Corrosion Science 65 (2012) 520527

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

Effects of pH and Cl concentration on corrosion behavior of the galvanized steel

in simulated rust layer solution
Shuan Liu a,b, Huyuan Sun a,, Lijuan Sun a, Huiji Fan a,b
a
Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, PR China
b
Graduate University of Chinese Academy of Sciences, Beijing 100049, PR China

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

Article history: Effects of pH and Cl concentration on the corrosion behavior of galvanized steel in simulated rust layer
Received 17 June 2012 (SRL) solution have been investigated using measurements of weight loss, electrochemical impedance
Accepted 22 August 2012 spectroscopy (EIS), linear polarization combined with cyclic polarization experiment. In neutral SRL solu-
Available online 5 September 2012
tions, pitting corrosion occurred on the galvanized steel simultaneously. However, exposure to high alka-
line solutions resulted in passivation. Results revealed that the galvanized steel in SRL solution was
Keywords: susceptible to pitting corrosion in all chloride solution of concentration ranging between 0.1 and 0.6 M.
C. Rust
2012 Elsevier Ltd. All rights reserved.
B. EIS
C. Pitting corrosion

1. Introduction cryrust layer on zinc coating exposed to seawater. He found that

Galvanized steel is widely used for applications such as build-
ing, automotive body parts and water distribution systems. The
protection obtained by zinc coating is due to barrier and galvanic
double protective effect [14]. Zinc is anodic to iron and behaves
as sacricial material in the humid and aqueous environment
[5,6]. However, many cases of heavy damage of galvanized pipes
and tanks have been reported as being due to corrosion processes
in water hanging system, as clearly evidenced by the production of
rust layer in those systems after an unexpectedly short lifetime [7].
The accumulation of the corrosion products would affect corro-
sion-related processes, such as the mass transport of the dissolved
oxygen, the hydration of dissolved metal ions and the passivation
properties of zinc coating. The corrosion products play an impor-
tant role in the corrosion resistance of metals. In recent years,
the experiments, such as atmospheric exposure [8,9], seawater
immersion [10], wet and dry cycles [11] were carried out to study
the corrosion resistance of galvanized steel. However, the experi-
mental studies on the corrosion behaviors of galvanized steel un-
der rust layer environment have been seldom reported up to
present.
Extensive research data showed that the main corrosion product
detected on the Zn coating was basic zinc chloride (Zn5Cl2(OH)8) in
the marine corrosion environment, and this rust layer has a strong
correlation with the corrosion characteristics of the galvanized steel
[1215]. Li [6] used XRD and TEM to analyze the formation of nano-
Corresponding author. Tel./fax: +86 532 82898732.
E-mail address: sun@qdio.ac.cn (H. Sun).
nanometer was the main rust layer on the surface of zinc coating.
Our research work has been focused on the electrochemical and
surface studies of the Zn coating exposed to seawater [16]. We also
have analyzed the degradation mechanism of galvanized steel under
different Cl concentration [17].
In this paper, saturated Zn5Cl2(OH)8 solution was used to simu-
late the rust layer in the marine environment, the effects of the pH
value and Cl concentration on the corrosion behavior of galvanized
steel in SRL solution were investigated by various electrochemical
measurements, including linear polarization curves, cyclic polariza-
tion curves and electrochemical impedance spectroscopy (EIS). The
corrosion morphologies were investigated by scanning electron
microscopy (SEM) and the corrosion products were determined
using X-ray diffraction (XRD) and energy dispersive spectroscopy
(EDS). The results of this paper may provide an insight on improving
the corrosion resistance of galvanized steel in the marine
environment.
2. Experimental
2.1. Sample and SRL solution preparation
Galvanized steel was purchased from Shanghai BaoSteel and
used in the experiments. The nominal composition of zinc coating
(% by weight) is 0.04% C, 0.2% Mn, 0.01% P, 0.008% S, 0.036% Ti and
the rest zinc. Corrosion experiments were conducted on electrodes
made from galvanized steel, cold mounted in epoxy resin to give an
exposed area of 1 cm2 to the media. A copper wire was connected
to the backside of each specimen with a silver paste. Before each

0010-938X/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2012.08.056
 S. Liu et al. / Corrosion Science 65 (2012) 520527
experiment, the working surfaces of the electrodes were degreased
with ethanol, then cleaned with distilled water, and nally dried in
air. In order to avoid a prolonged exposure to the atmosphere, the
specimens were tested immediately after the degreasing and dry-
ing processes.
The test solution was prepared by adding distilled water and
self-made Zn5Cl2(OH)8. The reaction was given by (1):
5ZnCl2 8NH3  H2 O ! Zn5 Cl2 OH8 8NH4 Cl 1
The reaction temperature was 80 C and reaction time was 2 h.
Excessive Zn5Cl2(OH)8 was added in SRL solution in order to main-
tain its saturation. The pH of the solution was adjusted by using
analytical-grade reagent NaOH and NaHCO3. The Cl concentration
contained in the solution was 0.10.6 M (0.583.5 wt.%) by adding
NaCl, respectively.
2.2. Weight loss tests
According to ISO standards 8407-1991, weight loss tests were
conducted in breakers containing 0.6 M NaCl SRL solution of differ-
ent pH at room temperature. The specimens were weighed before
the tests. To determine the loss of weight, once the period of
immersion (30 days) was nished, the specimens were removed
from the solutions tests and the rust layer was scraped off by a sur-
gical blade, the residual rust on specimen was removed by immer-
sion in NH4Cl solution (100 g/L) at 70 C for 5 min, washed with
abundant distilled water, dried and then weighed to determine
their mass loss.
2.3. Electrochemical measurements
Electrochemical measurements were carried out in a conven-
tional three-electrode cell with a platinum counter electrode and
a saturated calomel electrode (SCE) as reference. All the potentials
in this paper are reported in the SCE scale. The volume of the cell
was 400 ml. The specimen was immersed in SRL solution and al-
lowed to attain a stable open circuit potential (OCP) before starting
the polarization scan. The polarization curves were recorded by
changing the electrode potential automatically with an EG&G
2273 potentiostat, at a scan rate of 0.5 mV/s. All the tests were per-
formed at room temperature (25 C).
For the cyclic polarization curves, the polarization curves were
plotted by starting scanning electrode potential from an initial po-
tential of 250 mV below the open circuit potential (OCP) up to 0 V.
When the electrode potential reached the anodic potential of 0 V,
the potentials were scanned back to the initial potential. A vertex
current density of 0.001 A/cm2 was used. For the linear polariza-
tion measurement, a sweep range of 10 to +10 mV versus OCP
at a sweep rate of 0.166 mV/s was used, and the polarization
resistance (Rp) was determined from the slope of the potential
(E) versus current (i) curve in the vicinity of the corrosion potential.
The EIS measurements were carried out using ac signals of ampli-
tude 10 mV peak to peak at OCP in the frequency range of 100 kHz
to 10 mHz, with 10 points per decade. Zview software was used to
analyze the EIS data with equivalent circuit.
To determine the reproducibility of the data, three parallel spec-
imens were performed for polarization curves and representative
results were selected. The same ve parallel specimens were car-
ried out for weight loss tests and average values were listed.
2.4. Observation and characterization of corrosion products
XRD analysis was used to determine the corrosion products
formed on the zinc coating under different conditions. An X-ray
diffractometer with Cu ka radiation (k = 0.154 nm) and 1080
scanning range was used to obtain XRD patterns form the powder
521
scraped from the surface of the specimens. The microstructure of
the rust layer absorbed on the surface of electrode was observed
and recorded by using a KYKY-2800B SEM, and the eld emission
energy was 10 keV. The chemical composition of the corrosion
products was determined using a GENESIS 4000 energy dispersive
spectroscopy (EDS) attached to the SEM.
3. Results and discussion
3.1. Effects of Cl concentration in the SRL solution
EIS is an in situ, rapid and convenient technique useful for eval-
uating the corrosion performance of coated metals subjected to
aqueous environment [18,19]. It not only provides a non-destruc-
tive assessment of the corrosion rate, but also enables the determi-
nation of the corrosion mechanism. The state variables of the
corrosion process could be determined by the number of the time
constants in EIS spectroscopy. Also, the corrosion reaction mecha-
nism and dynamic processes could be quantitatively analyzed by
the EIS data which are tted by equivalent circuit [20,21] (see
Fig. 1).
The Bode plots in Fig. 5 showed that two time constants occurred
during the whole immersion times. Two equivalent electrical cir-
cuits were given in Fig. 2 and were employed to t the EIS of the gal-
vanized steel under SRL solution containing different Cl
concentration (pH 7.0). The rst equivalent circuit (Fig. 2A) was used
to t the EIS data only displaying two capacitive loops, whereas the
second one (Fig. 2B) was used to t the EIS data displaying a Warburg
impedance [22]. In the two equivalent circuit models, Q is the
constant phase angle element, expressed as xn/Y0(cos np/2 + j
sin np/2), where Y0 and n are the constant and exponent, respec-
tively, and x is the angular frequency in rad s1 (x = 2p f), and
j2 = 1 is an imaginary number. Rs is the solution resistance of SRL
solution, the high-frequency circuit Rf  Q1 corresponds to the
capacitance and resistance of the surface lm of rust layer; the med-
iumlow frequency circuit Rct  Q2 is the double-layer capacitance
and charge transfer resistance, and W represents the Warburg diffu-
sion impedance appearing in the low-frequency region. For the
capacitive loops, the coefcients n1 and n2 represent a depressed
feature in the Nyquist diagram.
When the galvanized steel immersed in chloride-free SRL med-
ium, the radius of capacitive loops were much larger than that in
chloride-contained SRL solution, and the size of the capacitive
loops did not change with time, indicating that the galvanized steel
has excellent passivation property in the SRL solution. According to
the tting results in Table 1, the Rs value decreased with the in-
crease of Cl concentration, indicating that Cl could decrease
the resistance of the solution. The change of Q2 was attributed to
the change of real area of the corroded electrode during the corro-
sion process [19]. The impedance measured in SRL solution con-
taining 0.4 and 0.6 M NaCl exhibited a tail corresponding to the
Warburg impedance in the low frequency region in the Nyquist
plots, indicating that a oxygen diffusion-controlled corrosion pro-
cess occurred on the rust layer of the galvanized steel. The changes
of the impedance spectra in both size and shape with the extension
time, including the appearance of the Warburg impedance and de-
crease in the capacitive loop in size, showed that the rust layer was
thinned and the protection afforded by the rust layer was de-
stroyed under the Cl erosion [23].
The reciprocals of Rct are used to represent corrosion rate of gal-
vanized steel, because the Rct is more intimately correlated to the
corrosion rate than Rp when there state variable, such as corrosion
products, to affect the EIS apart from potential [24,25]. Fig. 3
showed the time dependence of 1/Rct of galvanized steel under
SRL solution at different Cl concentration from the curve tting
522 S. Liu et al. / Corrosion Science 65 (2012) 520527

1.172 kHz
1200 blank 2d blank
672 Hz 50
0.03 Hz 7d
14d 2d
21d 40 7d
900 14d

phase angle/deg.
21d

-Z'' / cm2
30
7.88 Hz
600
20

300 0.09Hz
2.043 kHz 10
3.562 kHz
0 0

0 1000 2000 3000 4000 5000 6000 -2 -1 0 1 2 3 4 5

Z' / cm2 log f / Hz

0.03 Hz
0.1M NaCl 0.1M NaCl
500 50
2 d 2d
400 7 d 40 7d
14 d 7.88 Hz 0.017Hz 14d
cm2

phase angle/deg.
300 21 d 0.01 Hz 0.01 Hz 21d
30
-Z'' /

200
20
100 23.95 Hz
10
0 10.82 kHz
0
0 500 1000 1500 2000 -2 -1 0 1 2 3 4 5
Z' / cm2 log f / Hz

400 50
0.2 M NaCl 0.09 Hz 0.2 M NaCl

320 1d
1d 40 7d
7d 14 d
phase angle/deg.

240 14d 21d

21d 30
-Z'' / cm2

160
0.28 Hz 20
0.16 Hz
80
10
18.87 kHz
0 10.82 kHz
0 -2 -1 0 1 2 3 4 5
0 300 600 900 1200
log f / Hz
Z' / cm2

500 90
0.4 M NaCl 0.4 M NaCl
80
2d 2d
400 70
7d 7d
14 d 0.01Hz 60
14d
phase angle/deg.

300 21d
-Z'' / cm2

0.49 Hz 50 21d
72.79 Hz
40
200
30
0.28 Hz
20
100
7.88 Hz 10
32.90 kHz
0 57.36 kHz 0
0 400 800 1200 1600 -2 -1 0 1 2 3 4 5
Z' / cm2 log f / Hz

400 0.6 M NaCl 90

0.161 Hz 0.6 M NaCl
80
2d 2d
7d 70 7d
300 41.75 Hz 0.161 Hz
14d
phase angle/deg.

60 14d
21d 21d
-Z'' / cm2

50
7.88 Hz
200 40
30
100 20
4.52 Hz 10
0.28 Hz
0
0
0 500 1000 1500 2000 -2 -1 0 1 2 3 4 5
Z' / cm2 log f / Hz

Fig. 1. Nyquist and Bode plots of galvanized steel under different Cl concentration of SRL solution.

data. Apparently, the corrosion rate of galvanized steel in layer and react with the metal directly [23]. By comparing the
0.10.6 M NaCl increased with time, indicating that Cl can corrosion rate at the same time in the chloride-free medium, the
penetrate from the rust layer, destruct the structure of the rust corrosion rate kept invariant and much lower than that in
 S. Liu et al. / Corrosion Science 65 (2012) 520527 523

Fig. 2. Equivalent circuit models used to t the experiment impedance data of galvanized steel under different Cl concentration in SRL solution.

Table 1
Values of electrochemical parameter in different Cl concentrations in SRL solution.

T (days) Rs (X cm2) Q1 (lF cm2) n1 Rf (X cm2) Q2 (lF cm2) n2 Rct (X cm2) W (X cm2)
0M 1 120.7 47.2 0.55 565.1 0.43 0.80 6467
3 150.3 28.3 0.62 653.4 0.65 0.78 6530
7 286.6 1.61 0.78 654.2 1.02 0.63 6460
10 186.4 2.65 0.83 756.2 5.32 0.56 6825
14 183.7 1.41 0.81 858.2 10.1 0.42 5593
21 101.3 152.1 0.72 967.8 1.02 0.81 6988
0.1 M 1 17.47 230 0.28 195.3 2.12 0.82 2363
3 18.32 56.9 0.65 173.5 3.21 0.65 1986
7 11.50 1.02 0.88 188.9 2.42 0.31 1527
10 19.23 5.23 0.32 175.8 5.62 0.48 1563
14 15.81 102.3 0.29 276.2 5.91 0.80 2473
21 16.33 7.62 0.71 180.7 750.4 0.44 2642
0.2 M 1 15.32 113.2 0.27 88.46 1.23 0.81 3055
3 29.34 86.2 0.36 96.3 56.3 0.68 2056
7 12.19 65.2 0.80 67.07 98.5 0.58 1976
10 11.23 94.2 0.64 59.3 231.3 0.64 1635
14 10.36 45.2 0.61 93.8 862.2 0.62 1974
21 7.51 51.2 0.59 103.7 761.2 0.62 859.5
0.4 M 1 3.21 2.62 0.84 66.8 47.6 0.83 883.7
3 5.36 56.3 0.82 88.6 91.2 0.34 795.6
7 1.17 160.2 0.25 95.6 1.47 0.81 875.2 0.00012
10 2.39 521.3 0.56 88.6 58.4 0.65 723.5 0.00026
14 2.25 980.1 0.24 73.2 8.01 0.72 516.1 0.00035
21 4.95 27.5 0.67 50.7 384.2 0.48 705.1 0.00139
0.6 M 1 2.01 39.2 0.56 83.6 222.6 0.92 1887
3 2.58 18.6 0.85 76.8 364.2 0.65 1125
7 0.35 52.3 0.61 52.6 298.3 0.54 607.5 0.0114
10 6.59 48.6 0.65 68.6 263.3 0.59 586.3 0.00963
14 3.56 28.6 0.73 58.6 253.5 0.73 561.2 0.00356
21 3.86 26.3 0.82 61.2 301.2 0.63 362.4 0.00268

0.003
1000
0 M NaCl
0.1 M NaCl
0.2 M NaCl 800 0 M NaCl
0.4 M NaCl
0.002 0.1 M NaCl
cm-2)

0.6 M NaCl
cm2

600 0.2 M NaCl

0.4 M NaCl
-1

0.6 M NaCl
1/Rct(

Rf /

400
0.001

200

0.000 0
0 7 14 21 0 7 14 21
Time /day Time /day

Fig. 3. The change of 1/Rct on galvanized steel under different Cl concentration in Fig. 4. The change of Rf on galvanized steel under different Cl concentration in SRL
SRL solution. solution.

chloride-contained medium, indicating that the rust layer could
inhibit the corrosion of the zinc coating.
The Rf of the galvanized steel in the SRL solution containing
different Cl concentration were showed in Fig. 4. It can be clearly
observed that Rf value increased from 565.1 to 967.8 X cm2 with
the increase of the immersion time in SRL solution in a chloride-
free medium, indicating that new corrosion products generated
and absorbed on the electrode surface, the protective effect of rust
layer on galvanized steel was gradually enhanced. However, in the
chloride-contained medium, the Rf value decreased gradually with
the increase of immersion time, and the Rf value decreased as the
Cl concentration increased, indicating that corrosion products
lm absorbed on the electrode surface gradually damaged under
the erosion of Cl.
524 S. Liu et al. / Corrosion Science 65 (2012) 520527

The different corrosion behavior of galvanized steel under
0.10.6 M NaCl and chloride-free SRL solution can be explained
as followed: Cl is a strong anodic activator because of its smallest
radius and volume, so it can penetrate from the rust layer, destruct
the structure of the rust layer and react with the substrate metal
directly. After the Cl destroyed some of the rust layer, the
substrate metal appeared and acted as an anode, and the others
of the intact rust layer acted as a cathode, therefore, an activa-
tioninactivation corrosion cell was formed, owing to the smaller
anode vs. the larger cathode, this resulted in accelerating the
corrosion of galvanized steel [26].
According to the above discuss, it is clear that corrosion resistant
of galvanized steel under SRL solution at various Cl concentration is
signicantly different from that in the chloride-free medium.
3.2.2. Linear polarization in the SRL solution
A similar results to the weight loss measurements were drawn
from the analysis of the reciprocal values of polarization resistance
(1/Rp) calculated from the corresponding curves of linear polariza-
tion. Fig. 6 showed the values of 1/Rp of galvanized steel vs. pH in
SRL solution containing 0.6 M NaCl.
It can be clearly seen from the gure that, the corrosion rate
(1/Rp) decreased gradually with the increase of pH values from
7.0 to 13.0, which can be attributed to the effect of corrosion prod-
ucts. Yeomans [27] demonstrated that a passive lm generated on
the zinc coating in high alkaline solution. Therefore, it is possible
that a stable passive lm formed on the galvanized steel and acted
as protector against corrosive medium.

3.2. Effects of the pH in the SRL solution

3.2.1. Weight loss measurements 0.0

The weight loss of specimens in SRL solution containing 0.6 M pH=7.0
NaCl at different pH values, after 30 days immersion at room tem-
-0.3

potential (vs.SCE), V
perature were obtained and showed in Fig. 5. The corrosion rate of
galvanized steel decreased from 4.52 to 1.87 lg cm2 h1 with the
increase of pH values from 7.0 to 13.0. The results from this gure
-0.6
demonstrated that, the corrosion resistance of galvanized steel in-
creased with the increase of pH values, and galvanized steel has a
good corrosion resistance under high alkalinity. -0.9

-1.2
5

-5 -4 -3 -2 -1 0
log (i,A cm-2)
Weight loss (g/cm h)

4
2

0.0 pH=10.0
3
potential (vs. SCE), V

-0.3
2
-0.6

1
6 7 8 9 10 11 12 13 14 -0.9
pH values
-1.2
Fig. 5. weight loss of galvanized steel under different pH values in SRL solution
containing 0.6 M NaCl.
-6 -5 -4 -3 -2 -1 0
log (i,A cm-2)

0.0016 0.0 pH=13.0

potential (vs. SCE), V

-0.3
0.0012
cm-2)

-0.6
-1
1/Rp(

0.0008
-0.9

0.0004
-1.2

7 8 9 10 11 12 13 -7 -6 -5 -4 -3 -2 -1
pH values log (i,A cm-2)

Fig. 6. The change of 1/Rp of galvanized steel under different pH values in SRL Fig. 7. The cyclic polarization curves of galvanized steel under different pH values
solution containing 0.6 M NaCl. in SRL solution containing 0.6 M NaCl.
 S. Liu et al. / Corrosion Science 65 (2012) 520527 525

120
3000 Rf
2500 Rct
90
2000
icorr, A cm-2

R/ cm2
60 1500

1000
30
500

0
0 7 8 9 10 11 12 13
7 8 9 10 11 12 13
pH value
pH Values
Fig. 10. The change of Rf and Rct on galvanized steel under different pH values in
Fig. 8. The change of icorr of galvanized steel under different pH values in SRL
SRL solution containing 0.6 M NaCl for 2 days.
solution containing 0.6 M NaCl.

3.2.3. Cyclic polarization in SRL solution containing 0.6 M NaCl
One of the tests to assess the susceptibility of galvanized steel
to passive stability was the cyclic potential dynamic polarization
technique at low scan rate. As the corrosion susceptibility could
be predicted from the anodic portion reliably [28].
Typical cyclic potential dynamic polarization curves obtained
for sample of galvanized steel in SRL solution containing 0.6 M
NaCl with pH = 7.0, 10.0 and 13.0 were shown in Fig. 7, respec-
tively. The solid arrows next to the forward and the reverse anodic
branches indicated potential scan directions. When the pH of SRL
solution was 7.0, the galvanized steel did not show a classical pas-
sive region, and the current density increased abruptly until it
reached the value of nearly 0.01 A/cm2 and then it continued to in-
crease slowly as the potential applied increased. The highest polar-
ization was near 0 V vs. SCE. When the pH of SRL solution was 10.0,
the reverse anodic curve showed that the pitting potential was al-
most the same as the open circuit potential, indicating that a tran-
sition from unpassivated to passivated corrosion behavior occurred
on the specimen. Fig. 7 (pH 13.0) showed a classical passive region
with the current density practically independent of applied poten-
tial up to pitting potential Epit = 0.56 V vs. SCE. Then, the current
density increased abruptly until reaching certain value after that it
continued to increase very slightly with the increase of potential.
When the pH of SRL solution was 13.0, the reverse anodic curve
shifted to higher currents than the forward curve, indicating that
some new corrosion products (maybe passive lm) were generated
on the electrode [29]. Indeed, the Zn5Cl2(OH)8 absorbed on the
electrode was thermodynamically unstable at high alkalinity and
proned to form ZnO [30]. Fig. 8 showed the icorr vs. pH curve of gal-
vanized steel under SRL solution containing 0.6 M NaCl. Evidently,
it can be seen that the corrosion current density decreased from
108 to 9.0 lA cm2 with the increase of pH values from 7.0 to
13.0, and galvanized steel exhibited excellent corrosion resistance
in the high alkaline SRL solution. These results were in good agree-
ment with the weight loss measurement.
3.2.4. EIS measurement in SRL solution containing 0.6 M NaCl
Fig. 9 showed the Nyquist and Bode diagrams measured on gal-
vanized steel in SRL solution containing 0.6 M NaCl under various
pH values for 2 days. The equivalent circuit (Fig. 2A) was used to
t the EIS data and the corresponding electrochemical parameters
(Rf and Rct) were listed in Fig. 10. According to the tting results in
Fig. 10, both of the Rf and Rct values increased with the increase of
the pH of the SRL solution, indicating that the rust layer absorbed
on the electrode was thickened and the production afforded by the
rust layer was improved in high alkaline environment. This trend
was consistent with that of the linear polarization measurement.
3.3. Morphology of corrosion attack
XRD, SEM and EDS characterizations were performed to investi-
gate further the corrosion behavior of galvanized steel under SRL
solution containing 0.6 M NaCl at different pH values.
Fig. 11 showed the XRD spectra of the galvanized steel under pH
7.0 and pH 13.0 in SRL solution containing 0.6 M NaCl for 21 days.
The main products in the pH 7.0 (Fig. 11A) and pH 13.0 (Fig. 11B)
were Zn5(OH)8Cl2, Zn(ClO4)2, Zn(OH)2 and ZnO. In the pH 13.0
system, the XRD peaks of these corrosion products gradually became

800 126.9 Hz 60
pH 7.0 pH 7.0
pH 10.0 pH 10.0
50
600 pH 13.0 pH 13.0
phase angle/deg.

0.28 Hz
40
-Z'' / cm2

400 0.092 Hz
30

20
200
0.052 Hz
2.59 Hz 10
0 6.21 kHz
0
0 1000 2000 3000 4000 5000 6000 -2 -1 0 1 2 3 4 5
Z' / cm 2 log f / Hz

Fig. 9. Nyquist and Bode of galvanized steel in different pH values in SRL solution containing 0.6 M NaCl for 2 days.
526 S. Liu et al. / Corrosion Science 65 (2012) 520527

7000 Table 2
EDS results of the chemical compositions of the rust layer in SRL solution containing
(A) 1 ZnO
0.6 M NaCl under different pH values.
6000 3 2 Zn(OH)2
3 Zn5(OH)8Cl2 Element (wt.%) pH 7.0 pH 9.0 pH 11.0 pH 13.0
5000
4 Zn(ClO4)2 Zn 63.03 63.76 64.58 64.10
Intensity (a.u.)

4
4000 O 26.32 27.65 28.62 30.21
4 Cl 10.35 8.36 6.54 5.39
3000 4
3
3 C 0.04 0.04 0.05 0.04
2 2
2 Ti 0.04 0.03 0.03 0.04
2000 3 4 P 0.02 0.01 0.01 0.01
2 3 3
4 Mn 0.18 0.15 0.17 0.21
33 1 2 3
1000 3
41
4
1 4
3 3 2 Fe 2.18 1.23 0 0
3 33 2 312 3 2
0
10 20 30 40 50 60 70 80 a low electronic conductivity, was responsible to the high resistance
2 (degree)
of the zinc coating in high alkaline solution [31].
Fig. 12 showed the SEM images of the galvanized steel in pH 7.0
20000
(B) 1 1 ZnO and pH 13.0 under SRL solution containing 0.6 M NaCl in different
2 Zn(OH)2 immersion times. Fig. 12(a) presented the SEM images of the as-
16000 3 Zn5(OH)8Cl2 received sample of galvanized steel before the tests. These images
4 Zn(ClO4)2 presented here were for comparison with those of corroded
Intensity (a.u.)

12000 3 samples. Evidently, the zinc coatings were compact, smooth and
4
1
completely covered on the zinc coating surface, no corrosion was
3 found before immersion on the electrode surface. In the SRL solu-
8000 2
1 tion containing 0.6 M NaCl, rust layer absorbed on the electrode
2
4 1 3 surface and pitting corrosion occurred on the electrode surface
4000 3 2
2 2 2 1 after 21 days in the pH 7.0 solution (Fig. 12b). zinc coating was
1 3 1 1 21 1 gradually damaged and non-uniform corrosion occurred on the
0 galvanized steel after removing the rust layer (Fig. 12c). However,
10 20 30 40 50 60 70 80 much needle-like rust layer was adherent and compactly absorbed
2 (degree) on the electrode surface in the pH 13.0 solution during the immer-
sion time (Fig. 12b), the color of the surface became murky gray
Fig. 11. XRD spectra of rust layer in SRL solution containing 0.6 M NaCl under
and little pitting was found on the zinc coating (Fig. 12c). The
different pH values. (A): pH 7.0; (B): pH 13.0.
SEM images indicated that passivation occurred on the galvanized
steel under high alkaline environment. These results were in good
agreement with the weight loss experiments.
shallow and sharp and the diffraction intensity increased, indicating Table 2 showed the EDS results of the chemical composition of
that there was a slight increase in crystallinity and grain size of these the corrosion products on the specimen surface of galvanized steel
products under high alkaline solution. It was also found that the in SRL solution containing 0.6 M NaCl under different pH values
number and intensity of ZnO peak in pH 13.0 was more than that after 21 days of immersion. Obviously, Fe element was observed
of pH 7.0, indicating that the ZnO was the main corrosion product in the pH 7.0 and pH 9.0 SRL solution, indicating that zinc coating
in the high alkaline solution. ZnO was a semiconductor, which had was damaged under Cl erosion. The oxide concentration increased

(a) (b) (c)

10 m 10 m

10 m 10 m

Fig. 12. The SEM images of galvanized steel in pH 7.0 (the upper row) and in pH 13.0 (the lower row) in SRL solution containing 0.6 M NaCl for different immersion times: (a)
before immersion; (b) 21 days; (c) 21 days (rust layer was scraped from the electrode surface).
 S. Liu et al. / Corrosion Science 65 (2012) 520527
and the chloride concentration decreased with increasing the pH
values, indicating that the zinc oxide generated in the high alkaline
solution [30,32]. The corrosion of galvanized steel was inhibited by
increasing the pH values of the SRL solution.
4. Conclusion
The effects of pH values and Cl concentration on the corrosion
behavior of galvanized steel were studied under simulated rust
layer (SRL) solution. The corrosion behavior of the galvanized steel
was found to be dependant on the pH values and Cl concentration
under SRL solution. The results obtained by weight loss, linear
polarization and cyclic polarization curve demonstrated that the
galvanized steel possessed good passivation property under high
alkaline SRL solution. The EIS data showed that the rust layer ab-
sorbed on the galvanized steel surface could inhibit the corrosion
of the substrate metal. However, under the chloride-contained
environment, the Rf of the rust layer, the Rct of corrosion reaction,
combined with the Rs of the solution were decreased with the in-
crease of Cl concentration. The protective effects provided by
the rust layer were destructed by the erosion of Cl in SRL solution.
Acknowledgment
The authors wish to acknowledge the nancial support of the
National Science Foundation of China (No. 41076046).
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