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Contents lists available at ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Short communication

Superhydrophobic surface constructed on electrodeposited silica

films by two-step method for corrosion protection of mild steel
Xue-Fen Zhang, Rui-Jiao Chen, Ji-Ming Hu ∗
Department of Chemistry, Zhejiang University, Hangzhou 310027, China

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

Article history: Super-hydrophobic surfaces are fabricated on mild steel substrates via two-step methodologies. Firstly,
Received 11 August 2015 highly porous and hierarchically nano/micro-structural silica films are prepared by electrodeposition
Received in revised form technology. Superhydrophobicity is then achieved by further modification with a long alkyl-chained
31 December 2015
dodecyltrimethoxysilane. The superhydrophobic film provides effective protection for the mild steel
Accepted 31 December 2015
Available online xxx
when immersed in aggressive sodium solution by monitoring the change of contact angle, by iron dis-
solution test and by electrochemical measurements. The superhydrophobic surface as-prepared by this
method shows high mechanical durability for abrasion against SiC paper. Furthermore, the superhy-
Keywords:
A. Mild steel drophobicity provided by the rigid SiO2 matrix exhibits good reparability for heat destruction treatment.
B. EIS © 2016 Elsevier Ltd. All rights reserved.
C. Electrodeposited films

1. Introduction Electrochemically assisted technique has opened a new

approach to prepare more controllable, thicker and rougher
Chromate and phosphate-based coatings are of the majority sol–gel films in comparison with conventional dip-coating,
using for the corrosion inhibition of metals, due to their highly spinning-coating or spraying method [19,30,31]. Films with above-
effective corrosion protection properties [1–4]. Unfortunately, mentioned credits are deposited as a result of generating the
environmental regulations have restricted their use in corrosion necessary catalyst (OH− ions) for condensation reaction of sol–gel
protection systems due to the high toxicity of CrVI and eutrophica- components by increasing the local pH at conducting substrates
tion caused by phosphate [5–7]. Searching for an environmentally under negative potentials [32,33]. Investigations of electrode-
benign method to protect metals against corrosion is still the sub- posited silica-based sol–gel film materials are attracting extensive
ject of intensive research in spite of a number of methods have been attention in the application field of electroanalysis [34,35], biosen-
developed. sors [36,37] and corrosion protection of metal [32,38], etc.
Superhydrophobic films (with water contact angle ≥150◦ and Recently, we have taken advantage of the highly porous and
sliding angle less than 10◦ ) have recently been proposed as cor- rough microstructure of the electrodeposited silica sol–gel films
rosion inhibitors of various metallic substrates [8–15]. They can to fabricate superhydrophobic surface on conducting substrates
serve as effective barriers to keep water, moisture, and atmo- [33,39]. The fabrication is accomplished by either one-step or two-
spheric oxygen from reaching surfaces of the metal substrates. step route. The former is achieved by one-step electrodeposition
It is believed that two requirements, high surface roughness of inorganic and organic silica films from a mixed precursor solu-
and low-surface-energy materials, are desirable for fabrication of tion, while the latter is obtained by electrodeposition of inorganic
super-hydrophobic surfaces [16–18]. Different approaches have silica film followed by low-energy surface modification with a long
been developed to fabricate super-hydrophobic films, such as alkyl-chained organic silane. One-step superhydrophobic surface
immersion treatment [19–22], chemical vapor deposition (CVD) has been attempted to use for corrosion protection of mild steel
[18,23], hydrothermal method [24], chemical etching [15,25], [40].
anodic oxidation [26,27], template synthesis [11], and electro- However, the high content of organosilane component in the
chemical process [28,29] etc. above-described one-step superhydrophobic films makes them
presenting worse mechanical properties than pure inorganic silica
films. The films thereby are unable to be resistant to mechanical
destruction. In addition, since the organic component itself exists
∗ Corresponding author. Fax: +86 571 87951895 as the matrix structure in the hybrid films, the superhydropho-
E-mail address: kejmhu@zju.edu.cn (J.-M. Hu). bicity would be unrecoverable after heated at high temperature

http://dx.doi.org/10.1016/j.corsci.2015.12.028
0010-938X/© 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: X.-F. Zhang, et al., Superhydrophobic surface constructed on electrodeposited silica films by two-step
method for corrosion protection of mild steel, Corros. Sci. (2015), http://dx.doi.org/10.1016/j.corsci.2015.12.028
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(above 200 ◦ C) due to the irreversible micro-structural changes Meanwhile, hybrid superhydrophobic silica films were also pre-
of the matrix. In addition, although the hybrid films provide pared on MS substrate by one-step electrodeposition process from
organic coating-like corrosion resistance to metal substrate initially a mixed precursor of TEOS and DTMS [40], for the purpose of
(impedance value as high as 100 M cm2 at 0.1 Hz), they degrade comparison of mechanical property and reparability to thermal
rapidly in the first days’ immersion in NaCl solution [40]. destruction. The mixed precursor (pH 4.0, adjusted by HCl) con-
To overcome the above-mentioned drawbacks, two-step route sisted of 20 mL 0.2 M potassium nitrate (KNO3 ), 80 mL ethanol, 2 mL
is proposed to prepare superhydrophobic films in the present work TEOS and 2 mL DTMS. Prior to use, the mixed solution was vigor-
for the purpose of corrosion protection application. The experi- ously stirred for at least 12 h at room temperature to ensure the
mental results show that the as-prepared films present enhanced silane solution was hydrolyzed completely. The electrodeposition
mechanical properties and improved anticorrosive durability in was carried out at −1.3 V vs. Ag/AgCl for a duration time of 300 s.
comparison with those obtained by one-step method. Meanwhile,
the films are repairable in response to thermal destruction. These
merits are believed as the result of the existence of robust silica
matrix in the films. 2.3. Surface characterization.

The surface morphology of E-SiO2 films were characterized by

2. Experimental
scanning electron microscopy (ULTRA-55 FE-SEM, Zeiss Company,
Germany) at an operating voltage of 5.0 kV. Profilometry (Dektak
2.1. Materials and chemicals
150, Veeco, USA) was used to measure the roughness and thick-
ness of E-SiO2 films and a scratch was manually made by a wooden
Mild steel (MS, kindly supplied by Pentatomic Science & Tech-
stick. The contact angles (CA) of 5 ␮L Millli-Q water droplet on as-
nology, Hangzhou, China, wt.%: C 0.01, Si 0.35, P 0.018, Cr 0.04,
prepared surfaces were measured on a JC2000DF contact angle
Mo 0.03, Ni 0.017, Cu 0.02, Al 0.06; Fe balance) was cut into
instrument (Shanghai Zhongchen Digital Technic Apparatus Co.,
4.0 cm × 3.0 cm (0.1 cm thickness). Prior to electrodeposition, the
Ltd., China) equipped with a high speed CCD camera. The final CA
samples were abraded consecutively with finer SiC papers to 400
values were obtained by averaging five measurements on differ-
grade, degreased with home-made alkaline solution (composition:
ent positions of each surface. The indentation measurements were
sodium carbonate (Na2 CO3 ) 8 g/L, sodium metasilicate nonahy-
evaluated in a DUH-211S dynamic ultra hardness tester (Shimadzu,
drate (Na2 SiO3 ·9H2 O) 5 g/L, sodium polyphosphate (Na5 P3 O10 )
Japan) equipped with a conospherical diamond tip, which consists
8 g/L, sodium laurylsulfonate (C12 H25 NaO3 S) 1 g/L, Triton X-100
of a 115 conical indenter with a spherical end of 0.1 ␮m. Load-
5 mL/L) at 60 ◦ C for 10 min under sonication, then rinsed with de-
displacement curves were obtained by increasing indenter load at
ionized (DI) water, and finally blow-dried with warm air. High
a constant velocity of 0.1 mN/s up to a maximum of 19.6 mN with
temperature insulation paster was used to seal the back of the MS
a preset maximal depth of 1.0 ␮m. The abrasion tests were carried
substrates to leave the grinding side using as the working elec-
out on a home-made scratch tester. Twelve hundred grit SiC papers
trode. Two kinds of silane agents were used: tetraethoxysilane
were used as the abrasion surface with which the samples surfaces
(TEOS) (>98.5%, Sinopharm Chemical Reagent Co., Ltd., Shanghai,
contacted by varying the applied load and distance. The abrasion
China) and dodecyltrimethoxysilane (DTMS) (>93%, Tokyo Chem-
linear speed was 2.0 cm s−1 . To evaluate the weight percentage of
ical Industry Co., Ltd., Japan). The precursor solution (pH 4.0,
organic silane, thermogravimetric analysis (TGA, STA 409 PC, MET-
adjusted by acetic acid) used for electrodeposition was composed of
ZSCH, German) measurements were performed at air atmosphere
50 mL ethanol, 5 mL TEOS and 50 mL 0.2 M sodium nitrate (NaNO3 )
from 30 ◦ C to 800 ◦ C at a heating rate of 10 ◦ C/min. The thermosta-
aqueous solution and stirred for 12 h at 25 ◦ C before use. The DTMS
bility was evaluated by heating the superhydrophobic film in an
solution (pH 4.5, adjusted by acetic acid) used for low-energy sur-
oven for 2 h at consecutively increased preset temperature till the
face modification consisted of 3.0 vol.% DTMS dissolving in 75/25
superhydrophobicity was lost. The repairable property was charac-
(v/v) ethanol/water mixed solvent. The obtained solutions were
terized by CA measurements of films surface repaired with DTMS
pre-hydrolyzed at 35 ◦ C for 48 h. All the chemical reagents were
modification after the loss of superhydrophobicity.
used as received.

2.2. Preparation of hydrophobic films.

2.4. Electrochemical measurements
The electrodeposition was performed on a CHI 630d elec-
trochemical working station (CHI Instrument, Shanghai, China) All the electrochemical measurements were carried out in a
in a classical three-electrode compartment in which a Pt plate three-electrode cell filled with 3.5 wt.% NaCl solution on a CHI
(2.5 cm × 2.0 cm) and a commercial Ag/AgCl electrode (in the satu- 630d electrochemical working station. Before measurements, the
rated KCl solution) were used as counter and reference electrode, edge area of the superhydrophobic film-coated samples was sealed
respectively. The silica film was deposited onto MS substrate with epoxy resin with an exposure area of 7.5 cm2 to neglect the
(working electrode) from the TEOS precursor solution by applying un-uniformity. The Tafel curves were recorded at a sweep rate of
a cathodic potential ranging from −1.0 V to −1.5 V vs. Ag/AgCl for a 1 mV/s from –250 mV to +250 mV vs. the open circuit potential
certain duration time (from 10 s to 500 s). After electrodeposition, (OCP). The final corrosion current density (Icorr ) was obtained from
the electrodeposited SiO2 film (notated as E-SiO2 film) was rinsed the intersection of the two Tafel curves in the cathodic and anodic
with DI water and absolute EtOH successively and cured in an oven polarization regions. The electrochemical impedance spectroscopy
at 40 ◦ C for 3 h. To prepare hydrophobic surface, the obtained E- (EIS) measurements were performed on a M273 model potentiostat
SiO2 films were immersed in the DTMS precursor solution for 300 s (Princeton Applied Research, USA) combined with a M5210 model
(refer to [33]). For comparison, a conventionally protective DTMS lock-in amplifier (Signal Recovery, USA) at room temperature. The
film was also prepared by directly immersing the MS substrates into measured frequency was varied from 100 kHz to 0.01 Hz at OCP
the DTMS precursor solution for the same time. After surface mod- with an AC excitation amplitude of 10 mV amplifier (peak-to-zero).
ification, all the samples were rinsed in EtOH solution to remove All measurements were performed after samples were immersed
any excess solution, and cured at 40 ◦ C for 3 h in an oven. in the testing solution for ∼10 min.

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Fig. 1. SEM images of bare MS (a), E-SiO2 films prepared at −1.3 V for 10 s (b), at −1.1 V for 300 s (c) and at −1.3 V for 300 s (d): the insets are corresponding water drop
images on the prepared film after DTMS modification.

2.5. Iron dissolution determination inhibitor to avoid undesired dissolution of the intact MS substrate.
The dissolution process was lasting for 5 min.
The amount of dissolved iron in 50 mL 0.6 mol/L NaCl solu-
tion (25 ◦ C) was examined by a UV–vis spectrometer (New 3. Results and discussion
Century T6, PERSEE, China) according to ISO 6332-1988 “water
quality—determination of iron” using 1,10-phenanthroline as the The success of electrochemical deposition of silica films is a
indicator. Prior to measurements, samples with an exposure area result of electrochemical generation of condensation catalyst, OH− ,
of 3.0 cm × 2.5 cm were immersed in 3.5 wt.% NaCl solution for 24 h. whose kinetics depends, to a great extent, on the applied potential
After then, the superhydrophobic silica films were scraped off the and deposition time. The SEM images dependence on electrode-
MS substrate by a wood stick and dispersed in the same immersion position potential and time are summarized in Fig. 1. The abraded
solution. Finally, 2 mL H2 SO4 (98%) was added into the solution bare MS presents smooth and compact morphology (Fig. 1a). Only
to entirely dissolve the corrosion products embedded in the silica a small part of the substrate is covered by silica particles after elec-
films, attached on the MS substrate and those precipitated in the trodeposition for a short time (10 s, Fig. 1b). The as-prepared E-SiO2
testing solution. 0.05 wt.% thiourea was introduced together as the film (after DTMS modification) provides a low CA value (∼113◦ ).

Fig. 2. Electrodeposition time (a, at −1.3 V vs. Ag/AgCl) and potential (b, for 300 s) dependent thickness and roughness (upper) and contact angle (bottom) of the E-SiO2 films
coated on MS. For CA measurements, films were modification with DTMS.

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Similarly, noble deposition potential (e.g. −1.1 V vs. Ag/AgCl, Fig. 1c) -0.3
gives low roughness of the derived silica films, which is adverse

OCP/ V vs. Ag/AgCl

to the fabrication of superhydrophobic surface. The films exhibit 4
-0.4
highly rough and hierarchical morphology with prolonging the
deposition time to 300 s and potential negatively shifting to −1.3 V
vs. Ag/AgCl (Fig. 1d). At these conditions superhydrophobicity was -0.5
achieved (CA = 155◦ ). Quantitative measurements suggest that sil-
ica films continuously grow on MS substrate with prolonging the 3
-0.6 2
electrodeposition time (Fig. 2a, upper part) and the superhydropho-
1
bicity is obtained after electrodepositing for 100 s at −1.3 V vs.
Ag/AgCl (Fig. 2a, lower part). Film formation is undoubtedly facil- -0.7
itated by applying more negative potential (Fig. 2b, upper part), 0 10 20 30 40 50 60
under which more amount of OH− catalysts are generated, pro- Time / min
ducing bigger driving force for sol–gel film formation. Accordingly, Fig. 3. Time dependent the open circuit potential, OCP, for bare MS (1), DTMS dip-
CA values increase when potential shifts negatively and reach over coated (2), E-SiO2 coated (3) and superhydrophobic E-SiO2 coated (4) MS electrodes
150o at potentials below −1.2 V vs. Ag/AgCl (Fig. 2b, lower part). in 3.5 wt.% NaCl solution.
In the present study, unless otherwise mentioned the superhy-
drophobic films used for the investigation of corrosion protection
vs. Ag/AgCl (curve 1) to −0.60 V vs. Ag/AgCl (curve 2) and −0.57 V
are prepared at an electrodeposition potential of −1.3 V vs. Ag/AgCl
vs. Ag/AgCl (curve 3) when the substrate is covered by DTMS-only
for a duration time of 300 s.
and E-SiO2 film-only films, respectively. The most positive poten-
As a kind of short-term protection system, superhydrophobic
tial value (−0.40 V vs. Ag/AgCl) is detected on superhydrophobic
films are generally used in atmosphere environment. In the present
samples (curve 4), i.e. the electrodes covered with E-SiO2 film fol-
work, however, an aggressive medium (3.5 wt.% NaCl solution)
lowed by low-energy surface modification with DTMS. The more
was chosen to evaluate the inhibitive property of the obtained
positive potential indicates the decreasing corrosion tendency of
superhydrophobic surface, in order to shorten the testing time. In
the electrode system. As shown from the figure, stable OCPs are
fact, this aggressive solution was also used to assess the corrosion
obtained for all four electrodes after immersion for 10 min.
protection capacity of other superhydrophobic surfaces on met-
The in-situ corrosion behaviours of superhydrophobic surface
als [40–42]. Potential-time curves (Fig. 3) show that the OCP of MS
are examined by EIS. Nyquist diagrams (Fig. 4a) clearly show much
substrate in 3.5 wt.% NaCl solution is positively shifted from −0.64 V
higher impedance values of superhydrophobic sample (curve 4),

Fig. 4. Nyquist diagrams (a), Bode phase angle plots (b), Bode log (|Z|) vs. log (f) plots (c) after immersion for 0.5 h in 3.5 wt.% NaCl solution of bare MS (1), DTMD-only treated
(2), E-SiO2 film-only coated (3) and superhydrophobic E-SiO2 film coated (4) MS electrodes. (d) Evolution of low-frequency impedance with immersion time (at 0.01 Hz).
The error bar was also given in Fig. 4d.

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155

150

Contact angle / °
145

140

135

130
0 25 50 75 100 125 150 175
Immersion time / h
Fig. 5. Tafel curves in 3.5 wt.% NaCl solution of bare MS (1), DTMD-only treated
(2), E-SiO2 film-only coated (3) and superhydrophobic E-SiO2 film coated (4) MS Fig. 6. CA change of the superhydrophobic surface over time of the immersion in
electrodes. 3.5 wt.% NaCl solution. The error bar was also given in the figure.

in comparison with other specimens (curves 1–3). Warburg char- entrapped air layer in this porous structure induced by the contin-
acteristic appears in the superhydrophobic surface in the low uous attack of water and other aggressive ions. It is worth noting
frequency domain (curve 4), indicating the restriction of diffusion that even though immersed in 3.5 wt.% NaCl solution for 120 h,
of corrosion products from MS substrate to bulk solution or that the superhydrophobic sample still has relatively higher impedance
of oxidants (e.g. dissolved oxygen) from the opposite direction module, which is about 23 times and 35 times higher than E-SiO2
[43]. This phenomenon is believed as a result of promising bar- film-coated and DTMS-only-silanized MS substrates, respectively.
rier property of superhydrophobic films. Phase angle plot (Fig. 4b) Though the superhydrophobic silica films prepared by one-step
shows a simple single relaxation for bare MS electrode (curve 1), method provided nearly 2 orders of magnitude higher impedance
corresponding to electrochemical corrosion reaction occurring in value (∼100 M cm2 at 0.1 Hz) [40] in the very initial immer-
electrode/electrolyte interface. Two time constants are observed sion stage than those prepared by two-step method presented in
on MS substrates covered with DTMS (curve 2) or E-SiO2 (curve this investigation, they rapidly decreased in impedance value dur-
3) films. The high-frequency loop is assigned to the existence of ing the first two days’ immersion. After immersed for 120 h, both
the protective films. A similar capacitive loop is also observed on the above-mentioned samples prepared by one-step and two-step
superhydrophobic surface in high frequency domain (curve 4). It methods have almost identical impedance values (∼30 k cm2 at
is clearly shown that the phase angle values of this sample at high 0.1 Hz). This comparison indicates greatly enhanced durability of
frequencies are much higher than other coating samples, suggest- two-step superhydrophobic surface.
ing again the good barrier behavior of superhydrophobic films. Tafel curves measurement is an effective method to rapidly
Impedance module plots (Fig. 4c) indicate that, compared with bare evaluate the corrosion resistance of samples and the results are
MS specimen (curve 1, Fig. 4c), silanization treatment with DTMS summarized in Fig. 5. As showed in Fig. 5, no obvious improve-
on bare MS substrate exhibits almost no improvement in barrier ment in corrosion resistance performance is provided either by
property (curve 2, Fig. 4c). E-SiO2 films only provide a little but traditional silanization process (Icorr = 1.5 × 10−5 A cm−2 , curve 2,
very limited protection effect on steel substrate (curve 3, Fig. 4c), Fig. 3c) or by covering E-SiO2 film (Icorr = 1.2 × 10−5 A cm−2 , curve 3
due to their high porosity and superhydrophilic property. However, in Fig. 5) with respect to bare MS substrate (Icorr = 2.2 × 10−5 A cm−2 ,
the superhydrophobic surface prepared by DTMS-modification on curve 1, Fig. 5). However, the corrosion current density is dramati-
E-SiO2 films shows significantly enhanced inhibition against corro- cally reduced to 2.5 × 10−7 A cm−2 after modification of E-SiO2 with
sion of the substrate (curve 4, Fig. 4c). Evolution of low-frequency DTMS (curve 4, Fig. 5), which is 2 orders of magnitude lower than
impedance module (|Z|lf ) with the immersion time more clearly the others, indicating that superhydrophobic films can serve as an
shows the good corrosion performance of the superhydrophobic effective barrier layer to hinder the diffusion of corrosive species.
films (Fig. 4d). |Z|lf values of the superhydrophobic sample are ∼1 CA change with the immersion time in 3.5 wt.% NaCl solution is
and ∼2 orders of magnitude higher than the E-SiO2 film-covered also monitored (Fig. 6). The film keeps its stable superhydropho-
and conventional DTMS-silanized substrates, respectively. The bicity in the first two days’ immersion. After 93 h of immersion,
impedance values of the superhydrophobic sample decrease with the CA slightly decreases to 148.7◦ and still maintains a high value
increasing the immersion time in the first days, suggesting a degra- ∼137.2◦ though immersion for 170 h. Such a high stability against
dation process of superhydrophobic films due to the escaping of the the change of CA value in corrosive NaCl solution reduces the risk of

Fig. 7. Optical images of bare MS (a), DTMD-only treated (b), E-SiO2 film-only coated (c) and superhydrophobic E-SiO2 film coated (d) MS electrodes after immersed in
3.5 wt.% NaCl aqueous solution for 10 min, 0.5 h, 5.5 h and 60 h, respectively.

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(a) 100 (b) 0.52

2
2
90
1
0.39

Force / mN
Weight / %
80
3
0.26
70

3 0.13
60

50 0.00
0 200 400 600 800 0.0 0.5 1.0 1.5 2.0 2.5
Temperature / °C Depth / m
(c) 160 (d) 160
2
155
Contact angle / °

Contact angle / °
2
140

150

120 3 3
145

100 140
0 2 4 6 8 0.0 0.1 0.2 0.3 0.4 0.5 0.6
Abrasion length / m Applied pressure / kPa

Fig. 8. The TGA profiles (a) and load-displacement curves (b) of E-SiO2 film (1), superhydrophobic film prepared by two-step (2) and one-step (3) methods. (c and d) Changes
of water contact angle of two-step (2) and one-step (3) superhydrophobic surface over the abrasion length at 0.55 kPa (c) and applied pressure after 1 meter abrasion (d).
The error bar was also given in Fig. 8c and d.

absorption of aggressive species on the surface of superhydropho- hydrophobic sample is dramatically reduced to 2.35 mg cm−2 h−1 ,
bic film, resulting in consecutive corrosion protection for duration. showing the superior corrosion performance of superhydropho-
Optical observation shows that serious corrosion occurs as soon bic surface, which is in good agreement with the EIS, Tafel curve
as the bare MS is immersed in 3.5 wt.% NaCl solution (∼5 min, measurements and optical observation.
Fig. 7a). DTMS-treated MS substrate corrodes intensively after The poor protective property of conventional DTMS-treated
immersion for only 30 min. After this time, the whole surface area MS is mainly due to the low thickness and coverage and high
is covered with red rust (Fig. 7b). After immersed in 3.5 wt.% NaCl non-uniformity of the thin sol-gel film generated by dip-coating
solution in less than 6 h, E-SiO2 coated substrate is inevitably sub- technique [44,45]. The superhydrophilicity and high porosity of E-
ject to certain degree of corrosion (Fig. 7c), indicating that the SiO2 films facilitate the electrolyte penetration, which results in
porous silica films can only provide slight but very limited improve- a limited inhibition capacity. In contrast, greatly improved pro-
ment in corrosion protection performance. The superhydrophobic tectiveness is obtained for DTMS-modified E-SiO2 films, because
surface, however, remains its high resistance against the attacking large amount of trapped air existed in these superhydrophobic
of corrosive media and no obvious corrosion reaction occurs until films greatly reduces the risk of attack of water and corrosive media
the immersion time is lasting for 60 h (Fig. 7d). [46–48]. In addition, DTMS film itself on superhydrophobic surface
Iron-dissolution test determines the iron dissolution rate of also provides a certain extent of inhibiting property to the metal
47.2 mg cm−2 h−1 and 15.9 mg cm−2 h−1 for conventional DTMS- substrate [49].
silanized and E-SiO2 film-coated samples, respectively. However, TGA measurements are carried out to determine the load capac-
after modification of E-SiO2 with DTMS, the corrosion rate of super- ity of organic component (mainly the DTMS) in superhydrophobic

Fig. 9. Changes in CA values of one-step (a) and two-step (b) superhydrophobic films with the heat temperature. Solid and open scatters stand for the CA values before and
after repairing, respectively.

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E-SiO2 films (Fig. 8a). The weight loss below 200 ◦ C is attributed electrodeposited silica films, as well as the low-surface-energy
to desorption of water molecular and physically adsorbed organic property of dodecyltrimethoxysilane used for hydrophobic mod-
materials. The sharp decrease between 200 ◦ C and 450 ◦ C is ascribed ification. The surface hydrophobicity of mild steel is tunable by
to the removal of DTMS. The entirely overlapped TGA profiles of E- adjusting the deposition time and applied potential during the
SiO2 films before (curve 1, Fig. 8a) and after (curve 2, Fig. 8a) DTMS electrodeposition of silica films. The as-prepared superhydropho-
modification indicate a small amount of DTMS assembles onto the bic surface presents much higher corrosion resistance properties
silica surface. However, the TG curve of superhydrophobic silica when immersed in 3.5 wt.% NaCl aqueous solution, as compared
films prepared by one-step technique gives a high content of DTMS to a conventionally dodecyltrimethoxysilane-silanized mild steel
(∼36.6 wt.%) in the hybrid films (curve 3, Fig. 8a). substrate. More importantly, the superhydrophobic E-SiO2 film
The low content of organic components in two-step superhy- exhibits good mechanical abrasion resistance, thermal stability
drophobic films may predict their improved mechanical property and outstanding reparability in comparison with superhydropho-
as compared with those obtained by one-step process. The load- bic film prepared by one-step method due to the existence of rigid
displacement curves achieved from indentation tests confirm the SiO2 backbone in the former film.
above-mentioned prediction (Fig. 8b). The robustness of the as-
fabricated superhydrophobic surfaces is then investigated by a Acknowledgement
home-made scratch tester with twelve hundred grit SiC papers
used as the abrasion surface. As shown in Fig. 8c, the surface of This work was financially supported by the NSFC (nos. 21173187
two-step sample still has superhydrophobicity with CA of 151.8◦ and 51371159).
after abrasion for 1.0 m at 0.55 kPa in contrast to the one-step
hybrid superhydrophobic film, which loses its superhydrophobicity
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Please cite this article in press as: X.-F. Zhang, et al., Superhydrophobic surface constructed on electrodeposited silica films by two-step
method for corrosion protection of mild steel, Corros. Sci. (2015), http://dx.doi.org/10.1016/j.corsci.2015.12.028
G Model
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Please cite this article in press as: X.-F. Zhang, et al., Superhydrophobic surface constructed on electrodeposited silica films by two-step
method for corrosion protection of mild steel, Corros. Sci. (2015), http://dx.doi.org/10.1016/j.corsci.2015.12.028