Corrosion Science 69 (2013) 23–30

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

Super-hydrophobic film prepared on zinc and its effect on corrosion

in simulated marine atmosphere
Peng Wang a, Dun Zhang a,⇑, Ri Qiu a,b, Jiajia Wu a,b, Yi Wan a
a
Key Lab of Corrosion Science, Shandong Province, Institute of Oceanology, Chinese Academy of Sciences, 7 Naihai Road, Qingdao 266071, China
b
Graduate School of the Chinese Academy of Sciences, 19 (Jia) Yuquan Road, Beijing 100039, China

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

Article history: Zinc–laurylamine complex film with super-hydrophobicity is fabricated on zinc surface with electrolysis
Received 2 July 2012 method. Super-hydrophobicity of film results from papillae and ridge-like structures, which form due to
Accepted 29 October 2012 uneven corrosion of zinc at high anodic potential. The film obtained can maintain super-hydrophobic
Available online 7 November 2012
property in solution system, and can inhibit corrosion effectively. However, saline water penetrates into
super-hydrophobic film during deliquescence process of NaCl particle in simulated marine environment.
Keywords: This behavior is induced by capillary condensation in groove of film, and it declines the advantage of
A. Zinc
using super-hydrophobic film as corrosion barrier in marine atmosphere.
B. SEM
B. XPS
Ó 2012 Elsevier Ltd. All rights reserved.
B. EIS
C. Atmospheric corrosion

1. Introduction air trapped in film is the essential contributor to excellent anti-

Atmospheric corrosion of zinc occurs in almost every atmo-
spheric environment, and marine environment is the most aggres-
sive one due to the highly corrosive nature of airborne pollutants
[1]. In marine environment, the deposition of salt particles on me-
tal surfaces plays a vital role in atmospheric corrosion. Bubbles
that form from ocean waves can generate marine aerosols contain-
ing of small salt droplets or particles. These aerosols can be carried
by wind and deposit on metal surface. When the relative humidity
reaches a critical value, hygroscopic salts can absorb moisture and
form salty droplets, which can greatly accelerate the corrosion of
metals [2].
Until now, a great deal of research work has aimed at increasing
lifetime of zinc. An effective method is to fabricate a compact coat-
ing on zinc surface to inhibit aggression of corrosive medium [3–8].
Generally, premature degradation of coating is due to a double
negative effect of soluble salts at the metal/paint interface. On
one hand, they cause the appearance of blisters of osmotic origin
on paint film. On the other hand, they accelerate the corrosion pro-
cess of metallic substrate under paint [9] . Thus, the anti-corrosion
performance of coating is related to its effect of preventing electro-
lyte permeation into coating/metal interface.
For its water-repellent property, fabrication of artificial super-
hydrophobic surface is regarded as a potential method for corro-
sion protection of metal in aqueous solution. It was proven that
⇑ Corresponding author. Tel./fax: +86 532 82898960.
E-mail address: Zhangdun@qdio.ac.cn (D. Zhang).
corrosion effect [10–17]. In atmospheric environment, air is
trapped in grooves of super-hydrophobic film, and it can prevent
electrolyte to penetrate for capillary effect [18,19]. Furthermore,
super-hydrophobic surface can keep away the salt and water,
because water droplet on super-hydrophobic surface can easily roll
off from the surface and take away salt aerosol. Accordingly, it
seems that modification with super-hydrophobic film is an effec-
tive corrosion protection method for metal in atmospheric envi-
ronment. To the best of our knowledge, there is no report about
corrosion inhibition of super-hydrophobic film to metal in atmo-
spheric environment.
In this paper, super-hydrophobic film was fabricated on zinc
surface with electrolysis method, and it was characterized with
contact angle test, electrochemical measurements and so on. Based
on these results, formation mechanism of super-hydrophobic film
on zinc was proposed, and inhibition effect of super-hydrophobic
film to marine atmospheric corrosion induced by deliquescence
of NaCl particle was investigated.
2. Experimental
2.1. Materials and reagents
Zinc (P99.99 wt.%) foil and a series of chemicals, including lau-
rylamine, sodium chloride (NaCl) and ethanol, were purchased
from Sinopharm Chemical Reagent Co., Ltd. Water used was
Milli-Q water (Milli Q, USA).

0010-938X/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2012.10.025
24 P. Wang et al. / Corrosion Science 69 (2013) 23–30

2.2. Modification of zinc surface

In a typical procedure, zinc foil was abraded with emery paper

(400 grade), and rinsed with ethanol. The growth of super-hydro-
phobic film was performed in a two-electrode cell, in which zinc
sample and a platinum wire acted as an anode and a cathode,
respectively. Film was electrochemically grown at a constant po-
tential of 30 V for 30 min in 0.1 M laurylamine/ethanol solution
with direct current power supply at 25 °C. The width between an-
ode and cathode is 3 cm, and the area of both anode and cathode
exposed to electrolysis solution is 2 cm2. After that, zinc sample
was brought out, washed with ethanol, and dried naturally in
atmosphere.

2.3. Surface characterization

Morphology of surface was characterized with FE-SEM (JSM-

6700F). Contact angles of 4 lL water droplet on bare and filmed
zinc were measured with contact angle meter (JC2000C1, Shanghai
Zhongchen Digital Technic Apparatus Co., Ltd.) at ambient temper-
ature. X-ray photoelectron spectroscopy (XPS) measurement was
carried out on a Thermo ESCALAB 250 photoelectron spectrometer
equipped with an Al-anode at a total power dissipation of 150 W
(15 kV, 10 mA), and the binding energies were referenced to the
C 1s line at 284.8 eV from adventitious carbon.

2.4. Monitoring of deliquescence process of NaCl

Marine atmospheric environment was simulated in a condition-

ing chamber, where the relative humidity (RH) was controlled by
means of aqueous glycerin solution according to the Standard
ASTM D 5032-97 (Reapproved 2003). In conditioning chamber,
the filmed zinc sample was placed above aqueous glycerin solu-
tion, and a single NaCl particle was transferred gently onto sample
surface to avoid destroying micro-structure of film. Then, forma-
tion process of saline water droplet due to deliquescence of NaCl
was recorded with CCD camera.

2.5. Electrochemical experiments

Open circuit potential (Eoc)  t curves and electrochemical

impedance spectroscopy (EIS) were obtained with a computer-
controlled electrochemical system (CHI 760C, CH Instruments
Inc.) in 3.5 wt.% NaCl solution with temperature of 25 °C. These
experiments were performed in a three-electrode cell with a plat-
inum electrode as counter electrode, zinc / filmed zinc as working
electrode, and a silver/silver chloride (Ag/AgCl, 3 M KCl) electrode
as reference electrode. EIS experiments were carried out after an
immersion of sample in 3.5 wt.% NaCl for 30 min. They were car-
ried out at frequencies ranging from 105 to 102/102 Hz at open cir-
cuit potential with amplitude of perturbation voltage of 10 mV. For
this measurement, 12 points are recorded per decade. Each test
was repeated more than three times to verify repeatability of re- Fig. 1. XPS spectra of filmed zinc (a)XPS survey spectra, (b) N1s spectra and (c) O1s
sults. EIS results were analyzed by fitting data using Zsimpwin spectra.
software.
and the weak peak at 400.0 eV is consistent with that of a free
3. 3. Results and discussion amine group [20]. O 1s peak (Fig. 1c) is decomposed into two com-
ponents. The oxygen peak registered at binding energy of 531.5 eV
3.1. Composition, wetability and morphology confirms presence of water molecules [21,22], a weak peak at
530.6 eV can be ascribed to zinc oxide [21]. It is implied that the
Fig. 1 shows XPS spectra of filmed zinc. From XPS survey spectra film obtained is mainly composed of complex zinc–laurylamine.
(Fig. 1a), it can be found that C and N elements exist in film, indi- There are some free laurylamine and zinc oxide in film.
cating existence of laurylamine species. N1s spectra (Fig. 1b) exhi- Fig. 2 shows contact angle photographs of bare and filmed zinc
bit two distinct peaks at 399.4 eV and 400.0 eV. The main peak at specimens. It is found that bare zinc surface is hydrophilic with
399.4 eV corresponds to amine group coordinated with zinc ions, water contact angle of 62 ± 3° (Fig. 2a), and filmed zinc presents
 P. Wang et al. / Corrosion Science 69 (2013) 23–30
Fig. 2. Contact angle photographs of (a) bare and (b) filmed zinc.
super-hydrophobic property with water contact angle of 151.2 ± 3°
(Fig. 2b). After exposure in ambient condition for 1 month,
water contact angle of filmed zinc is 150.5 ± 3°, indicating that
it can maintain super-hydrophobic property in atmospheric
environment.
In case of super-hydrophobicity, air is believed to be trapped in
groove of film, and Cassie model is usually introduced to explain
wettability of film. Assuming that water contact angle for air is
180°, apparent contact angle (hr) of filmed zinc can be expressed
as follows [23]:
cos hr ¼ f1 cos h  f2
In Eq. (1), f1 and f2 are fractions of solid surface (zinc–
laurylamine) and air in contact with water; hr and h are water con-
tact angles on rough and smooth solid surfaces (zinc–laurylamine),
respectively. According to Eq. (1), air trapped in groove can mini-
mize real contact area between a water droplet and solid surface.
Consequently, the hydrophobicity of surface is dramatically
intensified. According to previous reports [23,24], contact angle
is generally in the range 113°–115° when a compound with group
CH3(CH2)m(m P 10) forms self-assembled monolayer on flat metal
substrate. Thus, f1 value of the super-hydrophobic film with water
contact angle of 151.2° (Fig. 3b) is 0.2030, and the air fraction is
0.7970.
Fig. 3. Morphology and cross section of filmed zinc (a) bar = 100 lm, (b) bar = 10 lm and (c) bar = 200 lm.
25
Fig. 3 presents morphology and cross section of film.
Micrometer-sized papillae structures are found on filmed zinc
surface (Fig. 3a), and they connect with each other by ridge-like
structure (Fig. 3b). From SEM picture of cross section (Fig. 3c), it
can be observed that film presents rough structure with a thickness
of about 200 lm. Generally, super-hydrophobicity of film is
assumed to be related to its morphology. In order to understand rel-
evance of wettability to micro-morphology of film, image binariza-
tion method is employed to simulate contact interface between
water droplet and filmed zinc surface, and it is performed through
a self-written program running on the Visual Basic.net platform.
Before image binarization process, some assumption should be
made in advance. In a SEM image, the distance between a pixel
point and substrate can be reflected by its gray scale ranging from
0 to 255. Generally, pixel point with low gray scale in image indi-
cates that it is far away from substrate, and it is more likely to con-
nect with water droplet. Thus, there must be a critical value for the
gray scale to determine whether a pixel point contacts with water
droplet. Base on this assumption, a black-white two-colored image
can be extracted from gray scale image (SEM image) by assigning a
ð1Þ
threshold value with image binarization. In details, if the gray scale
value is lower than a threshold value, the pixel point can be set as 0;
otherwise, it is set as 1. In black-white two-colored image obtained,
the point with white color is the most possible contact region of so-
lid with water, and the point with black color indicates the region
trapped by air. As we have calculated above, the solid fraction of
super-hydrophobic film with a water contact angle of 151.2°
(Fig. 3a) is 0.2030. In this case, a black–white two-colored image
with the proportion of white pixel of 20.26% (Fig. 4) can be trans-
ferred from Fig. 3a by setting threshold value as 136. From this im-
age, it can be observed that white pixels mainly come from top of
papillae and ridge-like structure. When a water droplet is dropped
on the surface, it connects with surface through the top of papillae
26 P. Wang et al. / Corrosion Science 69 (2013) 23–30
Fig. 4. Black-white two-colored image transferred from Fig. 3a with threshold
value of 136.
and ridge-like structures, and air is trapped among these structures.
So the presence of papillae and ridge-like structure on filmed zinc
surface is main reason for its super-hydrophobicity.
3.2. Formation mechanism of super-hydrophobic film
Fig. 5 is morphology of zinc substrate after removing super-
hydrophobic film with ultrasonic vibration. It can be observed that
pits are dispersed on zinc surface (Fig. 5a), and space between two
pits ranges from 10 to 40 lm (Fig. 5b), which is the same to the
range of distance between two papillae on film (Fig. 3). This result
implies that appearance of papillae structure on filmed zinc surface
is related to formation of pits under film during electrolysis
process.
Based on these results above, the formation mechanism of
super-hydrophobic film is proposed as follows: under high anodic
potential, Zn2+ ions are released from zinc surface. These released
Zn2+ ions can be captured by laurylamine moiety in solution imme-
diately to form zinc–laurylamine complex according to reaction
(2):
Zn2þ þ CH3 ðCH2 Þ11 NH2 ! Zn½CH3 ðCH2 Þ11 N þ 2Hþ
2+
It can be inferred that the releasing speed of Zn at pits is high-
er than other places, and the concentration of zinc–laurylamine
complex over pits is the highest in solution. Thus, zinc–
laurylamine is prone to precipitate over pits at anode when it is
Fig. 5. Morphology of the zinc substrate after removing super-hydrophhobic film (a) bar = 100 lm and (b) bar = 10 lm.
supersaturated. As a result, rough film with papillae structure is
formed on zinc surface. Furthermore, during electrolysis process,
oxygen in solution can induce formation of zinc oxide, and water
molecule dissolved in solution can also combine with Zn2+ to form
zinc oxide. These two aspects can explain the existence of zinc
oxide on zinc surface (Fig. 1c).
3.3. The deliquescence process of NaCl particle on super-hydrophobic
film
Generally, salt particle in the environment with RH higher than
a critical value (saturated relative humidity of salt solution) can ab-
sorb water molecule to deliquesce. The deliquescence of salt parti-
cle is a common phenomenon in nature, especially in the marine
atmospheric environment with high relative humidity (RH). It is
regarded as one of the important reasons that induce atmospheric
corrosion. Thus, to monitor deliquescence process of salt particle
on super-hydrophobic surface can help to reveal possibility of
using it as atmospheric corrosion barrier. Fig. 6 shows evolution
process of NaCl particle on super-hydrophobic film in simulated
atmospheric environment with RH of 90%, which is higher than
the critical value for NaCl (76%) [25]. It can be observed that edges
of NaCl particle become dark within 6 min (Fig. 6b), indicating that
these areas deliquesce preferentially. After exposure of 12 min,
NaCl particle surface is enwrapped by saline water droplet, which
appears as hemisphere structure for action of surface tension
(Fig. 6c). With process of deliquescence, more water molecule ad-
sorbs onto salt particle surface, and saline water droplet gets larger
(Fig. 6d-h). After the exposure of 60 min, NaCl particle transfers to
saline droplet completely (Fig. 6h). It should be noticed that con-
tact angle of the saline water on filmed zinc is 117.1 ± 3°, implying
that water droplet penetrates into groove of film during deliques-
cence process, and it contacts with film in Wenzel mode [18,26]. In
order to prove this point, filmed samples before and after deliques-
cence processes are immersed into water, and observed at an obli-
que angle. Their optical photographs are shown in Fig. 7, and the
definition of abbreviations used is shown in Table 1. It is clear that
SS appears as a silver mirror (Fig. 7a), indicating that air can be
trapped in film, and water contacts with super-hydrophobic film
in Cassie mode. From the side view of SD at the same oblique angle
in water (Fig. 7b), it can be observed the area that was covered by
saline water droplet in atmospheric environment gets dark (the
area within the red circle in Fig. 7b), proving that saline water pen-
ð2Þ
etrates into film during the deliquescence process of NaCl particle.
As we have proven in reference [27], capillary condensation occurs
in groove of film in environment with high RH. This process allows
vapor to condense below saturation vapor pressure of pure liquid,
which can be attributed to intensified van der Waals interactions
 P. Wang et al. / Corrosion Science 69 (2013) 23–30
Fig. 6. Formation process of water droplet on super-hydrophobic film due to deliquescence of NaCl particle in simulated marine atmospheric environment (a) 0 min, (b)
6 min, (c) 12 min, (d)18 min, (e) 30 min, (f) 40 min, (g) 50 min and (h) 60 min.
Table 1
Definition of abbreviations used (BS, SS, SD and SR).
Abbreviation Definition
BS Bare sample
SS Super-hydrophobic film coated sample
SD SS after deliquescence process of NaCl
SR SD washed with water and then dried in atmospheric
environment with RH of 60% until water volatilizes
completely
between vapor phase water molecules inside the confined space of
groove filled with air. Thus, at pressures lower than the normal sat-
uration pressure, vapor condenses in groove, and it induces
replacement of air by water. Furthermore, micro-structure of film
might be an important factor that affects penetration process of
saline water into super-hydrophobic film. For super-hydrophobic
film connected with water, air can be trapped in groove of film,
and liquid forms a convex surface between interface of liquid
and air for capillary. At this interface, capillary pressure prevents
water to penetrate into film, and it can be calculated according
to the Young–Laplace equation:
2c cos h
Pc ¼ ð3Þ
r ine water into film weakens corrosion protection performance of
In this equation, Pc is capillary pressure, r the characteristic va-
lue of radius of cylindrical tube, c the surface tension of the liquid–
air interface, and h the contact angle of liquid to the cylindrical
tube.
According to Eq. (3), it is clear that the higher the value of r, the
lower the capillary pressure. Thus, the high value of distance be-
tween two papillae (Fig. 3a) on film facilitates contact mode trans-
fer of water droplet during NaCl deliquescence process.
27
In order to study the recovery property of super-hydrophobic
film, SD is washed with water and then dried in atmospheric envi-
ronment with RH of 60% until water volatilizes completely. When
the SD after drying (SR) is immersed into water, the entire surface
appears as silver mirror again (Fig. 7c), indicating that the film can
recover super-hydrophobicity, and it connects with water in Cassie
mode again.
3.4. The barrier effect of super-hydrophobic film in simulated marine
atmosphere
In order to clarify barrier effect of super-hydrophobic film to the
atmospheric corrosion induced by deliquescence of salt particle,
electrochemical measurements for BS, SS, SD and SR are carried
out in 3.5 wt.% NaCl solution. Fig. 8 shows Eoc values of the four
samples. Eoc of BS is stable at -1.02 V vs. Ag/AgCl (3 M KCl). In pres-
ence of super-hydrophobic film, Eoc of SS is unstable within testing
interval. This can be attributed to poor electrical conductivity for
air trapped in film. Furthermore, Eoc of SS is higher than that of
BS, indicating that the film that connects with corrosive medium
in Cassie mode can reduce susceptibility of underlying zinc corro-
sion, though Eoc value does not provide any direct information on
corrosion kinetics [28]. After saline water droplet penetrates into
film for deliquescence of NaCl, Eoc of SD decreases to about
0.8 V vs. Ag/AgCl (3 M KCl). It is suggested that penetration of sal-
film. After removing of saline water penetrated in film, Eoc of SR in-
creases to around 0.5 V vs. Ag/AgCl (3 M KCl). It results from the
behavior that SD recovers super-hydrophobicity and it contacts
with corrosive medium in Cassie mode again.
Fig. 9 presents (a) Nyquist, (b) Bode–phase angle versus fre-
quency and (c) Bode |Z| versus frequency plots for BS, SS, SD and
SR in 3.5 wt.% NaCl. EIS result of BS shows similar characteristics
with zinc immersed in 0.6 M NaCl [29]. For the existence of
28 P. Wang et al. / Corrosion Science 69 (2013) 23–30
Fig. 7. Optical photographs of (a) SS, (b) SD and (c) SR in water.
adsorbed species that contributes to the formation of corrosion
layer [30], EIS result can be analyzed with circuit shown in
Fig. 11a, in which Rs is solution resistance, Rt charge-transfer resis-
tance, Rf resistance of film (corrosion product), and Qdl and Qf con-
stant phase elements modeling capacitance of double and
corrosion layers, respectively [11]. The impedance of Q is defined as
Z Q ¼ 1=Y 0 ðjxÞn
where Y0 represents modulus, x angular frequency, and n the phase
[31].
In case of SS, EIS data can only be achieved within frequency
range of 105–102 Hz because of poor electro-conductivity of
super-hydrophobic film. Within frequency range, interface imped-
ance of super-hydrophobic film can be reflected. It can be observed
that phase angle is almost 90° (Fig. 9b), and the slope of the imped-
ance against the log (frequency) is about 1 (Fig. 9c). This behavior
is comparable to any high-performance coating [11]. Note that
impedance of SS is at least four orders higher than that of BS
(Fig. 9c), confirming the excellent anti-corrosion effect of super-
hydrophobic film on zinc, as well as the great contribution of air
in maximizing anti-corrosion property. According to the result
shown in Fig. 7a and related analysis, an interface model for SS im-
mersed in NaCl solution is proposed (Fig. 10a). Super-hydrophobic
film can easily trap air within groove between ‘‘hills’’ (metal com-
plex) in electrolyte, and liquid forms a convex surface between
Fig. 8. Eoc  t curves obtained on BS, SS, SD and SR in 3.5 wt.% NaCl solution.
interface of liquid and air for capillary. In this case, an air film
forms between film and liquid interface. Thus, equivalent circuit
shown in Fig. 11b is proposed to analyze EIS results of SS. In this
circuit, constant phase element Qair and resistance Rair are intro-
duced to characterize air film, and a parallel combination of con-
stant phase element Qf and resistance Rf is used to characterize
complex film.
ð4Þ Fig. 10b presents interface model of SD in 3.5 wt.% NaCl solu-
tion. As we have proven above, after deliquescence process, a drop-
let forms on super-hydrophobic film and it penetrates into film. In
this case, water droplet penetrated into film provides a pathway
with lower resistance for electron transfer. From Bode |Z| versus
frequency plots (Fig. 9c), it can be found that impedance of SD de-
creases for two orders of magnitude, indicating the failure of
super-hydrophobic film after deliquescence process of NaCl parti-
cle. According to the Bode –phase angle versus frequency plots of
SD shown in Fig. 9b, there are at least 3 time constants within
the frequency range, which can be associated with air film, com-
plex film and electron transfer at the interface. Furthermore, an
obvious inductive loop can be found from Nyquist plots in
Fig. 9a, and it represents pitting under super-hydrophobic film
(as proven in Fig. 5). Thus, an equivalent circuit shown in
Fig. 11(c) is proposed to fit EIS plots of SD. In this circuit, constant
phase element Qair and resistance Rair are introduced to character-
ize air film. A parallel combination of constant phase element Qf
and resistance Rf is used to characterize complex film. Qdl and Rt
represent double layer constant phase element and charge transfer
resistance, respectively. Rp and L are corresponding parameters for
pitting.
In case of SR, its impedance increases after water droplet that
penetrates into film is removed. This is the result of behavior that
SR recovers super-hydrophobicty, and it agrees with the conclu-
sion drawn from open circuit potential results (Fig. 8). In this case,
interface between liquid and super-hydrophobic film is similar
with SS, and the equivalent used for SS (Fig. 11b) can be used to
fit its EIS results. It is noteworthy that impedance of SR is a little
lower than that of SS, this might be related to micro-structure de-
stroy during water drying process due to high surface tension of
water.
Table 2 summarizes fitted electrochemical parameters for BS,
SS, SD and SR. The listed inhibition efficiency (g) is calculated with
following formula [32]:
!
R0t
gð%Þ ¼ 1   100 ð5Þ
Rt
 P. Wang et al. / Corrosion Science 69 (2013) 23–30
Fig. 9. EIS results obtained on BS, SS, SD and SR in 3.5 wt.% NaCl solution (a) Nyquist
plots, (b) Bode-phase angle versus frequency plots and (c) Bode |Z| versus frequency
plots.
where R0t is charge transfer resistance of BS, and Rt is charge transfer
resistance of SD. For SS and SR, Rf is used to substitute Rt for inhibi-
tion efficiency calculation.
It should be noticed that SS presents excellent inhibition effect
with an inhibition efficiency of 99.99%. The values of nair for SS and
SR are both 1, indicating that air film acts as a pure capacitor that
inhibits electron transfer between substrate and solution. Note
that Rair decreases from 2.181  108 X cm2 to 2.049  105 X cm2,
and Rf decreases from 2.085  108 X cm2 to 2.01  106 X cm2 after
deliquescence process of NaCl, indicating that saline water that
displaces air in film provides a pathway with low resistance for
29
Fig. 10. Interface model of (a) SS and (b) SD in 3.5 wt.% NaCl solution.
Fig. 11. Equivalent circuits for samples in 3.5 wt.% NaCl solution.
the electron transfer. It can provide a closed circuit for electron
transfer between anode and cathode, which is one of foundational
conditions for electrochemical corrosion process. In this case, the
advantage of applying super-hydrophobic film in marine atmo-
spheric corrosion protection is declined. As we expect, inhibition
efficiency of SR increases to 99.99% after water droplet penetrated
into film is removed. This is the result of behavior that the film
recovers super-hydrophobicty after drying, and it agrees with the
conclusion drawn from open circuit potential results (Fig. 8).
4. Conclusions
In summary, super-hydrophobic film composed of zinc–lauryl-
amine is fabricated on zinc surface with electrolysis method. The
image binarization result of SEM image proves that super-
hydrophobic property of film results from papillae and ridge-like
structures. Formation of papillae can be attributed to preferential
30 P. Wang et al. / Corrosion Science 69 (2013) 23–30

Table 2
The electrochemical parameters for BS, SS, SD and SR.

Samples Rs Cair nair Rair Cf nf Rf Cdl ndl Rt L Rp g (%)

(X cm2) (F cm2 1010) (X cm2 103) (F cm2 1010) (X cm2 103) (F cm2 106) (X cm2 103) (H cm2 103) (X cm2 103)
BS 4.3 - - - 475,000 0.82 0.188 194 0.41 0.575 – – –
SS 5.7 0.572 1 21,810 0.1664 0.93 208,500 – – – – – 99.99
SD 6.8 2.733 0.94 204.9 22,530 0.87 2010 0.00145 0.93 788.6 11.41 307.2 99.93
SR 5.3 0.973 1 13,770 0.2728 0.92 336,100 – – – – – 99.99

precipitation of zinc laurylamine over pits during uneven corrosion
of zinc at high anodic potential. The super-hydrophobic film can
present excellent anti-corrosion property with inhibition efficiency
of 99.99% to the underlying zinc. However, during deliquescence
process of NaCl in simulated marine atmosphere, capillary conden-
sation in groove of film can induce penetration of saline water into
film, and high value of distance between two papillae on film that
results in low capillary pressure facilitates this process. The pene-
tration behavior of saline water provides a closed circuit for elec-
tron transfer between anode and cathode of substrate, and
declines corrosion inhibition effect of super-hydrophobic film in
simulated marine atmospheric environment. After being washed
with water and dried in atmospheric environment with low rela-
tive humidity, the filmed zinc can recover super-hydrophobic
property and excellent anti-corrosion property.
Acknowledgements
This work was supported by National Natural Science Founda-
tion of China (Grant Nos. 41106069 and 51131008), Natural Science
Foundation of Shandong Province (Grant No. ZR2011EMQ008).
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