Received 4 April 2012 the present work. The superhydrophobic surface has been prepared by utilizing cationic poly
Received in revised form 16 August 2012 (dimethyldiallylammonium chloride) and silica particles together with subsequent modification of
Accepted 16 August 2012
(heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane. The size distribution of silica particles was mea-
Available online 25 August 2012
sured by Particle Size Analyzer. The cotton textiles before and after treatment were characterized
by using scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The wet-
Keywords:
ting behavior of cotton samples was investigated by water contact angle measurement. Moreover, the
Superhydrophobic
Layer-by-layer self-assembly deposition
superhydrophobic durability of coated cotton textiles has been evaluated by exposure, immersion and
Cotton fabrics washing tests. The results show that the treated cotton fabrics exhibited excellent chemical stability
Poly-DMDAAC aqueous solution and outstanding non-wettability with the WCA of 155 ± 2◦ , which offers an opportunity to acceler-
Silica nanoparticles ate the large-scale production of superhydrophobic textiles materials for new industrial applications.

© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Lots of fancy biological organisms in nature exhibit special sur-
face wettability, such as the self-cleaning property of lotus leaves
[1], the superior ability to float on the water of water striders [2],
the directional adhesion of butterfly wings [3] and the antifogging
functionality of mosquito eyes [4]. However, almost all of these fas-
cinating properties are attributed to not only their intrinsic material
properties but also their two dimensional hierarchical structure
ranging from micrometer-scale papilla to nanometer-scale gran-
ules [5]. Taking their inspiration, the specific hierarchical structure
of superhydrophobic materials should include the substrate, first
layer of protrusions (micro-scale), second layer of protrusions
(nano-scale), and final layer of low surface energy molecules [6–8].
So far, many efforts including etching technique [9], layer-by-layer
(LbL) self-assembly [7,10], lithographic patterning [11], electrode-
position [12,13], polymer-phase separation [14], sol–gel methods
[15], solvothermal technique [16], chemical vapor deposition [17]
and others have been carried out for attaining the superhydropho-
bic surfaces.
Superhydrophobic surface with the water contact angle (WCA)
larger than 150◦ is relevant in a wide range of applications such
as enhanced corrosion resistance, transparent and antireflective
coatings, functional textiles of special wettability, anti-freezing,
anti-fog and anti-snow to antennas and windows and bio-inspired
∗ Corresponding author.
E-mail address: wangcy@nefu.edu.cn (C. Wang).
aquatic materials and devices [6,18], etc. With the development
of textiles market in leisure and outdoor sporting, the needs for
water-repellent fabrics have dramatically increased. As a type
of soft, comfortable, warm, biodegradable and low cost textiles,
cotton fabrics have been selected to be the principal clothing
fabrics. However, the cotton fabrics can be easily wetted and
stained by liquids due to the abundant hydroxyl groups on its
surface [19]. Therefore, numerous fundamental researches and
practical applications have been devoted to change the cotton
wettability.
Xu et al. fabricated the superhydrophobic surface on cot-
ton fabrics by combining the surface roughness created by
silica nanoparticles and zinc oxide nanorods and low sur-
face energy modified by DTMS [20]. Qi et al. described an
inexpensive, facile and low-temperature route for the superhy-
drophobic brocades by growing c-axis oriented ZnO nanorods
on their surface [21]. Cotton fabrics grafted by 1H,1H,2H,2H-
nonafluorohexyl-1-acrylate under simultaneous radiation-induced
graft polymerization, which showed stable superhydrophobicity,
had been synthesized by Deng et al. [22]. Bae et al. pre-
pared superhydrophobic cotton fabrics by the combination of
the silica nanoparticles and a cost-effective water-repellent agent
[19]. In the present work, we report a facile, novel and feasi-
ble approach to superhydrophobic cotton fabrics. Typically, the
superhydrophobic cotton was synthesized by the layer-by-layer
self-assembly deposition of cationic poly (dimethyldiallylammo-
nium chloride) and negative charged silica particles, followed
with the modification of (heptadecafluoro-1,1,2,2-tetradecyl)
trimethoxysilane.

0169-4332/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2012.08.055
562 M. Zhang et al. / Applied Surface Science 261 (2012) 561–566
F FF FF F F F
O O
Si O
F in Fig. 2. The anionic cotton fabric was immersed in the prepared
F FF FF FF F
Fig. 1. Molecular structure of (heptadecafluoro-1,1,2,2-tetradecyl)trimeth-
oxysilane.
2. Experimental
2.1. Materials
The reagents employed for silica particles synthesis includ-
ing tetraethyl orthosilicate (TEOS) (98.0%), ammonium hydroxide
(NH4 OH) (27.0%), and ethanol (99.7%), were purchased from
Tianjin Kermel Chemical Reagents Development Centre, Tian-
jin Kaitong Chemical Reagent Co., Ltd and Tianjin Guangfu
Technology Development Co., Ltd, respectively. The aqueous solu-
tion of poly (dimethyldiallylammonium chloride) (poly-DMDAAC)
with the mass fraction of 40.0% was obtained from Shan-
dong. (Heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane with
the molecular formula of C13 H13 F17 O3 Si, as described in Fig. 1,
was obtained from Sicong New Material Development Co., Ltd.
Methanol (99.5%) was purchased from Tianjin Xinbote Chemical
Co., Ltd. All of the chemicals were used as received without further
purification. The de-ionized water was prepared locally, and the
commercial cotton fabrics were purchased from Harbin. Before the
experiment, the cotton fabrics were respectively purified by ultra-
sonic washing with acetone, ethanol, distilled water and de-ionized
water for 5 min, and then completely dried at 75 ◦ C.
2.2. Synthesis of silica particles
The silica particles were prepared by a sol–gel process. Con-
cisely, TEOS (5 mL) was hydrolyzed to form silica particles in
ethanol (45 mL) with NH4 OH (5 mL) as the catalyst at 40 ◦ C for
6 h. Followed the reaction products were collected and purified by
absolute ethanol for several times, and dried at 40 ◦ C in a preheated
oven. The as-obtained silica particles were hydrophilic due to the
plenty hydroxide groups on their surfaces.
2.3. Fabrication of silica-coated cotton fabrics
One gram poly-DMDAAC aqueous solution was dispersed in
20 ml de-ionized water, meanwhile, 0.2 g silica particles were ultra-
sonically dispersed in 20 ml de-ionized water for 10 min. Then we
will describe two experimental procedures to fabricate the silica-
coated cotton fabrics.
Fig. 2. Experimental strategy for the fabrication of multilayer films assembling on cotton fabric surface.
First, the silica-coated cotton fabric was prepared by layer-by-
layer self-assembly technology which has two main steps as shown
poly-DMDAAC solution for 20 min to render the charge of sub-
strate, followed by rinsing with de-ionized water for 1 min. Then
the cationic fabric was immersed in the solution of electronega-
tive silica particles for 10 min, followed by rinsing with de-ionized
water for 1 min. By repeating the two steps twice, the multilayer
films with poly-DMDAAC and silica particles were formed on cotton
fabric surface. Second, we prepared the silica-coated cotton fab-
ric by a simple deposition method. In detail, the cotton fabric was
immersed in the silica particles solution for 20 min, and then rinsed
with de-ionized water for 1 min.
2.4. Modification of silica-coated cotton fabrics
In the typical reaction, the as-obtained silica-coated cot-
ton fabrics were modified by (heptadecafluoro-1,1,2,2-tetradecyl)
trimethoxysilane as detailed in Fig. 3. The cotton samples were
immersed in a solution of (heptadecafluoro-1,1,2,2-tetradecyl)
trimethoxysilane (1%, m/v in methanol) at ambient temperature for
1 h, followed by rinsing with methanol and drying with N2 at ambi-
ent temperature. Subsequently, the two types of modified cotton
fabrics were kept in an oven at 60 ◦ C for 24 h.
2.5. Characterization
The surface morphology of cotton samples was characterized
by using scanning electron microscopy (SEM, FEI QUANTA200).
The size distribution of silica particles was measured by a Zeta
Potential and Particle Size Analyzer (Brookhaven, ZetaPALS) in de-
ionized water (volume fraction of silica particles was 0.4%) after
ultrasonic treatment for 15 min to minimize the presence of sil-
ica aggregates. The chemical composition of samples surfaces was
analyzed by using X-ray photoelectron spectroscopy (XPS, Ther-
mofisher Scientific Company, K-Alpha). The measurement of water
contact angle (WCA) was carried out by using a commercial con-
tact meter (Powreach, JC2000C) at ambient temperature, and the
WCA was determined by averaging the measurements taken from
five different positions on cotton samples with the water droplet
of 5 ␮L.
3. Results and discussion
3.1. Synthesis of silica particles
The silica particles were prepared by a typical sol–gel pro-
cess including the hydrolysis of TEOS and the condensation of
 M. Zhang et al. / Applied Surface Science 261 (2012) 561–566
Fig. 3. Experimental strategy for the modification of silica-coated cotton fabric sur-
face.
hydrolyzed silica species [15]. As we all know, the size distribution
of silica particles is very important to the Lotus effect. Therefore, in
this study, the reaction temperature and the amount of NH4 OH to
synthesize silica particles were strictly controlled according to the
well-known Stober method. The average diameter of as-obtained
silica particles is 266.7 nm, and the majority of particles have a
typical diameter of 250–300 nm as shown in Figs. 4 and 5, dis-
playing their favorable size distribution and monodispersity, which
play the vital roles in forming the nanometer-scaled roughness for
fabricating superhydrophobic films on cotton fabric surface.
3.2. Surface morphology of cotton fabrics
The geometric microstructure of the cotton surfaces before and
after treatment has been examined by using scanning electron
microscopy (SEM). From the SEM image of pristine cotton fabric
at low magnification (Fig. 6a), we can clearly observe the weave
structure and a lot of protruding fibers. In the high magnification
100
Mean Diam. 266.7
80
60
Volume
40
20
208.3
0 more peaks of F1s and FKLL appear in the XPS spectrum of super-
210 220 230 240 250 260 270 280 290 300
Diameter(nm)
Fig. 4. The size distribution of silica particles in de-ionized water.
563
Fig. 5. SEM image of pure silica nanoparticles at high magnification.
image (Fig. 6b), there are many native striations along the fiber, and
numerous interspaces among the highly intertwined fibers with the
diameters arranging from 10 ␮m to 20 ␮m, displaying the com-
parative microroughness of pristine cotton surface. Importantly,
the single fiber in Fig. 6c was densely and uniformly covered by
the silica spheres when the cotton surface was assembled with
poly-DMDAAC/SiO2 , but few silica spheres appeared on the cot-
ton fibers in the absence of poly-DMDAAC (Fig. 6d). It indicates
that the cationic poly-DMDAAC could uniformly attach to the cot-
ton surface, and enhance the adhesion between the anionic silica
spheres and the anionic fiber surface via electrostatic interaction.
To our knowledge, the arrangement of silica spheres creates
numerous interspaces or cavities between each sphere, which can
roughen the cotton surface in nanometer-scale. With the compari-
son between Fig. 6c and d, the presence of poly-DMDAAC obviously
accelerated the formation of nano-roughness on cotton surface. In
the literatures, the artificial superhydrophobic surfaces are usu-
ally accomplished by developing the dual-scale roughness and
tuning the surface energy, and hierarchical roughness can make
the superhydrophobicity of materials more stable [23,24]. Conse-
quently, with the combination of surface dual-scale roughness and
the layer of (heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane,
the treated cotton surface in the presence of poly-DMDAAC cannot
be wetted by water droplet and presents relatively stable superhy-
drophobicity with the WCA of 155 ± 2◦ .
3.3. Surface chemical composition
In this work, X-ray photoelectron spectroscopy (XPS) was
employed to characterize the chemical compositions of the coating
on cotton surface. Fig. 7a represents the XPS spectrum of the mul-
tilayer film prepared by layer-by-layer self-assembly technique,
where five sharp peaks corresponding to Si2p, Si2s, C1s, N1s and
O1s can be clearly observed. Except for the XPS peaks of Si2p, Si2s
and O1s corresponding to the pure silica, two new peaks of C1s
and N1s demonstrate the existence of poly-PMDAAC. It indicates
that the silica particles have adhered to the cotton fabric surface in
the presence of poly-DMDAAC by electrostatic interaction, which
has been verified by using quartz crystal microbalance (QCM) in
the doctoral dissertation of Zhang [25]. Compared with Fig. 7a, two
hydrophobic multilayer film (Fig. 7b), which demonstrates that the
hydrolyzed (heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane
has grafted on the multilayer film successfully.
564 M. Zhang et al. / Applied Surface Science 261 (2012) 561–566

Fig. 6. SEM images of pristine cotton fabric at (a) low and (b) high magnification; (c) superhydrophobic cotton fabric; (d) modified cotton fabric in the absence of poly-DMDAAC.

3.4. Surface wettability water droplets was reported. Fig. 8 shows the shapes of water
droplets on pristine cotton surface, silica-coated cotton surface,
The surface wettability is measured by the contact angle (CA) of superhydrophobic cotton surface, and modified cotton surface
liquid on the solid surface, and the CA is determined by the inter- without poly-DMDAAC. From Fig. 8a, it can be seen that the
actions across the three (vapor/liquid, vapor/solid and solid/liquid) pristine cotton fabric can be immediately wetted by the water
interfaces. However, it is noteworthy that the reliable determina- droplet, the outstanding hydrophilicity of which is attributed to
tion of cotton fabric baseline for the CA measurement is impossible the abundant hydroxyl groups and numerous holes in its woven
due to the macroscopic weave structure of textiles and the pres- structure. As shown in Fig. 8b, the WCA is nearly 0◦ for the
ence of protruding fibers [26]. Thus, only the CA interval for 5 ␮L silica-coated cotton fabric due to the presence of hydroxyl and
alkoxy groups on silica particles. Interestingly, when the cotton
O1s fabric was assembled with poly-DMDAAC/SiO2 and grafted by
(heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane, the water
F1s droplet could keep spherical and float on its surface with the max-
imum WCA of 157◦ (Fig. 8c). However, the WCA on the modified
b F KLL sample in the absence of poly-DMDAAC was 147◦ only (Fig. 8d),
C1s which cannot meet the standard of superhydrophobicity. These
Si2p Si2s
N1s observations indicate the importance of surface roughness and low
surface energy materials for the elaboration of superhydrophobic
cotton fabric. More importantly, it can be confirmed that the pres-
O1s ence of poly-DMDAAC not only accelerated the formation of surface
roughness but also increased the WCA on cotton sample, which is
in compliance with Cassie–Baxter theory [27].
C1s
a Si2p Si2s
N1s 3.5. Long-term stability of modified cotton fabrics

Durability of superhydrophobic cotton fabrics is an important

0 200 400 600 800 1000 1200 1400
aspect that needs to be investigated for industrial applications.
Binding Energy (ev)
Thus, we had evaluated the performance of superhydrophobic cot-
Fig. 7. XPS spectra of the treated cotton surfaces: (a) multilayer films; (b) superhy- ton fabric after exposure to ambient air for one month, being
drophobic multilayer films. immersed in tap-water for 24 h, or machine washing test according
 M. Zhang et al. / Applied Surface Science 261 (2012) 561–566 565

Fig. 8. Water droplet on (a) pristine cotton fabric (t < 1 s); (b) cotton fabric covered by multilayer films (t < 1 s); (c) superhydrophobic cotton fabric (t > 1 min); (d) modified
cotton fabric in the absence of poly-DMDAAC (t > 1min).

Fig. 9. A direct test of waterproof capability: (a) superhydrophobic cotton fabric immersed in tap-water; (b) treated and untreated cotton fabrics placed in tap-water; (c)
treated and untreated cotton fabrics removed from tap-water after a full immersion.
566 M. Zhang et al. / Applied Surface Science 261 (2012) 561–566
Fig. 10. SEM image of superhydrophobic cotton fabric after delicate washing test.
The inset of figure is the photograph of water droplet on the superhydrophobic
cotton fabric after washing test.
to ISO 6330:2000 [28]. Fortunately, the superhydrophobic cotton
sample after exposure test had no visible change, and the WCA
was still greater than 150◦ . In addition, as shown in Fig. 9a–b,
the superhydrophobic cotton could hardly immerse into the tap-
water and always float on the tap-water. However, the pristine
cotton was immediately drenched and sunk to the bottom of beaker
when it was placed in tap-water. From Fig. 9c, we can find that
the cotton surface after immersion test was completely dry, which
presents an outstanding water repellency. Unfortunately, after the
washing cycle, the certain mechanical and chemical degradation
have happened to the superhydrophobic cotton fabric. As shown
in the image of superhydrophobic cotton fabric after washing test
(Fig. 10), the dense and uniform silica coating has been damaged,
and the WCA got a decrease as well, which indicates that the
mechanical stability of silica coating still needs to be improved.
However, the WCA of the sample surface after washing is 149◦ ,
still displaying an outstanding water repellent property. Appar-
ently, the cotton fabric covered by silica multilayer with subsequent
modification of (heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysi-
lane possesses a very excellent superhydrophobic stability, which
is significant for future industrial applications.
4. Conclusion
As summary of this study, we have demonstrated a simple,
facile, novel and feasible procedure for generating superhydropho-
bic cotton fabric, which offers an opportunity to accelerate the
large-scale production of superhydrophobic textiles materials for
new industrial applications. The superhydrophobicity of treated
cotton fabrics surfaces in our study could be explained by the
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combination of two effects: firstly, the effect of the roughness
created by layer-by-layer self-assembly deposition of cationic poly-
DMDAAC and silica particles; and secondly, the contribution of
a hydrophobic layer coated on the surface during silanization by
(heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane molecules.
After the superhydrophobic treatment, the wettability of cot-
ton fabric has been transformed from superhydrophilicity to
superhydrophobicity with the WCA of 155 ± 2◦ . Importantly, the
superhydrophobic cotton fabric presents a very excellent stabil-
ity, even though it was undergoing the exposure, immersion and
washing tests.
Acknowledgments
This research was supported by Program for New Century Excel-
lent Talents in University (NCET-10-0311) and the National Natural
Science Foundation of China (31000271).
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