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Corrosion Science 65 (2012) 520–527 Contents lists available at SciVerse ScienceDirect Corrosion Science journal

Contents lists available at SciVerse ScienceDirect

Corrosion Science

Science journal homepage: www.else vier.com/locate/corsci Effects of pH and Cl concentration on corrosion behavior

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

article info

Article history:

Received 17 June 2012 Accepted 22 August 2012 Available online 5 September 2012

Keywords:

C.

Rust

B.

EIS

C.

Pitting corrosion

abstract

Effects of pH and Cl concentration on the corrosion behavior of galvanized steel in simulated rust layer (SRL) solution have been investigated using measurements of weight loss, electrochemical impedance spectroscopy (EIS), linear polarization combined with cyclic polarization experiment. In neutral SRL solu- 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 susceptible to pitting corrosion in all chloride solution of concentration ranging between 0.1 and 0.6 M. 2012 Elsevier Ltd. All rights reserved.

1. Introduction

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 [1–4] . Zinc is anodic to iron and behaves as sacrificial 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 (Zn 5 Cl 2 (OH) 8 ) in the marine corrosion environment, and this rust layer has a strong correlation with the corrosion characteristics of the galvanized steel [12–15]. 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).

0010-938X/$ - see front matter 2012 Elsevier Ltd. All rights reserved.

cryrust layer on zinc coating exposed to seawater. He found that 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 Zn 5 Cl 2 (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 cm 2 to the media. A copper wire was connected to the backside of each specimen with a silver paste. Before each

S. Liu et al. / Corrosion Science 65 (2012) 520–527

521

experiment, the working surfaces of the electrodes were degreased with ethanol, then cleaned with distilled water, and finally 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 Zn 5 Cl 2 (OH) 8 . The reaction was given by (1):

5ZnCl 2 þ 8NH 3 H 2 O ! Zn 5 Cl 2 ðOHÞ 8 þ 8NH 4 Cl

ð 1Þ

The reaction temperature was 80 C and reaction time was 2 h. Excessive Zn 5 Cl 2 (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 NaHCO 3 . The Cl concentration contained in the solution was 0.1–0.6 M (0.58–3.5 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 finished, 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 NH 4 Cl 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/cm 2 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 ( R p ) 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 five 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 k a radiation ( k = 0.154 nm) and 10–80 scanning range was used to obtain XRD patterns form the powder

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 field 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 fitted 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 fit the EIS of the gal- vanized steel under SRL solution containing different Cl concentration (pH 7.0). The first equivalent circuit ( Fig. 2 A) was used to fit the EIS data only displaying two capacitive loops, whereas the second one ( Fig. 2 B) was used to fit the EIS data displaying aWarburg impedance [22] . In the two equivalent circuit models, Q is the constant phase angle element, expressed as x n / Y 0 (cos n p /2 + j sin n p /2), where Y 0 and n are the constant and exponent, respec- tively, and x is the angular frequency in rad s 1 ( x = 2 p f ), and j 2 = 1 is an imaginary number. R s is the solution resistance of SRL solution, the high-frequency circuit R f Q 1 corresponds to the capacitance and resistance of the surface film of rust layer; the med- ium–low frequency circuit R ct Q 2 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 coefficients n 1 and n 2 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 fitting results in Table 1 , the R s value decreased with the in- crease of Cl concentration, indicating that Cl could decrease the resistance of the solution. The change of Q 2 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 R ct are used to represent corrosion rate of gal- vanized steel, because the R ct is more intimately correlated to the corrosion rate than R p 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/ R ct of galvanized steel under SRL solution at different Cl concentration from the curve fitting

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S. Liu et al. / Corrosion Science 65 (2012) 520–527

1.172 kHz blank blank 1200 2d 672 Hz 50 0.03 Hz 7d 14d 2d 21d
1.172 kHz
blank
blank
1200
2d
672 Hz
50
0.03 Hz
7d
14d
2d
21d
40
7d
900
14d
21d
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' /
cm 2
log f / Hz
0.03 Hz
0.1M NaCl
0.1M NaCl
500
50
2
d
2 d
400
7
d
40
7d
14
d
7.88 Hz
0.017Hz
14d
300
21
d
0.01 Hz
21d
0.01 Hz
30
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
log f / Hz
Z' /
cm 2
400
50
0.2 M NaCl
0.2 M NaCl
0.09 Hz
1d
320
1d
40
7d
7d
14 d
14d
21d
240
30
21d
160
20
0.28 Hz
0.16 Hz
80
10
18.87 kHz
0
10.82 kHz
0
-2
-1
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2
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5
0
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log f / Hz
Z' /
cm 2
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500
0.4 M NaCl
0.4 M NaCl
80
2
d
2
d
400
70
7
d
7
d
60
14 d
0.01Hz
14d
300
21d
0.49 Hz
50
21d
72.79 Hz
40
200
30
0.28 Hz
20
100
7.88 Hz
10
32.90 kHz
0
0
57.36 kHz
-2
-1
0
1
2
3
4
5
0
400
800
1200
1600
log f / Hz
Z' /
cm 2
90
400
0.6 M NaCl
0.6
M NaCl
0.161
Hz
80
2d
2d
7d
70
7d
300
41.75 Hz
14d
0.161
Hz
60
14d
21d
21d
50
7.88 Hz
200
40
30
100
20
4.52 Hz
10
0.28 Hz
0
0
0
500
1000
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-2
-1
0
1
2
3
4
5
Z' /
cm 2
log f / Hz
2
-Z'' /
cm 2
-Z'' /
cm 2
-Z'' /
cm 2
/ cm-Z''
-Z'' /
cm 2
phase angle/deg.
phase angle/deg.
phase angle/deg.
phase angle/deg.
phase angle/deg.

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 0.1–0.6 M NaCl increased with time, indicating that Cl can penetrate from the rust layer, destruct the structure of the rust

layer and react with the metal directly [23] . By comparing the corrosion rate at the same time in the chloride-free medium, the corrosion rate kept invariant and much lower than that in

S. Liu et al. / Corrosion Science 65 (2012) 520–527

523

S. Liu et al. / Corrosion Science 65 (2012) 520–527 523 Fig. 2. Equivalent circuit models

Fig. 2. Equivalent circuit models used to fit 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)

R s ( X cm 2 )

Q 1 ( l F cm 2 )

n 1

R f ( X cm 2 )

Q 2 ( l F cm 2)

n 2

R ct ( X cm 2 )

W ( X cm 2 )

0 M

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 0 M NaCl 0.1 M NaCl 0.2 M NaCl 0.4 M NaCl 0.002 0.6
0.003
0 M NaCl
0.1
M NaCl
0.2
M NaCl
0.4
M NaCl
0.002
0.6
M NaCl
0.001
0.000
0
7
14
21
Time /day
-1 cm -2 )
1/R ct (

Fig. 3. The change of 1/ R ct on galvanized steel under different Cl concentration in SRL solution.

chloride-contained medium, indicating that the rust layer could inhibit the corrosion of the zinc coating. The R f of the galvanized steel in the SRL solution containing different Cl concentration were showed in Fig. 4 . It can be clearly observed that R f value increased from 565.1 to 967.8 X cm 2 with the increase of the immersion time in SRL solution in a chloride- free medium, indicating that new corrosion products generated

1000 800 0 M NaCl 0.1 M NaCl 0.2 M NaCl 600 0.4 M NaCl
1000
800
0 M NaCl
0.1
M NaCl
0.2
M NaCl
600
0.4
M NaCl
0.6
M NaCl
400
200
0
0
7
14
21
Time /day
R f /
cm 2

Fig. 4. The change of R f on galvanized steel under different Cl concentration in SRL solution.

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 R f value decreased gradually with the increase of immersion time, and the R f value decreased as the Cl concentration increased, indicating that corrosion products film absorbed on the electrode surface gradually damaged under the erosion of Cl .

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S. Liu et al. / Corrosion Science 65 (2012) 520–527

The different corrosion behavior of galvanized steel under 0.1–0.6 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- tion–inactivation 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 significantly 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/ R p ) calculated from the corresponding curves of linear polariza- tion. Fig. 6 showed the values of 1/ R p of galvanized steel vs. pH in SRL solution containing 0.6 M NaCl. It can be clearly seen from the figure that, the corrosion rate (1/ R p ) 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 film generated on the zinc coating in high alkaline solution. Therefore, it is possible that a stable passive film 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 The weight loss of specimens in SRL solution containing 0.6 M NaCl at different pH values, after 30 days immersion at room tem- perature were obtained and showed in Fig. 5 . The corrosion rate of galvanized steel decreased from 4.52 to 1.87 l g cm 2 h 1 with the increase of pH values from 7.0 to 13.0. The results from this figure 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.

5 4 3 2 1 6 7 8 9 10 11 12 13 14 Weight
5
4
3
2
1
6
7
8
9
10
11
12
13
14
Weight loss (µg/cm 2 h)

pH values

Fig. 5. weight loss of galvanized steel under different pH values in SRL solution containing 0.6 M NaCl.

0.0016 0.0012 0.0008 0.0004 7 8 9 10 11 12 13 pH values 1/R p
0.0016
0.0012
0.0008
0.0004
7
8
9
10
11
12
13
pH values
1/R p ( -1 cm -2 )

Fig. 6. The change of 1/ R p of galvanized steel under different pH values in SRL solution containing 0.6 M NaCl.

0.0 pH=7.0 -0.3 -0.6 -0.9 -1.2 -5 -4 -3 -2 -1 0 log (i,A cm
0.0
pH=7.0
-0.3
-0.6
-0.9
-1.2
-5
-4
-3
-2
-1
0
log (i,A cm -2 )
0.0
pH=10.0
-0.3
-0.6
-0.9
-1.2
-6
-5
-4
-3
-2
-1
0
log (i,A cm -2 )
0.0
pH=13.0
-0.3
-0.6
-0.9
-1.2
-7
-6
-5
-4
-3
-2
-1
log (i,A cm -2 )
potential (vs. SCE), V
potential (vs. SCE), V
potential (vs.SCE), V

Fig. 7. The cyclic polarization curves of galvanized steel under different pH values in SRL solution containing 0.6 M NaCl.

S. Liu et al. / Corrosion Science 65 (2012) 520–527

525

120 90 60 30 0 7 8 9 10 11 12 13 pH Values -2
120
90
60
30
0
7
8
9
10
11
12
13
pH Values
-2
i corr µ A cm,

Fig. 8. The change of i corr of galvanized steel under different pH values in SRL solution containing 0.6 M NaCl.

3000 R f R 2500 ct 2000 1500 1000 500 0 7 8 9 10
3000
R f
R
2500
ct
2000
1500
1000
500
0
7
8
9
10
11
12
13
pH value
Fig. 10. The change of R f and R ct on galvanized steel under different pH values in
SRL solution containing 0.6 M NaCl for 2 days.
R/
cm 2

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/cm 2 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 E pit = 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 film) were generated on the electrode [29] . Indeed, the Zn 5 Cl 2 (OH) 8 absorbed on the electrode was thermodynamically unstable at high alkalinity and

proned to form ZnO [30] . Fig. 8 showed the i corr 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 l A cm 2 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. 2 A) was used to fit the EIS data and the corresponding electrochemical parameters ( R f and R ct ) were listed in Fig. 10 . According to the fitting results in Fig. 10 , both of the R f and R ct 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. 11 A) and pH 13.0 ( Fig. 11 B) were Zn 5 (OH) 8 Cl 2 , Zn(ClO 4 ) 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
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
0.28 Hz
40
0.092 Hz
400
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
2
/ cm-Z''
phase angle/deg.

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) 520–527

7000 (A) 1 ZnO 6000 2 Zn(OH) 2 3 3 Zn 5 (OH) 8 Cl
7000
(A)
1
ZnO
6000
2
Zn(OH) 2
3
3
Zn 5 (OH) 8 Cl 2
5000
4
Zn(ClO 4 ) 2
4
4000
4
3000
3
4
3
2
2
2
2000
4
3
3
2
3
4
1
2
3
3 3
1000
4
1
4
1
3
4
3
3
3 2
3
3
2
2
3
1
3
2
0
10
20
30
40
50
60
70
80
2
(degree)
Intensity (a.u.)
20000 (B) 1 1 ZnO 2 Zn(OH) 2 16000 3 Zn 5 (OH) 8 Cl
20000
(B)
1
1
ZnO
2
Zn(OH) 2
16000
3
Zn 5 (OH) 8 Cl 2
4
Zn(ClO 4 ) 2
12000
3
4
1
3
8000
2
1
2
4
3
1
4000
3
2
2
1
2 2
1
3
1 1
1
2
1
0
10
20
30
40
50
60
70
80
2
(degree)
Intensity (a.u.)

Fig. 11. XRD spectra of rust layer in SRL solution containing 0.6 M NaCl under different pH values. (A): pH 7.0; (B): pH 13.0.

shallow and sharp and the diffraction intensity increased, indicating that there was a slight increase in crystallinity and grain size of these products under high alkaline solution. It was also found that the number and intensity of ZnO peak in pH 13.0 was more than that of pH 7.0, indicating that the ZnO was the main corrosion product in the high alkaline solution. ZnO was a semiconductor, which had

Table 2

EDS results of the chemical compositions of the rust layer in SRL solution containing

0.6 M NaCl under different pH values.

Element (wt.%)

pH 7.0

pH 9.0

pH 11.0

pH 13.0

Zn

63.03

63.76

64.58

64.10

O

26.32

27.65

28.62

30.21

Cl

10.35

8.36

6.54

5.39

C

0.04

0.04

0.05

0.04

Ti

0.04

0.03

0.03

0.04

P

0.02

0.01

0.01

0.01

Mn

0.18

0.15

0.17

0.21

Fe

2.18

1.23

0

0

a low electronic conductivity, was responsible to the high resistance

of the zinc coating in high alkaline solution [31] . Fig. 12 showed the SEM images of the galvanized steel in pH 7.0

and pH 13.0 under SRL solution containing 0.6 M NaCl in different

immersion times. Fig. 12 (a) presented the SEM images of the as- received sample of galvanized steel before the tests. These images

presented here were for comparison with those of corroded samples. Evidently, the zinc coatings were compact, smooth and

completely covered on the zinc coating surface, no corrosion was

found before immersion on the electrode surface. In the SRL solu-

tion containing 0.6 M NaCl, rust layer absorbed on the electrode

surface and pitting corrosion occurred on the electrode surface

after 21 days in the pH 7.0 solution ( Fig. 12 b). zinc coating was

gradually damaged and non-uniform corrosion occurred on the galvanized steel after removing the rust layer ( Fig. 12 c). However, much needle-like rust layer was adherent and compactly absorbed

on the electrode surface in the pH 13.0 solution during the immer- sion time ( Fig. 12 b), the color of the surface became murky gray and little pitting was found on the zinc coating ( Fig. 12 c). The 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. Table 2 showed the EDS results of the chemical composition of the corrosion products on the specimen surface of galvanized steel in SRL solution containing 0.6 M NaCl under different pH values after 21 days of immersion. Obviously, Fe element was observed in the pH 7.0 and pH 9.0 SRL solution, indicating that zinc coating was damaged under Cl erosion. The oxide concentration increased

(a)

10 µ m
10 µ m
10 µ m
10 µ m

(b)

10 µ m
10 µ m
10 µ m
10 µ m

(c)

(a) 10 µ m 10 µ m (b) 10 µ m 10 µ m (c)
(a) 10 µ m 10 µ m (b) 10 µ m 10 µ m (c)

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 ti mes: (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) 520–527

527

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 R f of the rust layer, the R ct of corrosion reaction, combined with the R s 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 financial support of the National Science Foundation of China (No. 41076046).

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