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Accepted Manuscript

Title: A biomimetic nano hybrid coating based on the lotus


effect and its anti-biofouling behaviors
Author: Jiang Li Guoqing Wang Qinghua Meng Chunhua
Ding Hong Jiang Yongzeng Fang
PII: S0169-4332(14)01675-4
DOI: http://dx.doi.org/doi:10.1016/j.apsusc.2014.07.147
Reference: APSUSC 28394
To appear in: APSUSC
Received date: 2-3-2014
Revised date: 23-7-2014
Accepted date: 25-7-2014
Please cite this article as: J. Li, G. Wang, Q. Meng, C. Ding, H.
Jiang, Y. Fang, A biomimetic nano hybrid coating based on the lotus
effect and its anti-biofouling behaviors, Applied Surface Science (2014),
http://dx.doi.org/10.1016/j.apsusc.2014.07.147
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A biomimetic nano hybrid coating based on the lotus
effect and its anti-biofouling behaviors
Jiang Li
a
, Guoqing Wang
a,*
, Qinghua Meng
b,*
, Chunhua Ding
a
, Hong Jiang
a
,
Yongzeng Fang
b
a
School of Materials & Chemical Engineering/Key Lab of Special Glass, Hainan
University, Hainan 570228, P. R. China;
b
School of Chemistry & Chemical Engineering, Shanghai Jiao Tong University,
Shanghai 200240, P. R. China
* Correspondence author. Email: wangguoqing@hainu.edu.cn (G. Wang), Tel: +86-898-68683247.
* Correspondence author. Email: qhmeng@sjtu.edu.cn (Q. Meng), Tel: +86-13918184475.
Abstract:
To develop an environmentally friendly anti-biofouling coating in virtue of bionics, a block
copolymer containing fluorine (Coplm_F) of low surface energy was prepared by
copolymerization. The Ag-loaded mesoporous silica (Ag@SBA) acting as a controlled-release
antifoulant was prepared from the mesoporous silica (SBA-15). The nano hybrid coating
(Ag@SBA/Coplm_F) composing of the Coplm_F and Ag@SBA was to biomimetically simulate
the lotus microstructure. The concentration of fluorine element on surface was analyzed by the
energy dispersive spectroscopy (EDS) and found rising to 1.45%after hybridation, which could be
explained by the driving effect of SBA-15 via the hydrogen bond. This nanoscale morphology of
the hybrid coating was measured and found highly semblable to the microstructure of the lotus
surface. The contact angle was determined as 151 which confirmed the superhydrophobicity and
lotus effect. The adhesion behaviors of Pseudomonas fluorescens, Diatoms, and Chlorella on the
surface of the nano hybrid coating (Ag@SBA/Coplm_F) were studied and good effects of
anti-biofouling were observed.
Keywords: anti-biofouling; lotus effect; block copolymer; silver nanoparticle; biomimetics
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1. Introduction
The biofouling is a serious problem in all aspects of marine engineering such as shipping,
defense, recreation, harbors, drilling platforms and fishery, which are suffered from the
accumulation and settlement of barnacles, macroalgae, microbial slimes, and other organisms on
man-made surfaces immersed in seawater. Marine biofouling can significantly increase friction
resistance and lead to more fuel consumption. Thus, the anti-biofouling coatings are provided to
decrease the adhesion of marine organisms and remove them as well. In the recent decades, use of
environmentally friendly coatings to replace the traditional tributyl tin [1] and copper containing
coatings [2] has attracted researchers interests. In the last few years, the electrografting technique
for reduction of biofouling has been investigated as well [3].
The silver particle has been regarded as an effective, safe, broad and permanent fungicide, and
could be regarded as a candidate for the antifoulant [4,5]. Taking into account of both the cost and
sustained release, the silver particle is often loaded in mesoporous materials such as the molecular
sieves [6,7]. The SBA-15 mesoporous material has generated a great deal of interests in the field
of catalysis, drugs, sensing, and adsorption due to its high surface areas and large ordered
nano-pores with narrow size distributions [8]. In this study, the silver particle is designed to be
embedded into the nano-pores of SBA-15 by ions exchanging and the following reduction.
Another trend in the antifouling coating is the using of materials with low surface energy
specifically silicone or fluoropolymer based systems, which could minimize the adhesion strength
between fouling organisms and the surface of vessels [9-11]. Practically both control-release silver
particles and copolymers of low surface energy are complementary functional ingredients in
design of hybrid anti-biofouling coatings. The fluorinated multilayered polyelectrolyte films such
as PEI/PAA and PEI-Ag(I) complex were prepared and used as the anti-biofouling and
superhydrophobic coatings [12-14].
Meanwhile, materials possessing nanoscale topographical features also display the remarkable
hydrophobicity and bactericidal activity [15], in addition to the other bioinspired applications such
as anti-icing, anti-corrosion coatings, microfluidic devices, textiles, oil/water separation, water
desalination/purification, optical devices, sensors, batteries and catalysts [16]. H. Yang et al
reported a novel lotus-leaf-like antibacterial film fabricated by the microcapsule-supported Ag
nanoparticles which was prepared by adsorbing of Ag(I) ions on the surface of sulfonated
polystyrene beads via electrostatic interaction and protection by polyvinylpyrrolidone [17].
Then we are inspired to design a block copolymer containing fluorine in which the Ag-loaded
mesoporous silica (Ag@SBA) is embedded. The block copolymer containing fluorine (Coplm_F)
could be prepared from the styrene-butadiene-styrene polymer (SBS) and vinyl fluoride silicone
(BD-FT-LSR). The hydrogen bond will be formed between the polysiloxane unit and the hydroxyl
group in the outer edge of SBA-15, so a nanoscale hydrophobic region is constructed by the
fluorinated groups linking to the polysiloxane unit, which is a rigid phase separation region. The
SBS segments of the copolymer are flexible and may act as the molecular hooks to connect the
separated rigid regions containing Ag@SBA into a macroscopically homogeneous coating by
means of the Velcro Effect (Fig. 1). The design purpose of this nano hybrid coating is to
biomimetically simulate the lotus microstructure to achieve the marked effect in anti-biofouling.
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2. Experimental
2.1. Materials
The styrene-butadiene-styrene polymer (SBS) and vinyl fluoride silicone (BD-FT-LSR) were
supplied by Shanghai Sunvea Chemical Material Co., Ltd. The azodiisobutyronitrile (AIBN) was
crystallized from an industrial product (Tianjin Guangfu Fine Chemical Research Institute). The
other chemical reagents were used as commercially received (Sinopharm Chemical Reagent Co,
Ltd.). Pseudomonas fluorescens, Diatoms and Chlorella were supplied by Guangdong
Microbiology Culture Center.
2.2. Preparation of the block copolymer containing fluorine (Coplm_F)
10 g of SBS (0.16 mol of ethylene unit) and 100 mL of tetrahydrofuran (THF) were taken in a
500 mL round bottom flask and stirred for 0.5 hr at room temperature. Then 4.32 g of BD-FT-LSR
(0.12 mol of ethylene unit) and 0.1 g of AIBN were added to the flask and stirred for 5 hr at 65 .
The reaction mixture was left overnight and followed by addition of 300 mL of ethanol on stirring.
The product precipitated from the solution was filtrated and washed with 230 mL of ethanol.
After dried in a vacuum oven at 50 for 1 hr, 12 g of the white resin-like material (Coplm_F) was
obtained. The
1
H NMR spectra was recorded on a Mercury plus 400 instrument (Varian) for
solutions in CDCl
3
using (CH
3
)
4
Si as an internal standard.
1
H NMR for Coplm_F (400 MHz,
CDCl
3
, ): 7.09(Ar-H), 6.59(Ar-H), 5.40(-CH
2
-CF
3
), 4.95(Si-OH), 2.06(-CH
2
-C-CF
3
),
2.03(CH
3
-Si-C-C-CF
3
), 1.25-1.43(butadiene), 0.09 (Si-CH
3
). The infrared spectra (IR) were
recorded on a Tensor 27 FT-IR Spectrometer (Bruker). The number-average, weight-average and
viscosity-average molecular weight were measured as 114200, 124200 and 133800 respectively
by a gel permeation chromatography system (HLC-8320GPC EcoSEC, Tosoh) using
tetrahydrofuran (THF) as mobile phase and polystyrenes as the standards.
2.3 Preparation of the Ag-loaded mesoporous silica (Ag@SBA)
The mesoporous silica SBA-15 was prepared according to the literature [8]. 1.0 g of SBA-15
and 50 mL of AgNO
3
aqueous solution (0.01 mol/L) were mixed and stirred at room temperature
for 6 hr. The solid was recovered by filtration, washed with distilled water twice, and then mixed
with 20 mL of aqueous sodium borohydride solution (0.01 mol/L). The mixture was stirred at
room temperature for 2 hr, then followed by filtration and washing with distilled water. 1.0 g of
the solid product (Ag@SBA) was obtained after drying in a vacuum oven at 50 for 1 hr. The
concentration of the silver element in the product was determined as 1.2% (w/w) by an atomic
absorption spectrophotometer (Varian). The XRD analysis of the Ag-loaded mesoporous silica
(Ag@SBA) was conducted on a D8 Advance X-ray diffractometer (Bruker AXS). The
morphology analysis was analyzed by a S-3000N scanning electron microscope (Hitachi). The
nano structure was analyzed by a Sirion 200 transmission electron microscopy (FEI). The N
2
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adsorptiondesorption isotherms and pore sizes of the mesoporous materials were measured on an
ASAP 2010 surface area and porosimetry analyzer (Micromeritics).
2.4. Preparation of the nano hybrid coating (Ag@SBA/Coplm_F)
0.98 g of the block copolymer (Coplm_F) was dissolved in 10 mL of THF, and 0.02 g of
Ag@SBA was added. The mixture was stirred at room temperature for 2 hr and then sprayed on a
clean glass slide manually. After evaporation of the solvent, the hybrid coating of approximately
100 m thickness was then obtained for characterization. The morphology and elemental
analysis were analyzed by a S-3000N scanning electron microscope equipped with an energy
dispersive spectroscopy (EDS) analysis system (Hitachi). The static sessile drop contact angle was
measured with a XG-CAMA Contact Angle Measurement System (Xuanyichuangxi Industrial
Equipment Co., Ltd.) and for each measurement a 1 L drop of MilliQ water was used to
determine the contact angle of the sessile drop. The contact-angle hysteresis and the sliding angle
were measured using the tilted-drop method.
2.5. The anti-fouling tests
The antibacterial effect of the Ag-loaded mesoporous silica (Ag@SBA) on the Pseudomonas
fluorescens was carried out in the agar plating. Four agar platings containing Pseudomonas
fluorescens were added by the aqueous Ag@SBA solution and the final concentration of
Ag@SBA in each the agar plating was 0.00 0.01, 0.02, 0.03, 0.04 g/mL, respectively. The samples
were then incubated at 29 in a thermostat incubator for 24 hours. The number of bacterial
colonies (N) was counted using a colony counter and used for evaluation of the antibacterial effect
of Ag@SBA.
The anti-adhesion effects of the coatings to the Pseudomonas fluorescens were carried out in the
Pseudomonas fluorescens containing solution. The block copolymer coating on glass, the nano
hybrid coating (2% Ag@SBA) on glass as well as the blank glass slide were set vertically in the
Pseudomonas fluorescens containing solution. The samples were then incubated at 29 in a
thermostat incubator for 2 hours. For the feasibility of observation, the Pseudomonas fluorescens
on these coatings were washed with 10 mL aseptic water each which were then sprayed onto the
agar plating and incubated at 29 in a thermostat incubator for 24 hours. The adhesion numbers
of bacterial colonies were counted and used for evaluation of the anti-adhesion effect to the
bacteria.
The anti-adhesion effects of the coatings to the algae were carried out in the Diatoms or
Chlorella containing solutions. The block copolymer coating on the glass slide, the nano hybrid
coating on the glass slide as well as the blank glass slide were set vertically in the Diatoms or
Chlorella containing solutions. The samples were then incubated at 29 in a thermostat
incubator for 2 hours and washed by the aseptic water. The adhesion numbers of algae colonies
were counted in an optical microscope and used for evaluation of the anti-adhesion effect to algae.
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3. Results and discussion
The block copolymer containing fluorine (Coplm_F) was prepared from the
styrene-butadiene-styrene (SBS) and vinyl fluoride silicone (BD-FT-LSR). The vinyl groups at
both ends of the polysiloxane chain reacted with the ethylene bonds inside the SBS chain by
initiation of the AIBN (Scheme 1). The reaction could be confirmed from the their IR spectra in
which the typical absorption peaks involving the ethylene bonds were largely weakened such as
the C=C stretching vibration at 1602 cm
-1
, the C-H stretching vibrations in =C-H bond at 3060
cm
-1
and in =CH
2
bond at 2964 cm
-1
, respectively. Moreover, the absorption peak of C
sp3
-H
stretching vibration at 2918 cm
-1
was distinctly enhanced (Fig. 2). In the
1
H NMR spectrum of the
block copolymer (Coplm_F), the characteristic chemical shifts () of hydrogen atoms in styrene
units located at 6.59 and 7.09 ppm, accordingly, those in butadiene units located at 1.25-1.43 ppm,
and those in methylene groups near trifluoromethyl units located at 5.39 ppm respectively.
Therefore, the numbers of the styrene, butadiene and trifluoromethyl units in the block copolymer
could be calculated as 104, 13 and 520 from the number-average molecular weight (M
n
, GPC
method) 114200 g/mol and the integral area from the
1
H NMR.
The ample hydroxyl groups on the inside surface of the nano-pores of SBA-15 had been
considered as the platform for uploading metal ions via ions exchanging [18]. In this research, the
silver ions were imported into the nano-pores by ions exchanging and then reduced to silver atom
by the sodium borohydride. The silver atoms were subsequently aggregated to the silver
nanoparticles which sizes were limited by the the nano-pores of SBA-15 (Fig. 3). The SEM
images of the pure mesoporous silica SBA-15 and Ag-loaded mesoporous silica (Ag@SBA) were
shown in Fig. 4. Both samples had the similar shape of a twisted cylinder at the dimension of 1-3
m in length and 0.2-0.5 m in diameter, which indicated that the inclusion of silver
nanoparticles had almost no effect on the appearance shape of the crystals of the mesoporous
silica. The fact of no isolated silver nanoparticle locating outside mesoporous cavity supported the
ions exchanging mechanism during the Ag-loaded process. The Ag-loaded mesoporous silica
(Ag@SBA) indicated the typical 2D-hexagonal symmetry of mesoporous silica like SBA-15
which had the pore diameter of 8 nm approximately (Fig. 4f). The black dots or pearl-like
aggregates were observed embedding in channels of the mesoporous silica (Fig. 4d and 4f), which
prevented the silver nanopaticles from growing too large and controlled the release of silver for
the anti-fouling application.
The small-angle XRD analysis of the Ag-loaded mesoporous silica (Ag@SBA) was shown in
Fig. 5(a). The intensity of three peaks that assigned to (100), (110), and (200) in an ordered
2D-hexagonal symmetry was largely lower than that of the pure SBA-15 which might be ascribed
to the scattering by the silver particles. The wide-angle XRD analysis of pure SBA-15 and
Ag-loaded mesoporous silica (Ag@SBA) was shown in Fig. 5(b). In addition to the broad band at
23 characteristic of the morphous silica, four distinct diffractions at 38.0, 44.3, 64.3, and 77.3
corresponding to the lattice planes of (111), (200), (220), and (311) in Ag metal, respectively,
indicated the presence of silver nanoparticles. The N
2
adsorption desorption isotherms were
further conducted to evaluate the surface properties. In Fig. 6a, both samples of the pure SBA-15
and Ag@SBA showed the typical hysteresis loops with the sharp adsorption and desorption
branches, however, the adsorption volume of the Ag@SBA was reduced to nearly half of the
value of the pure SBA-15 due to the occupation of silver nanoparticles. The relatively smaller
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average pore size and wider pore size distribution were observed as well (Fig. 6b).
As the nano hybrid coating (Ag@SBA/Coplm_F) was prepared from hybridation of the
Ag-loaded mesoporous silica (Ag@SBA) in the block copolymer (Coplm_F) at the concentration
of 2% w/w, the elemental information on the surface was important for the anti-fouling behavior.
The EDS analysis of both surfaces of the block copolymer and nano hybrid coating were
conducted and the results were shown in Table 1. No silver information was obtained on the
surface of the Ag@SBA/Coplm_F which confirmed that all the silver particles were inclusion
inside the channels of the SBA-15 and none naked on the surface. Interestingly, only very low
concentration (0.06%) of fluorine was detected on the surface of the block copolymer (Coplm_F),
but the concentration of fluorine surprisingly rose to 1.45% after its hybridation with the
Ag@SBA. The vinyl fluoride silicone (BD-FT-LSR) part in the block copolymer was relatively
higher in density than the styrene-butadiene-styrene (SBS) part, so the BD-FT-LSR part located
below the surface layer, and the SBS part preferred the upper side in the surface layer (Scheme 2).
After addition of Ag@SBA, the hydrogen bond connecting the polysiloxane with the hydroxyl
group in the outer edge of SBA-15 drove the trifluoromethyl units migrating and stretching
upward, which led to the increasing of the fluorine concentration on surface (Scheme 2). On the
other side, the higher fluorine concentration could contribute to the low surface energy which was
beneficial to the anti-fouling.
The SEM images of the nano hybrid coating (Ag@SBA/Coplm_F) were shown in Fig. 7 and
the Ag-loaded mesoporous silica was finely dispersed in the block copolymer system. The lug
boss of approximately 90 nm in diameter was observed on the micron-sized Ag@SBA particles
(Fig. 7) which was speculated to be the phase separation of the block copolymer induced by the
Ag@SBA. This nanoscale morphology was highly semblable to the microstructure on the surface
of the lotus [19], which thus constructed a typical bio-mimetical superhydrophobic surface. The
contact angle of the nano hybrid coating was determined as large as 151, and by contrast that of
the block copolymer (Coplm_F) was only 92 (Fig. 8). The contact-angle hysteresis and the
sliding angle of the nano hybrid coating were determined as 15 and 9 respectively as well, which
indicated that the water adhesion on the nano hybrid coating was low. These results gave us the
innovation impetus to develop it into a novel biomimetical anti-biofouling coating.
The antibacterial effect of the Ag-loaded mesoporous silica (Ag@SBA) on the Pseudomonas
fluorescens was firstly assayed in the agar plating. The different concentrations of Ag@SBA were
used and incubated with the Pseudomonas fluorescens for 24 hours at 29 in a thermostat
incubator. The number of bacterial colonies (N) was counted using a colony counter and the
results were compared with the blank sample in ratio shown in Fig. 9. Obviously, better
antibacterial effects could be achieved at the higher concentrations of Ag@SBA. The usage of
high concentration was uneconomic because the silver was a noble metal. Thus the concentration
near 0.02 g/mL would be a preferential selection on accounting of both the antibacterial and the
economic factors.
Generally, the biofouling started from the adhesion of bacteria or algae on the surfaces
immersed in natural water [20]. The Pseudomonas fluorescens, Diatoms and Chlorella were then
used to evaluate the antimicrobial character of the surface of the nano hybrid coating. The blank
glass slide and the block copolymer coating were used for comparison. The coating samples were
immersed in the solutions containing the Pseudomonas fluorescens, Diatoms and Chlorella,
respectively. The Pseudomonas fluorescens was incubated on the coating at 29 for 24 hours.
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The Diatoms and Chlorella were incubated at 29 for 2 hours. The microbial adhesion on the
coatings was shown in Fig. 10. The hydrophilic surface of the blank glass slide had the serious
microbial adhesion. The coating of block copolymer (Coplm_F) could reduce the microbial
adhesion to a large extent due to its hydrophobicity, which had been recognized as one common
method for surface treatment for anti-fouling [21]. And furthermore, better antimicrobial adhesion
was achieved by hybridation of Ag@SBA into the block copolymer which was contributed by
both the silvers antimicrobial activity and the lotus effect. The multifunctional hybrid coatings
accompanied with the nano structure morphology in similar biomimics were reported in recent
literatures in the fields of anti-biofouling and superhydrophobic materials, too [12-17]. And
reasonably, good performances might be expected in the long life of the anti-fouling product on
accounting of slow release of the silver from the nano hybrid coating, which will be evaluated in
the future research in depth.
4. Conclusions
A block copolymer containing fluorine (Coplm_F) of low surface energy was prepared by
copolymerization between SBS and BD-FT-LSR. The Ag-loaded mesoporous silica (Ag@SBA)
was prepared from SBA-15 by ions exchanging and reduction. The adsorption volume of the
Ag@SBA was measured to be nearly half of the value of the pure SBA-15 due to the inclusion of
silver nanoparticles. The elemental information on the surface of the coatings were analyzed by
EDS and the concentration of fluorine was found rising to 1.45% after hybridation with the
Ag@SBA, which was explained by the driving effect of SBA-15 through the hydrogen bond. This
nanoscale morphology of the hybrid coating was measured by SEM and found highly semblable to
the microstructure on the surface of the lotus. The contact angle was determined as 151 which
confirmed the superhydrophobicity and lotus effect. The anti-biofouling behaviors of the nano
hybrid coating were studied through observing the adhesion of Pseudomonas fluorescens, Diatoms,
and Chlorella on the surface, and good anti-fouling effects were obtained in comparison with the
blank sample.
Acknowledgments
The work was supported by the Shanghai Talent Plan of Science and Technology (No.
12XD1421300) and the Locality Development Project of Hainan University (No. HDSF201308).
We also thank the Instrumental Analysis Center of Shanghai Jiao Tong University and the
Instrumental Analysis Center of Hainan University for provision of the professional service.
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Table 1 The elemental concentrations on the surface of the block copolymer (Coplm_F) and nano
hybrid coating (Ag@SBA/Coplm_F) measured by EDS.
The element atom %
Coatings
C O F Si Ag
Coplm_F 66.55 15.74 0.06 11.55 0.00
Ag@SBA/Coplm_F 48.47 26.86 1.45 22.60 0.00
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Fig. 1. The schematic view of the biomimetic nano hybrid coating for anti-biofouling.
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Fig. 2. The comparison of the IR spectra of the copolymer (Coplm_F, ), the
styrene-butadiene-styrene (SBS, ) and the vinyl fluoride silicone (BD-FT-LSR, ).
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Fig. 3. Preparation of the Ag-loaded mesoporous silica (Ag@SBA).
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Fig. 4. The micrograph images of the prepared SBA-15 and Ag@SBA mesoporous materials. The
surface patterns of SBA-15 (a) and Ag@SBA (b) were demonstrated by the Scanning Electron
Micrograph (SEM) at 15,000 magnification. The inner patterns of SBA-15 (c, e) and Ag@SBA (d,
f) were demonstrated by the transmission electron microscopy (TEM) at magnification of 30,000
and 80,000.
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0 1 2 3 4 5
0
1000
2000
3000
4000
5000
6000
(200)
(100)
(110)
2 (degree)
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
0 10 20 30 40 50 60 70 80
0
1000
2000
3000
4000
5000
6000
(311)
220
(200)
(111)
I
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s
i
t
y

(
a
.
u
.
)
2 (degree)
(a) (b)
Fig. 5. The XRD analysis of the pure SBA-15 () and Ag-loaded mesoporous silica (Ag@SBA,
) at the small-angle (a) and the wide-angle (b) regions.
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0.0 0.2 0.4 0.6 0.8 1.0
0
100
200
300
400
500
600
700
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n

v
o
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u
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e

(
c
m
3
/
g
)
Relative pressure (P/P
0
)
5 6 7 8 9
0
5
10
15
20
25
30
D
i
s
t
r
i
b
u
t
i
o
n

(
%
)
Pore size (nm)
(a) (b)
Fig. 6. The N
2
adsorptiondesorption isotherms (a) and pore size distributions (b) of the pure
SBA-15 () and Ag-loaded mesoporous silica (Ag@SBA, ).
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(a) (b)
Fig. 7. The SEM images of the nano hybrid coating (Ag@SBA/Coplm_F) at 250 (a) and 180,000
(b) magnification.
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(a) (b)
Fig. 8. The contact angles on the surfaces of the copolymer (Coplm_F, a) and the nano hybrid
coating (b). The insert is determination of the hysteresis and the sliding angles.
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0.00 0.01 0.02 0.03
0
20
40
60
80
100
N
u
m
b
e
r

o
f

b
a
c
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i
a
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c
o
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i
e
s

(
N
/
N
0
,
%
)
Concentration (g/mL)
Fig. 9. The antibacterial effects of the Ag@SBA at the different concentrations.
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20
0
100
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400
500
600
700
Ag@SBA/Coplym_F Coplym_F Blank
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o
f

b
a
c
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r
i
a

(

1
0
3
)
0
2
4
6
8
10
12
14
16
18
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o
f

a
l
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a
e
Fig. 10. The adhesion of bacteria (: Pseudomonas fluorescens) and algae (: Diatoms, :
Chlorella) on the surfaces of the blank glass slide, the block copolymer coating and the nano
hybrid coating.
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Si O Si
F F
F
O Si
m
a
Si O Si
F F
F
O Si
m
b
c
a
b
c
a
b
c
+
AIBN
SBS BD-FT-LSR
Coplm_F
Scheme 1 Synthesis of the block copolymer containing fluorine.
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Si O Si
F F
F
O Si O Si O Si
F F
F
F F
F
O O
Si
O
F F
F
Si
F F
F
Si
F F
F
Si
O
Si
O
H
O
H
O
H
O
H
Ag@SBA
Scheme 2 The distribution of the fluorine in the Coplm_F (left) and Ag@SBA/Coplm_F (right)
coatings.
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O O
Si
O
F F
F
Si
F F
F
Si
F F
F
Si
O
Si
O
H
O
H
O
H
O
H
Ag@SBA
Graph_abstract
0
100
200
300
400
500
600
700
Ag@SBA/Coplym_F Coplym_F Blank
A
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o
f

b
a
c
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r
i
a

(

1
0
3
)
0
2
4
6
8
10
12
14
16
18
A
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i
o
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o
f

a
l
g
a
e
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This manuscript contains the following highlights:
1) A nano hybrid coating was prepared from a block copolymer and Ag-loaded SBA-15.
2) The lotus-like morphology and the superhydrophobicity were confirmed.
3) The anti-biofouling behaviors of the nano hybrid coating were studied.