Int. J. Electrochem. Sci.

, 10 (2015) 7380 - 7391

International Journal of
ELECTROCHEMICAL
SCIENCE
www.electrochemsci.org

A Simple Process for Fabricating Organic/TiO2 Super-

Hydrophobic and Anti-Corrosion Coating
Chunyan Mo1, Yansheng Zheng1,2,*, Falong Wang1,Qian Mo1
1
College of Biological and Chemical Engineering, Guangxi University of Science and Technology,
Liuzhou 545006, Guangxi, PR China
2
Lushan College of Guangxi University of Science and Technology, Liuzhou 545616, Guangxi, PR
China
*
E-mail: [email protected]

Received: 2 June 2015 / Accepted: 9 July 2015 / Published: 28 July 2015

Fluoro-methylhydro-silicone oil was blended with nano TiO2 particle after it was prepared by
methylhydro-silicone oil and dodecafluoroheptyl-propyl-trimethoxysilane as raw materials. The
Organic/TiO2 composite coating was fabricated on steel substrate by sol-gel method. The
hydrophobicity and surface structure of composite coating were described by Infrared spectroscopy,
Scanning electron microscopy, thermogravimetric analysis and Contact angle analyzer. In addition,
Electrochemical methods were measured in order to characterize the corrosion of the as-prepared
coating. The results indicated that the final composite coating with rich surface structure had a good
anti-corrosion performance and exhibited superhydrophobic.

Keywords: Organic/TiO2 composite coating; super-hydrophobic; anti-corrosion

1. INTRODUCTION

The wettability of solid surface, which governed by not only the morphology of the solid
surface but also its intrinsic chemical compositions, is one of the most important properties of solid
surface[1,2]. It’s characterized by contact angle and sliding angle. We call the solid surface as super-
hydrophobic surface when its contact angle (CA) is larger than 150° while sliding angle (SA) is smaller
than 10°[3-5]. These special surface can be commonly found in biological system such as animal
bodies and plants. for example, the lotus leaf is a typical model with both super-hydrophobicity and
low adhesive force, whereas[6], the gecko is a typical model which represents the Cassie impregnating
wetting state with super-hydrophobicity but high adhesive force[7,8]. In recent years, Super-
hydrophobic materials have gained a significant interest and are of interest for various fields such as
Int. J. Electrochem. Sci., Vol. 10, 2015 7381

metal anti-corrosion[9], self-cleaning[10,11], building waterproof[12], fluid drag reduction[13] and

anti-fouling[14] as well owing to their peculiar and improved features.
As we all know, numerous of coating techniques for fabricating super-hydrophobic surfaces
have been reported, including chemical vapor deposition, phase separation, sol-gel process, electro-
spinning and etching (plasma etching, photo etching, acid etching ) method[15-18]. The principle of all
the methods mentioned above in fabricating super-hydrophobic surfaces is widely accepted as either
creating the rough structure on the surface of hydrophobic materials directly or modifying a rough
surface by materials with low surface free energy, or combining both[19-21]. Some materials such as
glass, wood, cotton cloth, paper, plastics and metals are used as substrates to create artificial
superhydrophobic surfaces[22-24]. In the meantime, a large number of chemical substances including
Silane[25], Fluoroalkylsilane[26] and Teflon[15] are used to modify the surface with micro/nanometer
scale during the modification process. Thanks to the special apparatus for limited base materials,
rigorous conditions and multi-step, the cost of most techniques seems to be unacceptable and the time
consuming seems to be impractical [27]. How to develope preparation process, especially easy-to-
prepare, high-efficiency, low-cost and large-scale, plays a key role in fabricating super-hydrophobic
surfaces. And, for now at least, much effort has been put toward expanding applications of artificial
superhydrophobic surfaces[28].
In the few past decades, composite material has attracted considerable attention within
fundamental research as well as potential application industry because of its special advantages[26]. In
addition, it had an incredible tremendous progress in such a short period of time because of the huge
demand for more functional and advanced materials. Compared with the properties of a single
material, composite materials have more advantages including higher thermal stability, better
dimensions, better mechanical behavior[29,30]. For instance, as a new composite between organic
polymer and inorganic polymer, the organic-inorganic nano-meter composite material can overcome
the disadvantages of single organic or inorganic nano-particle in order to satisfy utilization
requirements. For now, the composite material have concurrently characteristic of inorganic-organic
matter. What’s more, the organic-inorganic nano-meter composite material with special functions has
been widely used in many applications. Throughout this process, nano-meter inorganic powders are
usually used as filling materials to be combined with organics by chemical bound in order to endued
the product with excellent properties such as super-hydrophobic performance because of its
micro/nano secondary structure. As super-hydrophilic substance, the nano-particles of titanium dioxide
has a large number of hydroxyl groups on its surface, they are easily agglomerated in the water
emulsion due to the high surface energy, in fact, the modification of nano-titanium dioxide powder is
necessary so that the super-hydrophobic coating can be obtained. Silane coupling agent and fatty acids
are the common modifiers. Hu et al.[31] fabricated the nano-titanium dioxide (nano-TiO2) super-
hydrophobic surface on Hastelloy substrate after suitable thermal treatment through simple dip-
coating. The nano-TiO2 solution was used as precursor solution and fluorinealkylsiloxane was used as
modifier, the results showed the as-obtained sample had excellent superhydrophobicity with water
contact angle higher than 170◦. Ramanathan [32] Fabricated superhydrophobic surfaces in
aqueous(ethanol/water) or non-aqueous(xylene) solvent via a very simple and inexpensive method by
using titanium dioxide and trimethoxypropyl silane as raw materials. The results showed the surfaces
Int. J. Electrochem. Sci., Vol. 10, 2015 7382

formed in different solvents had same static contact angle as high as 160° but different adhesion and
contact angle hystersis. Based on a convenient and controllable strategy, Wang et al.[33] prepared a
superhydrophobic TiO2 film on glass substrate followed by thermal treatment and modification with
stearic acid, the as-prepared film exhibited improved transparency, good bounce performance and high
superhydrophobicity, the water contact angle as high as 157◦, in contract, the low roll-off angle was 2◦.
In this letter, we developed a simple method for fabricating superhydrophobic and anti-corrosive
composite coating by nano modified TiO2 and Fluoro-methylhydro-silicone oil. the CA is up to 151.5°
± 1° and SA is down to 6°. The morphological and wetting properties of the coating surfaces are
investigated as well as the anticorrosion performance of the composite coating. The results show the
composite had rough surface with rich structure and good anticorrosion performance.

2. EXPERIMENTAL DETAILS

2.1 Materials

TiO2 with average particle size 10-30 nm was purchased from Shanghai jiang titanium dioxide
chemical products co., LTD. Methylhydro-silicone oil with hydroxylgroup content between 6 and 10
was obtained from Jinan heng Feilong chemical co., LTD. Stearic acid was obtained from Guangdong
Shantou Xilong chemical plant. Dodecafluoroheptyl-propyl-trimethoxysilane (DFPT) was obtained
from Haerbing Xeogia fluoro-silicone Chemical Reagent Co.,Ltd. Sodium Dodecyl Benzene Sulfonate
(SDBS) was obtained from Shantou guanghua chemical plant. ammonia solution (NH3H2O) and
ethanol were analytical grade and used as received.

2.2 Modification of nano TiO2 particles

First of all, orderly add TiO2 (5g) and stearic acid (0.4 g) that was well dissolved in ethanol (40
mL) into 40 mL of DI water under magnetic stirring for more than 2h at 80 °C followed by adding
suitable SDBS. The pH of TiO2 hybrid emulsion was adjusted to 5.0 by the addition of acetic acid.
Finally, the modified-nano TiO2 was dried at the temputure of 130 °C for 2 h。

2.3 Fabrication of fluoro-methylhydro-silicone oil

The fluoro-methylhydro-silicone oil was prepared by dehydrogenation coupling reaction. First,

Mix SDBS (0.1 g) and DI water (20 mL) with a low speed for 5 min at room temperature. Then,
slowly add Dodecafluoroheptyl-propyl-trimethoxysilane: methylhydro-silicone oil (1:1), ethanol (10
mL) and suitable catalyst Karstedt into the solution above. The mixture was called solution A and it
was vigorously stirred for another 3 h until the reaction was complete.
Int. J. Electrochem. Sci., Vol. 10, 2015 7383

2.4 Fabrication of superhydrophobic composite coating

The as-prepared modified TiO2 powder was slowly added into solution A as well as
silane coupling agent (3-(Methylacryloxyl) propyltrimethoxy silane ) and two drops of catalyst
(ammonia solution). Followed, a homogeneous white viscous liquid was obtained after the mixture had
been stirred for 4 h and aged at room temperature for 12 h. Based on the combined effect of the
chemical bonding force among particles and the absorption force of substrate surface, the
Organic/TiO2 coatings were directly made on cleaned substrate after dip-coating and a series of heat-
treatment process. Fig. 1 shows the schematic illustration of preparing superhydrophobic composite
coating.

Figure 1. The process of formating the composite coating

2.5 Characterization

The final composite particle was tested with thermal analysis (TG, Netzsch STA449F3A-1103-
M) and its surface morphology structure was characterized by digital scanning electron microscopy
(SEM, S-3400 N), The water CA and SA of the composite coating surface were obtained by averaging
the measurements on five positions of the examined surface through sessile drop method (Dataphsics
OCA20), and the corrosion of the composite coating was characterized by electrochemical methods
such as polarization measurement and alternating current impedance spectroscopy through CHI 660D
electrochemical analyzer, Fourier transform infrared (FTIR) spectra were recorded with a Nicolet 380
spectrometer in the range 4000-500 cm-1.
Int. J. Electrochem. Sci., Vol. 10, 2015 7384

3. RESULTS AND DISCUSSION

3.1 FT-IR spectra

Fig. 2 shows the FTIR spectras of original and fluorinated methylhydro-silicone oil with DFPT.
In the low frequency region, the Si-O-Si group and -CH2- group stretching vibration peaks appear at
around 800 cm-1 and 1100 cm-1 in both methylhydro-silicone oil and fluoro-methylhydro-silicone oil
spectra. The -OCH3 group in DFPT will be hydrolyzed into hydroxyl radica(-OH) and then reacted
with the Si-H group in methylhydro-silicone oil when the catalyst Karstedt exists[34], so the presence
of the absorption band at 2167 cm-1 in methylhydro-silicone oil spectra which is atrributed to Si-H
stretching vibration disappears after the reaction with DFPT. What’s more, The two other absorption
bands at 1710 cm-1 and 2925 cm-1 in fluoro-methylhydro-silicone oil are due to the stretching vibration
of -CH3 and CF2-CF2 groups[35]. The results further confirm that the methylhydro-silicone oil has
been successfully fluorinated.

a
Si-H Si-CH2
-CH2-
Si-O-Si

CF2-CF2

b Si-O-Si
-CH2- -CH2-
-CH3
4000 3500 3000 2500 2000 1500 1000 500
-1
wavenumber/cm

Figure 2. The infrared spectrograms of samples: (a) methylhydro-silicone oil; (b) fluoro-methylhydro-
silicone oil

3.2 Thermal analysis

As we all know, heat treatment has an effective influence on surface chemical composition and
the microstructure of composite particles[36]. Furthermore, both surface chemical composition and
microstructure will determine the wettability of the composite coating[37,38]. Reacting process of the
composite particles with temperature is understood through determining its thermal analysis curves.
Fig. 3 shows the effect of heat treatment on the hydrophobicity of the TiO2-fluoro-methylhydro-
silicone oil composite coatings, The samples were heated at different temperatures including 60, 90,
120, 130, 150 and 180 °C for 1 h. We can see from Fig. 3 that the coating attained the best
hydrophobic property (WCA =151.5 ± 1°) when the temperature was 130 °C. Fig. 4 presents the TG-
DSC curve of the as-prepared composite particles when the temperature was about 130 °C. According
to the TG-DSC curve. The exothermic peak and weight loss at about 160 °C in the TG-DSC curve is
Int. J. Electrochem. Sci., Vol. 10, 2015 7385

mainly due to the microscopic chemical reagents and physical absorbed water’s desorption behaviours.
In addition, The obvious exothermic phenomenon and mass-loss rate of composite particles achieves
when the temperature is between 300 °C and 800 °C especially at about about 670 °C, which mean the
composite particles are suffering from damage thermally during this period. This may because of the
oxidative and decomposition of stearic acid, alkyl groups, organofluorine and other organic material.

155

WAC
150

145

140
0
WCA/

135

130

125

60 80 100 120 140 160 180

o
Temperature/ C

Figure 3. Effect of heat treatment on water contact angle

DSC/(mW/mg)
TG/%
2.0 102

exo 100
1.5
98

96
1.0

94

0.5
92

90
0.0
88

-0.5 86
0 100 200 300 400 500 600 700 800
O
T/ C

Figure 4. Thermal analysis curves of as-prepared composite particles

3.3 Morphological studies

Wettability of solid surface is governed by both the chemical composition and the surface
microstructure roughness. Fig.5 shows the microstructures of the as-prepared samples in our case. The
fluoro-methylhydro-silicone oil particles showed in Fig. 5a-b exhibit unique hierarchical soft air-
cushion structures that can adsorb a large fraction of air. After reacted with nano-modified TiO2,
these soft air-cushion structures are full of inorganic powder so the morphology structures of
composite particles are more abundant (Fig. 5c-d). Accoring to the famous Cassie and Baxter
module[39], instead of being full filled with liquid directly, there has a large quantity of air between
the grooves on solid surface and the liquid. Such special gas-liquid-solid composite interface, which is
Int. J. Electrochem. Sci., Vol. 10, 2015 7386

closely related to the micro/nano double structures on the hierarchically rough surface, is required for
superhydrophobicity. This configuration is described by the following Eq. (1): cosθCB=ƒcosθ+ƒ-
1(1)[39-42]. Where θCB and θ respectively denote the contact angle of a water droplet on a rough
surface and on a smooth surface, ƒ is the liquid-solid surface fraction. It is easy to deduce from Eq. (1)
that the more hydrophobic the composite coating appears as the CA of the rough surface (θ CB) increase
and the liquid-solid surface fraction (ƒ) decrease. In our study, the images of the super-
hydrophobic properties of the uncoated and coated coatings are showed in Fig.6, showing the water
contact angle of TiO2/fluoro-methylhydro-silicone oil composite coating reaches 151.5 ± 1° .

Figure 5. SEM images of the samples:(a-b) fluoro-methylhydro-silicone oil particles, (c-d) modified
nano TiO2/fluoro-methylhydro-silicone oil composite particles

a b

151.5±1°

Figure 6. Images of the water droplets on the as-prepared coating surface: (a) TiO2 /fluoride-
methylhydro-silicone oil particles, (b) uncoated steel substrate
Int. J. Electrochem. Sci., Vol. 10, 2015 7387

3.4 Electrochemical measurements

The anti-corrosion performance of five different samples were described based on a series of
electrochemical measurements in order to further examine their corrosion behaviors. All samples were
tested after being immersed in 3.5 wt% NaCl aqueous for 48 h under air-open condition with a three-
electrode system at room temperature. The coating specimen was used as the working electrode. A
saturated calomel electrode and a platinum electrode were used as reference electrode and auxiliary
electrode, respectively.[19,43] The polarization measurements were conducted at a scanning rate of 5
mV/s, the potential range was from -1.4 to 0.6 V.
Fig. 7 shows the Tafel plots of uncoated/coated steel samples and the parameters obtained from
potentiodynamic polarization measurements including corrosion potential (Ecorr), corrosion current
density (jcorr), anodic and cathodic Tafel constants (ßa and ßc ) are given in Table 1. According to Fig. 7
and table 1, Ecorr increased to -0.91 V, -0.98 V and -0.93 V from -1.15 V for bare steel after being
coated with modified nano-TiO2, methylhydro-silicone oil and fluoro-methylhydro-silicone oil,
respectively. We can also observed that TiO2/fluoro-methylhydro-silicone oil exhibited the most
positive Ecorr compared to the other samples. It’s corrosion potential was -0.85 V. These positive
shifted in Ecorr confirms the protection of steel substrate surface when the composite was coated on.
someone believed that the shifts in Ecorr might due to the development of more stable passive films,
similar to anodic protection.[44,45] In addition, the similar trend was observed in ßa and ßc. Compared
with the bare steel substrate, the samples coated with modified nano-TiO2, methylhydro-silicone oil
and fluoro-methylhydro-silicone oil, respectively showed a rising trend in whole though with a minor
fluctuation. This may account for the positive shifts in Ecorr. Morever, according to Table 1, the
corrosion current density (jcorr) of TiO2/fluoro-methylhydro-silicone oil was 3.44×10-5 A/cm2, which
was 223.26, 4.85, 4.56, 2.85 times lower than that of uncoated, TiO2, methylhydro-silicone oil and
fluoro-methylhydro-silicone oil films. The significant decrease in jcorr suggested that the organic/ TiO2
composite coating was of good sealing type.[46]
The Nyquist plots of the measured samples are showed in Fig. 8, Where Z' ( Z") mean the real
(imaginary) part of the impedances. The charge transfer resistance, which can be obtained from the
diameter of the EIS curve, is used to evaluate wether the coating exhibit good anti-corrosion
performance or not[42,47]. Generally, the slower corrosion rate is, the higher corrosion resistance is,
the bigger charge transfer resistance with higher corresponding curve radius is, and vise verse. As
easily unsterstood from Fig. 8, the diameter of the EIS curve of bare steel substrate was much smaller
than other samples. The methylhydro-silicone oil showed similar anti-corrosion performance compared
with pure modified TiO2 coating but poorer than fluoro-methylhydro-silicone oil. what’s more, the
diameter of the EIS curve of TiO2/fluoro-methylhydro-silicone oil was the highest one.
Based on the results above, we do believe that the TiO2/Organic coating exhibited the best
corrosion protection on steel substrate, which may due to the effective interactions between fluoro-
methylhydro-silicone oil organic macromolecule and nano-TiO2 inorganic powders. the presence of
TiO2 nanoparticles significantly improved a micro/nano double rough surface[48], which created a
gas-liquid-solid composite interface, neither active chloride ions nor water molecules in NaCl solution
that would promote corrosion to accelerate the damage to coating[49] can readily penetrate the
Int. J. Electrochem. Sci., Vol. 10, 2015 7388

composite structure. What’s more, the organic macromolecule fluoro-methylhydro-silicone oil with
hydrophobic alkyl groups and a network of Si-O groups can decreases the effective area for corrosion
reaction by blocking the reaction sites in order to prevent the substrate being corroded. the anti-
corrosive mechanism of as-prepared Organic/TiO2 composite coating is showed in Fig.9. However,
both methylhydro-silicone oil and fluoro-methylhydro-silicone oil were somhow more sticky to water
as well as the pure TiO2 film, thus showed poorer anti-corrosion performance (higher jcorr and lower
Ecorr) than TiO2/organic composite coating. Last but not least, the bare steel substrate was immersed in
corrosive medium directly so it is unable to protect itself from being corroded.

-1

-2

a
-3
log[j/A.cm )]
-2

b
-4

-5 c
d
-6 e

-7
-1.4 -1.2 -1.0 -0.8 -0.6

Potential(E vs.SCE/V)

Figure 7. Tafel plots of steel specimens: (a) uncoated; coated with: (b) modified TiO2, (c) pure
methylhydro-silicone oil, (d) fluoro-methylhydro-silicone oil, (e) TiO2/fluoro-methylhydro-
silicone oil in 3.5% NaCl solution

Table 1. Corrosion potentials and corrosion current densities of different samples

Coating Corrosion corrosion current ßa(V/dec) ßc(V/dec)

potential/V density(A/cm2)
Bare steel substrate -1.15 7.68×10-3 0.07 0.13
Nano modified TiO2 -0.91 1.67×10-4 0.09 0.14
methylhydro-silicone oil -0.98 1.57×10-4 0.12 0.13
fluoro-methylhydro-silicone oil -0.93 9.82×10-5 0.11 0.14
TiO2/fluoro-methylhydro-silicone oil -0.85 3.44×10-5 0.16 0.16

3000

2500 e

2000
-Z''/(Ω.cm )
2

d
1500

1000

c
500
b
a
0
0 50 100 150 200 250 300 350
2
Z'/(Ω.cm )
Figure 8. EIS curves of steel specimens:(a) uncoated; coated with: (b) modified TiO2, (c) pure
methylhydro-silicone oil, (d) fluoro-methylhydro-silicone oil, (e) TiO2-fluoro-methylhydro-
silicone oil in 3.5% NaCl solution
Int. J. Electrochem. Sci., Vol. 10, 2015 7389

Figure 9. Anti-corrosive mechanism of TiO2/ organic composite coating

4. CONCLUSION

In this paper, we fabricated TiO2/fluoro-methylhydro-silicone oil composite coating with

abundant surface microstructures via a simple method by using nano-TiO2 particle and methylhydro-
silicone oil as raw materials. The hydrophobicity and surface structure of the composite coating were
described by thermo gravimetric analysis, Scanning electron microscopy, Fourier transform infrared
and Contact angle analyzer. The results showed the final composite coating exhibits superhydrophobic
performance with a static contact angle of 151.5 ± 1° and a rolling angle of 6°. The corrosion of the
hybrid coating was characterized by electrochemical methods, such as polarization curve measurement
and Electrochemical impedance measurements. The results indicated that the TiO2/fluoro-
methylhydro-silicone oil composite coating both had good hydrophobicity and anti-corrosion
performance.

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© 2015 The Authors. Published by ESG (www.electrochemsci.org). This article is an open access
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© 2015 The Authors. Published by ESG (www.electrochemsci.org). This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution license
(http://creativecommons.org/licenses/by/4.0/).