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Surface & Coatings Technology 276 (2015) 1622

Contents lists available at ScienceDirect

Surface & Coatings Technology


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

Fabrication of superhydrophobic uorine-free lms on cotton fabrics


through plasma-induced grafting polymerization
of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane
Yan Zhang a, Yongqiang Li a,b,, Jianzhong Shao a,b, Chao Zou a
a
b

Engineering Research Center for Eco-Dyeing & Finishing of Textiles, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, China
Textile Fiber Materials And Processing Technology Local Joint National Engineering Laboratory, Zhejiang Sci-Tech University, Hangzhou 310018, China

a r t i c l e

i n f o

Article history:
Received 16 May 2015
Revised 19 June 2015
Accepted in revised form 21 June 2015
Available online 24 June 2015
Keywords:
Superhydrophobic surface
Cotton fabric
Air low-temperature plasma
Grafting polymerization
D4Vi
Heat resistance

a b s t r a c t
A facile and cost-effective technique was designed to construct uorine-free superhydrophobic lms on cotton
fabrics in the present paper. Superhydrophobic lms were fabricated by immersing cotton fabrics in the monomer solution of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (D4Vi) and followed by the treatment of
the air low temperature plasma with glow discharge at a pressure of 10 Pa. The cotton fabrics before and after the
plasma treatment were characterized by eld emission scanning electron microscopy (FESEM), infrared spectroscopic analysis (FTIR), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), and
thermogravimetric analysis (TGA). The wetting behavior of the cotton fabrics was evaluated by the water contact
angle (WCA) measurement. The results showed that polymer lms could be coated on the cotton bers through
the plasma induced grafting polymerization of D4Vi. The glow discharge power and the treating time of lowtemperature plasma were critical to the grafting polymerization of D4Vi to the cotton fabrics. Moreover, the treated cotton fabric demonstrated an extraordinary superhydrophobicity with a WCA more than 150 for a 5 L
water droplet and excellent thermal stability and durability of washing 30 cycles.
2015 Elsevier B.V. All rights reserved.

1. Introduction
The superhydrophobic phenomenon is widespread in nature, such as
lotus leaf effect [1]. The excellent features of self-cleaning and anti-stain of
superhydrophobic surfaces have drawn intensive attention in the past
years [2]. Inspired by the microstructure of lotus leaves, construction of
rough surfaces with a sophisticated micro/nanostructure and a low surface energy is the main strategy to fabricate superhydrophobic surfaces
with a water contact angle larger than 150 [3].
Currently, superhydrophobic lms are widely used in selfcleaning coatings, oil/water separation materials, and functional
textiles with a special wettability [4]. Cotton fabric, as a principal
and popular clothing material, has excellent comfort, softness and
biodegradability [5]. However, the cotton fabric is easily soaked
and stained by liquids due to the abundant hydroxyl groups on its
surface [6]. Typically, many novel methods have been designed to
prepare superhydrophobic cotton fabrics, such as solgel, chemical
vapor deposition, and Layer-by-Layer assembly technique [7].
Recently, plasma technique has been proved to be a very promising

Corresponding author at: Engineering Research Center for Eco-Dyeing & Finishing of
Textiles, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, China.
E-mail address: yqqli@163.com (Y. Li).

http://dx.doi.org/10.1016/j.surfcoat.2015.06.050
0257-8972/ 2015 Elsevier B.V. All rights reserved.

approach to functionalize various substrates though taking advantage of the highly reactive plasma species. The surface chemistry
and roughness may be tuned simultaneously, which makes it possible to fabricate superhydrophobic surfaces in a one-step process [8].
Low-pressure plasma and atmospheric plasma processing technologies have been commonly used for surface modication and graft

Fig. 1. Molecular structure of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane.

Y. Zhang et al. / Surface & Coatings Technology 276 (2015) 1622

17

Fig. 2. Schematic representation of the structure of the plasma apparatus.

polymerization [9]. Active particles can be produced at low pressure


through the generation of the glow discharge plasma. The active particles have a relatively strong capability to induce surface modication
and graft polymerization on a substrate [10]. In comparison to conventional wet chemical modication techniques, plasma surface modication is a simple, efcient, and cost-effective dry technique without the
use of a large amount of water and chemicals [11,12]. Therefore, this
technique is benign to the environment. In addition, the lms formed
by the plasma induced grafting polymerization may display controllable
thickness, composition uniformity, dense membrane, and less pinhole.
Therefore, the plasma-induced grafting polymerization technique has
been used to prepare a variety of lms, like metals lms, amorphous inorganic lms, and organic lms [13].
In the present paper, we reported a simple and uoride-free method
to prepare superhydrophobic cotton fabrics though constructing lms
with a sophisticated micro/nanostructure and a low surface energy via
air glow discharge plasma grafting polymerization with 1,3,5,7tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (D4Vi) at the low
pressure. The superhydrophobic lms were formed due to polymerization with the vinyl of D4Vi by the plasma. More importantly, even after
30 cycles of washing, the treated cotton fabrics can still keep excellent
hydrophobicity.

2. Experimental section
2.1. Materials and devices
Desized, scoured, and bleached woven cotton fabrics (32 branch
twill cotton fabric and 100% cotton) were supplied by Esquel Textile
Industrial Co. Ltd (Guangdong, China). The fabrics were washed by
absolute ethanol (99.7%) supplied by Hangzhou Gaojing Fine Chemical
Co. Ltd (Zhejiang, China) and distilled water for 5 min and were dried
in an oven at 80 C prior to use. Air (99.5%) was supplied by Hangzhou
Electrochemical Group Co. Ltd. Detergent 209 was purchased from
Nanjing East Mu Fine Chemical Co. Ltd (Jiangsu, China). D4Vi (90%,
CAS#27342-69-4) was purchased from Zhejiang Quzhou Jun Shun
silicone Co. Ltd (Zhejiang, China). The molecular structure of 1,3,5,7tetravinyl-1,3,5,7-tetramethylcyclotetr-asiloxane was showed in Fig. 1.
The low-temperature plasma was produced by a conventional radio
frequency (RF) capacitance coupling plasma device (Model: HD-1A,
Changzhou Changtai Plasma Technology Development Ltd.) with a
frequency of 13.56 MHz and the RF power continuously adjusted from
0 W to 500 W. The reaction chamber was a hard glass cylinder
withstanding high temperatures with a size of 230 mm 250 mm. A
schematic representation of the plasma device is shown in Fig. 2.

Fig. 3. Fabrication process of superhydrophobic cotton fabric treated with air LT-plasma.

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Y. Zhang et al. / Surface & Coatings Technology 276 (2015) 1622

Fig. 4. FESEM images of the surfaces of the cotton fabrics: (a) control sample (100); (b) control sample (2000); (c) treated sample (2000, 80 W, 2 min); (d) treated sample (2000,
120 W, 2 min), (e) treated sample (2000, 80 W, 5 min); (f) treated sample (2000, 80 W, 7 min).

2.2. Fabrication process


The cotton fabric in a size of 5 cm 5 cm was immersed in D4Vi for
30 min and dried at room temperature. The grafting polymerization

reaction with air was carried out on a LT-Plasma equipment operating


at a RF power from 60 W to 160 W and time value from 2 min to
10 min (Fig. 2). The working pressure was kept constant at about
10 Pa. The treated cotton fabrics were immersed in absolute ethanol

Fig. 5. Photographs of cotton fabrics: (a) water drops on the control and treated samples (80 W, 2 min); (b) the treated sample on the surface of water.

Y. Zhang et al. / Surface & Coatings Technology 276 (2015) 1622

19

Fig. 6. (a) The curve of treated time of the plasma-induced graft polymerization of D4Vi onto the weight uptake of cotton fabrics; (b) the curve of RF power of the plasma-induced graft
polymerization of D4Vi onto the weight uptake of cotton fabrics; (c) the relationship of the contact angle on the mass uptake of cotton fabrics which are graft polymerized with D4Vi;
(d) stability of the water contact angle on the treated cotton fabrics.

for 20 min, then sufciently washed with distilled water for 5 min and
dried in an oven at 80 C before being weighed. The fabrication process
of the superhydrophobic cotton fabrics through the low-temperature
plasma is shown in Fig. 3.

The amount of the grafted polymers was determined through


measuring the weight difference between the cotton fabrics before
and after plasma-induced grafting polymerization. The mass uptake
was calculated using Eq. (1).

2.3. Instruments and characterization

G m1 m0 =m0   100%

The surface morphology of the control and treated cotton fabrics was
observed on a eld emission scanning electron microscopy (FESEM,
Ultra55, Zeiss, Germany) with a resolution of 1.7 nm. The accelerating
voltage was 1 kV. Simultaneously, the elemental composition and the
elemental relative weight of the samples were measured by Energy
dispersive X-ray spectroscopy (EDX). The variation of the functional
groups during the plasma treatment was monitored through Fourier
infrared spectroscopy (FTIR, Vertex70, Bruker company, Germany).
The spectra were recorded in the range of 4000400 cm1 with a
resolution of 4 cm1. The surface chemical composition of cotton fabrics
was analyzed by using X-ray photoelectron spectroscopy (XPS, K-Alpha,
Thermo Scientic Company). The thermogravimetric analysis (TGA) of
the samples was performed under a continuous argon atmosphere on
a Perkin Elmer (USA) Pyris1 analyzer. The samples were scanned from
20 C to 750 C at a heating rate of 20 Cmin1. The hydrophobicity
was evaluated by measuring the contact angle of samples through
sessile drop method on a contact angle measurement (Model: DSA20,
Krss, Germany) at ambient temperature. The volume of water droplets
was 5 L. The water contact angle (WCA) of the samples was
determined as the average of ve measurements at different positions
on the samples. The washing durability was measured according to
AATCC 22-1997 standard. The cotton fabric samples were washed for
5 min each cycle by the conditions as detergent 209 1 g/L, bath ratio
1:30, temperature 40 C in oscillation water-bath pot and then dried
at 80 C.

where G is the mass uptake of the cotton fabrics before and after the
plasma treatment; and m0 and m1 are the weight of the control and
treated cotton fabrics, respectively.

3. Results and discussion


3.1. Effects of the grafting polymerization on the surface morphology of
cotton fabrics
The surface microstructures of the control and treated cotton fabrics
were observed by FESEM. As shown in Fig. 4a, the control cotton fabric
displayed a regular weave structure accompanying with a lot of
protruding bers on its surface. At a higher magnication, many native
strips along the bers and numerous interspaces among the highly
intertwined bers with the diameters varied from 12 m to 16 m
were observed in Fig. 4b. It means the control cotton fabric has a
relatively rough surface in the micrometer scale. The cotton fabric was
coated by a dense and uniform lm through the air low pressure plasma
with a RF power of 80 W for 2 min (Fig. 4c). The lm may cover a single
ber or multiple bers of the cotton fabrics. All the results indicate that a
polymer lm has been successfully formed on the cotton fabric through
the low-temperature plasma induced grafting polymerization of D4Vi. A
dense and uniform thin lm could also be formed on the surface of
cotton fabric when the RF power was increased to 120 W (Fig. 4d) or
the treatment time is prolonged to 5 min (Fig. 4e). It should be pointed

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Y. Zhang et al. / Surface & Coatings Technology 276 (2015) 1622


Table 1
Atomic concentration of the control and treated cotton fabrics by XPS.

Fig. 7. FTIR-ATR spectra of D4Vi (a), the control cotton fabric (b), and the treated samples
(c) 80 W and 2 min; (d) 80 W and 5 min; and (e) 80 W and 7 min).

out that many small particles and some bulk objects could also been
found on the lm surface. We believe that they are also the reaction
products of D4Vi polymerization. When the treatment time of the lowtemperature plasma was increased to 7 min, the lms covering the
ber surfaces slough fractionally, probably caused by etching of active
particles produced by the low pressure glow discharge plasma [14]. Furthermore, the longer the plasma-treated time, the more serious the
etching effect is [15].
3.2. Surface wettability analysis
Surface wettability was evaluated by WCA measurements on the
surfaces of the cotton fabrics. The photographs of water drops on control

Sample

Treatment condition

Atomic concentration/%
C1s

O1s

Si2p

O/C

Si/C

S0
S1
S2
S3

Control
80 W, 2 min
80 W, 5 min
80 W, 7 min

69.70
65.1
63.32
63.99

30.30
18.03
19.34
19.22

0
16.87
17.34
16.79

0.43
0.28
0.30
0.30

0
0.26
0.27
0.26

and treated cotton fabrics are shown in Fig. 5a. We can see that the
water droplet was soaked by the control cotton fabric within 60 s. Exhilaratingly, the cotton fabric treated by the low-temperature plasma with
a RF power 80 W for 2 min displayed a superhydrophobicity with a WCA
of 150. The treated cotton fabric could oat on the water surface for a
long time (Fig. 5b), indicating that the fabric has excellent water repellency after coated the polymers through the plasma-induced grafting
polymerization of D4Vi.
The curve of treated time of the plasma-induced graft polymerization of D4Vi onto the weight uptake of cotton fabrics at the RF power
of 80 W is shown in Fig. 6a. With the increase of the treated time,
more polymers were produced through low-temperature plasmainduced grafting polymerization of D4Vi, leading to the increase of the
mass of the treated cotton fabrics. The cotton fabric treated for 5 min
reaches a maximum value of 3.83%. However, the mass uptake will decrease when the treated time increases longer than 5 min because the
polymer lms of the cotton fabrics would be fractured by the active particles after the complete conversion of D4Vi with a long treated time as
shown in Fig. 4f. The inuence of the plasma RF power on the WCAs
displayed an analogue trend (Fig. 6b). The concentration of active particles in the reaction system depends on the plasma RF power [16,17].
With the increase of the plasma RF power, more active particles will
be produced to induce more D4Vi to undergo the grafting polymerization. Therefore, more polymers were produced with the increase of
the plasma RF power, leading to the increase of the mass of the treated
cotton fabrics. Simultaneously, the polymer lms may be fractured with
a large plasma RF power due to the presence of the excessive active particles. The fragments of the polymer lms would be removed in the
washing process, leading to the decrease of the mass of the treated cotton fabrics. Furthermore, the defects of the polymer lms may lead to
the exposure of the raw cotton bers, resulting in the decrease of the
WCAs. The curve indicates that the WCA of the treated cotton fabric
quickly increases with growing mass uptake and nally exceeds 150
after the mass uptake is greater than a certain value as shown in
Fig. 6c. It will be identied as the required mass uptake of 2.65% in
order to achieve superhydrophobicity for cotton. Stability of the water
contact angle on the treated cotton fabrics is shown in Fig. 6d, the
water contact angle values are nearly constant, and the size of the droplet does not decrease signicantly for 540 s. This result indicates that the

Fig. 8. XPS spectra of the control (a) and (b) plasma treated cotton fabrics (80 W, 2 min).

Y. Zhang et al. / Surface & Coatings Technology 276 (2015) 1622

21

Fig. 9. EDX spectra of the control (a) and (b) treated cotton fabrics (80 W, 2 min) by the plasma.

cotton fabrics have excellent hydrophobicity stability by the plasma


grafting polymerization with D4Vi.

3.3. FTIR analysis


The FTIR spectra of D4Vi, control and the low-temperature plasma treated cotton fabrics are shown in Fig. 7, respectively. The
spectrum of D4 Vi in Fig. 7a shows a strong band around
1054 cm 1 corresponding to SiOSi stretching, a band at
1260 cm 1 belonging to CSi stretching, and bands in the spectral
range of 700800 cm 1 belonging to CSi deformation vibration.
Additionally, the characteristic bands belonging to vinyl groups at
3062 cm 1 and 3016 cm 1 (CH stretching vibrations), at
1596 cm 1 (C_C stretching vibrations), as well as at 1016 cm 1
and 953 cm 1 ( CH bending vibrations) could also been found in
the FTIR spectrum of D4 Vi [18]. The broad band around
3330 cm 1 in the FTIR spectrum of the control cotton fabric could
be assigned to hydroxyl group ( OH) and the characteristic double
peak in 1054 cm 1 and 1026 cm 1 could be assigned to the COC
stretching (Fig. 7b) [19]. The new peaks at 1596 cm 1, 1256 cm 1
and 1048 cm 1 corresponding to C_C, CSi, and SiO bands [20],
respectively, appeared in the spectra of the treated cotton fabrics
(Fig. 7ce). The intensity of the hydroxyl groups in the FTIR spectra
of the treated samples decreased (Fig. 7c, d, and e). A new peak at
about 1596 cm 1 (Fig. 7c, d, e) belonging to the C_C bond appeared in the FTIR spectra, indicating the introduction of the C_C
groups to the surface of the cotton fabrics. Moreover, the results
also mean that the CSi band linked to the vinyl group of D4 Vi
may break or the vinyl groups underwent polymerization gradually.
The intensity enhancement of the peak of the CSi band at 1256 cm1
(Fig. 7d, e) indicates the breakage of the CSi bands which were linked
to the methyl groups. Meanwhile, SiOSi bond at 1048 cm 1 and
1037 cm 1 became a double peak (Fig. 7c, d, e) when the treatment
time increased from 2 min to 7 min, indicating the SiOSi band in
the annular siloxane participated in the polymerization reaction.
These observations conrm the creation of new groups on the cotton
fabrics through the plasma induced grafting polymerization of D4Vi.

Table 2
Elemental composition for control and treated cotton fabrics by EDX.
Sample

Control cotton
Treated cottona
a

Elemental composition (at.%)


C

Si

55.16
49.89

44.84
30.01

0
20.10

The cotton fabric was treated with the power of 80 W and time of 2 min.

3.4. XPS and EDX analyses


The surface chemical compositions of the control and treated cotton
fabrics were investigated by XPS. Two banding energies at 284 eV and
532 eV could be clearly observed in the XPS spectrum of the control
cotton fabric (Fig. 8), which belong to C1s and O1s, respectively [21].
Compared with Fig. 8a, two new peaks belonging to Si2p and Si2s
appeared in the XPS spectrum of the treated cotton fabric (Fig. 8b),
indicating that D4Vi has been grafted to the surface of the cotton fabric.
The survey scan of the XPS data (Table 1) show that the atomic content of silicon of the control cotton fabric is 0 (S0), while it increased to
16.87%, 17.34% and 16.79% corresponding to S1, S2 and S3, respectively,
with the increase of the plasma treatment time from 2 min to 7 min. Simultaneously, the O/C atomic ratio changed from 0.43 to 0.28, 0.30,
0.30, while the Si/C atomic ratio changed from 0 to 0.26, 0.27, and 0.26, respectively. All these data indicate the reduction of the hydrophilic groups
and increase of the silicon content after the treatment of the cotton fabrics
through the plasma-induced grafting polymerization of D4Vi.
The surface elemental compositions of the control and treated cotton bers were measured EDX as well. The EDX spectra of control and
plasma treated cotton fabrics are shown in Fig. 9. We can observe the
decay of signals derived from silicon atoms. As listed in Table 2, the
atomic content of silicon, carbon, and oxygen on the surface of the treated cotton bers were about 20.10%, 49.89%, and 30.01%, respectively. It
means that the superhydrophobic polymer lms formed by the plasmainduced grafting polymerization of D4Vi are mainly composed of silicon,
carbon, and oxygen.
3.5. Thermal stability and washing durability analysis of the cotton fabrics
The thermal stability of the control and treated cotton fabrics were
characterized by TGA and DTG. As shown in Fig. 10a, the initial decomposition temperature of the treated cotton fabric is approximately the same
as that of the control cotton fabric. The weight loss of the treated cotton
fabric below 100 C could be ascribed to the evaporation of the physically
absorbed moisture. The maximum rates of the weight loss (and temperature) of the control and treated cotton fabrics are 44.75%/min
(378 C) and 42.096%/min (385 C), respectively (Fig. 10b), indicating
a slight decrease of the maximum rate of weight loss of the treated sample. It again conrms the successful coating of polymer lms on the cotton
ber, leading to the increase of the thermal stability of the material.
The washing durability is also reected by the relationship between
washing cycles and WCA value. From the washing durability curves of
treated cotton fabric by the plasma induced graft polymerization with
D4Vi in Fig. 10c, the WCA slightly decreases with the washing cycle increase, while WCA of treated cotton fabrics with mass uptake of 3.83%
and 2.65% decreased to 150 and 140 after 30 cycles respectively. It
indicates the polymer lms have excellent washing durability and is
closely adhered together with the cotton fabric by the plasma inducing
graft polymerization with D4Vi.

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Y. Zhang et al. / Surface & Coatings Technology 276 (2015) 1622

Fig. 10. (a) TG and (b) DTG curves of control and treated cotton fabrics (80 W, 2 min); (c) washing durability curves of treated cotton fabric by the plasma. Inserted images: the image of a
water droplet on the treated Cotton (80 W, 5 min) before (left) and after (right) washing cycles of 30.

4. Conclusions

References

In summary, superhydrophobic polymeric lms were successfully


constructed on the surface of cotton fabrics through a low pressure
plasma induced grafting polymerization of 1,3,5,7-tetravinyl-1,3,5,7tetramethylcyclotetrasiloxane. The siloxane cycle and vinyl groups of
D4Vi could be broken to undergo polymerization by the lowtemperature plasma glow discharge. The WCAs of the treated cotton
fabrics reached more than 150, suggesting that the polymer lms
contributed to lower the surface energy of the cotton fabrics signicantly.
The polymer lms with different WCSs could be obtained by controlling
the plasma RF power or the treating time. The proposed lowtemperature plasma technique to construct superhydrophobic lms
on cotton fabrics is simple, cost-effective, and environmental friendly,
which may have a profound effect on the construction of uorine-free
superhydrophobic lms on fabric surfaces.

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Acknowledgments
This work is supported by the National Natural Science Foundation
of China (No. 51403189), Science Foundation of Zhejiang Sci-Tech
University (ZSTU) (No. 13012139-Y), Open Foundation of Zhejiang Provincial Top Key Academic Discipline (2013YXQN10), and Zhejiang Provincial Top Key Academic Discipline of Chemical Engineering and
Technology (ZYG2012006).