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Available online at www.sciencedirect.com Corrosion Science 50 (2008) 365–371 www.elsevier.com/locate/corsci Characterization of the rust formed onqxli@imr.ac.cn (Q.X. Li). 0010-938X/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2007.06.020 rust layer against further corrosion [4,7,8] . Asami et al. [6] studied the rust on steels exposed to coastal-industrial atmosphere for 17 years and reported that all rust was composed of a -FeOOH, b -FeOOH, c -FeOOH, Fe O and amorphous rust. b -FeOOH was mainly present at thick parts of rust layers. Nishimura et al. [9] took a wet/dry corrosion test of steels in laboratory. It was observed that the content of b -FeOOH in rust increased with increasing the concentration of Cl in the environ- ment and b -FeOOH was translated from green rust I (GRI). Townsend et al. [10] investigated the corrosion products on weathering steel exposed to industrial and rural environments for 11 years, respectively. It was found that the rusts on the steel in both environments were com- posed of a -FeOOH, c -FeOOH, a -Fe O and Fe O . a -Fe O and Fe O were existed in the outer layer of rusts and they were important to the formation of protective rust. However, up to now, little work has been addressed in the corrosion of weathering steel in salt lake environments. Qinghai salt lake is located in the northwest of China. " id="pdf-obj-0-2" src="pdf-obj-0-2.jpg">

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Available online at www.sciencedirect.com Corrosion Science 50 (2008) 365–371 www.elsevier.com/locate/corsci Characterization of the rust formed onqxli@imr.ac.cn (Q.X. Li). 0010-938X/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2007.06.020 rust layer against further corrosion [4,7,8] . Asami et al. [6] studied the rust on steels exposed to coastal-industrial atmosphere for 17 years and reported that all rust was composed of a -FeOOH, b -FeOOH, c -FeOOH, Fe O and amorphous rust. b -FeOOH was mainly present at thick parts of rust layers. Nishimura et al. [9] took a wet/dry corrosion test of steels in laboratory. It was observed that the content of b -FeOOH in rust increased with increasing the concentration of Cl in the environ- ment and b -FeOOH was translated from green rust I (GRI). Townsend et al. [10] investigated the corrosion products on weathering steel exposed to industrial and rural environments for 11 years, respectively. It was found that the rusts on the steel in both environments were com- posed of a -FeOOH, c -FeOOH, a -Fe O and Fe O . a -Fe O and Fe O were existed in the outer layer of rusts and they were important to the formation of protective rust. However, up to now, little work has been addressed in the corrosion of weathering steel in salt lake environments. Qinghai salt lake is located in the northwest of China. " id="pdf-obj-0-6" src="pdf-obj-0-6.jpg">

Corrosion Science 50 (2008) 365–371

Available online at www.sciencedirect.com Corrosion Science 50 (2008) 365–371 www.elsevier.com/locate/corsci Characterization of the rust formed onqxli@imr.ac.cn (Q.X. Li). 0010-938X/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2007.06.020 rust layer against further corrosion [4,7,8] . Asami et al. [6] studied the rust on steels exposed to coastal-industrial atmosphere for 17 years and reported that all rust was composed of a -FeOOH, b -FeOOH, c -FeOOH, Fe O and amorphous rust. b -FeOOH was mainly present at thick parts of rust layers. Nishimura et al. [9] took a wet/dry corrosion test of steels in laboratory. It was observed that the content of b -FeOOH in rust increased with increasing the concentration of Cl in the environ- ment and b -FeOOH was translated from green rust I (GRI). Townsend et al. [10] investigated the corrosion products on weathering steel exposed to industrial and rural environments for 11 years, respectively. It was found that the rusts on the steel in both environments were com- posed of a -FeOOH, c -FeOOH, a -Fe O and Fe O . a -Fe O and Fe O were existed in the outer layer of rusts and they were important to the formation of protective rust. However, up to now, little work has been addressed in the corrosion of weathering steel in salt lake environments. Qinghai salt lake is located in the northwest of China. " id="pdf-obj-0-10" src="pdf-obj-0-10.jpg">

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Characterization of the rust formed on weathering steel exposed to Qinghai salt lake atmosphere

Q.X. Li * , Z.Y. Wang, W. Han, E.H. Han

Environmental Corrosion Centre, Institute of Metal Research, Chinese Academy of Sciences, Wencui Road 62, Shenyang 110016, PR China

Received 11 August 2006; accepted 22 June 2007 Available online 26 July 2007

Abstract

The product formed on weathering steel exposed to salt lake atmosphere for 12 months was investigated by X-ray diffraction (XRD), infrared transmission spectroscopy (IRS), scanning electron microscopy (SEM), electron probe micro analyzer (EPMA) and electro- chemical techniques. The rust was mainly composed of b-FeOOH, Fe 8 (O,OH) 16 Cl 1.3 and a little c-FeOOH. Amorphous d-FeOOH was only on skyward surface. The rust layer suppressed anodic reaction and facilitated the cathodic reaction. The very small value of rust resistance R r in this work indicated that the rust had poor protective ability. Cl element was rich in the whole rust layer and played an important role in accelerating the corrosion of weathering steel in salt lake atmosphere. 2007 Elsevier Ltd. All rights reserved.

Keywords: A. Weathering steel; C. Atmospheric corrosion; C. Salt lake

1. Introduction

Weathering steel is often used in the atmospheric environment without paint or other protective coatings. Atmospheric corrosion is an important cause of destruc- tion of weathering steel constructions and has received much interest in recent years [1,2]. When the same steel is exposed to different environments, the characteristics of corrosion products vary due to different environmen- tal factors [3]. Therefore, it is significant to study the rust on weathering steel in a given atmospheric environment. Studies on atmospheric corrosion of weathering steels have been carried out in many countries [1–11]. Wang et al. investigated the corrosion of weathering steel exposed to industrial atmosphere for 6 years in Taiwan and concluded that the phase transformation of c-FeO- OH into a-FeOOH contributed to the resistance of the

* Corresponding author. Tel.: +86 24 2389 3544; fax: +86 24 2389 4149. E-mail address: qxli@imr.ac.cn (Q.X. Li).

0010-938X/$ - see front matter 2007 Elsevier Ltd. All rights reserved.

doi:10.1016/j.corsci.2007.06.020

rust layer against further corrosion [4,7,8]. Asami et al. [6] studied the rust on steels exposed to coastal-industrial atmosphere for 17 years and reported that all rust was composed of a-FeOOH, b-FeOOH, c-FeOOH, Fe 3 O 4 and amorphous rust. b-FeOOH was mainly present at thick parts of rust layers. Nishimura et al. [9] took a wet/dry corrosion test of steels in laboratory. It was observed that the content of b-FeOOH in rust increased with increasing the concentration of Cl in the environ- ment and b-FeOOH was translated from green rust I (GRI). Townsend et al. [10] investigated the corrosion products on weathering steel exposed to industrial and rural environments for 11 years, respectively. It was found that the rusts on the steel in both environments were com- posed of a-FeOOH, c-FeOOH, a-Fe 2 O 3 and Fe 3 O 4 . a-Fe 2 O 3 and Fe 3 O 4 were existed in the outer layer of rusts and they were important to the formation of protective rust. However, up to now, little work has been addressed in the corrosion of weathering steel in salt lake environments. Qinghai salt lake is located in the northwest of China.

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Table 1 Environmental conditions of the exposure location

Average temperature ( C year 1 )

Average rainfall (mm year 1 )

Average evaporation (mm year 1 )

Saline particles (mg m 2 day 1 )

Natural deposition (g cm 2 month 1 )

 

Soluble

Insoluble

17.5 a

38.3 a

3067.0 a

19.16 b

23.19 b

20.98 b

a The data were reported by Communication of National Network for Environment Corrosion Survey of Materials, China. b Average of natural deposition values in a year were provided by Wuhan Institute for Materials Protection, Wuhan, China.

The concentration of Cl ions in salt lake water is 34 wt.%, 1 which is 10 times more than that in sea water. And the water possesses a low pH value of 5.0. High salinity of salt lake water and high deposition rate of sea-salt particles facilitate the atmospheric corrosion of weathering steels in the salt lake region. With the fast development of local economy, it becomes very important to investigate the atmospheric cor- rosion process of weathering steel and reduce the cost. There- fore, in this work, a kind of weathering steel was exposed to a salt lake region for 12 months. The rust formed on the steel was characterized and the corrosion process was proposed.

2. Experimental methods

  • 2.1. Atmospheric rusting

Corten A weathering steel was selected and its composi- tion (wt.%) is C 0.09, S 0.005, P 0.081, Mn 0.35, Si 0.3, Cr 0.48, Ni 0.27, Cu 0.28, Al 0.037 and Fe balance. The four parallel samples (three for weight loss measurement and one for rust layer analysis) were cut into the sizes of 100 mm 50 mm 5 mm and degreased with acetone. In order to completely evaporate the water on the surface, these samples were cleaned with ethanol and then kept in a desiccator for at least 24 h. After the treatments, the sam- ples were weighed using analytic balance (the precision is 0.0001 g). Samples for electrochemical analysis were mounted in epoxy resin at room temperature and the exposed area was 1 cm 2 . The electrode samples were ground on SiC paper successively to 1000 grit and then cleaned with ethanol. The exposure site was located on the roof of an office building about 40 m far away from the salt lake. The envi- ronmental parameters of the exposure locations are listed in Table 1. The weathering steel samples were exposed to south at an angle of 45 to horizontal under open condi- tions. After 12 months, the samples were taken back for analysis.

  • 2.2. Analysis of the rust powder

The rusts formed on the steel surfaces were character- ized by means of infrared transmission spectroscopy

1 The value was measured by Inspection and Testing Center for Agro- product Safety and Environment Quality, Institute of Applied Ecology, CAS.

(IRS) and X-ray diffraction (XRD). The powdered rust was scraped off from metallic substrate using a razor blade and desiccated for a week before the subsequent analysis in order to ensure the samples are completely dried. The rust powder was mixed with pure KBr and the mixture was pressed into a transparent circular flake. Nicolet Corpora- tion Model magna-IR560 (with Veemax accessory) infra- red spectrophotometer was used to determine the IR spectra of the rust powder in the ranges from 400 to 4000 cm 1 . The XRD data of the rust powder were col- lected by a step-scanning diffractometer and Cu Ka radia- tion (Rigaku D/max-2500PC Model, Japan).

  • 2.3. Analysis of the rust layer

The specimens were cut from rusted steel plates. Au was deposited on the rusted surface for reinforcing the rust layer and increasing the electric conductivity. The samples for cross-section analysis were fixed by an epoxy resin at room temperature. And then they were mechanically ground on SiC paper (grades 400–2000) and polished with diamond paste of 1.5 lm particle size in oil. After being cleaned with ethanol, the samples were stored in a desiccator. The micrographs of the surface rust layers and the ele- ments contents in the rusts were obtained using a FEI Company Model XL30 ESEM FEG environmental scan- ning electron microscopy (ESEM) and energy dispersive X-ray diffraction (EDX). The distributions of several important elements in the cross-sections of rust layers were detected by a Shimadzu Model EPMA-1610 electron probe micro analyzer at 15 kV accelerated voltage and 0.08 lA sample current.

  • 2.4. Electrochemical measurements

Electrochemical tests were performed using a Princeton Applied Research (PAR) 5210 lock-in amplifier and a PAR 263A potentiostat interfaced through an IEEE 488 bus to a compatible computer. And the experiments were carried out in 0.1 M Na 2 SO 4 electrolyte open to the air at 20 ± 1 C. The electrochemical cell consisted of three elec- trodes: a rusted working electrode, a saturated calomel ref- erence electrode (SCE) and a platinum plate auxiliary electrode. Prior to polarization and impedance measure- ments the samples were left freely immersed in the solution for 1 h.

Q.X. Li et al. / Corrosion Science 50 (2008) 365–371

367

Anodic and cathodic polarization measurements were taken on different samples using potential dynamic meth- ods at a sweep rate of 20 mV/min. A sinusoid AC voltage signal of amplitude 10 mV was applied during the imped- ance measurements. The impedance response was deter- mined in the frequency range from 10 5 to 10 2 Hz.

3. Results and discussion

The appearance of the skyward surface on the rusted steel was red brown and uniform, while the field-ward sur- face was dark brown and uneven. After removing the rust layers, average mass loss of weathering steel was deter- mined to be 138.12 g/m 2 . In order to know the structure of the rust layer, metallographic microscope was used to observe the cross-sections of the rusted samples (Fig. 1). From Fig. 1a and b, it could be seen that the steel was corroded unevenly and the rust layers on both sides were rough and not compact. For the skyward surface, its corro- sion product is comprised of only one layer. Whereas for the field-ward surface, some positions of its rust layer con- sisted of two layers (Fig. 1c). The inner layer was dark while the outer layer was bright. In addition, the average thickness of the rust on skyward and field-ward surfaces

Q.X. Li et al. / Corrosion Science 50 (2008) 365–371 367 Anodic and cathodic polarization measurements

Fig. 1. Metallographic cross-sections of rusted weathering steel: (a) skyward surface, (b) field-ward surface and (c) a section consisted of two layers on field-ward surface.

exhibited difference: they were 52 lm and 65 lm, respec- tively. Therefore, it can be concluded that after 12 months of exposure, the corrosion on field-ward surface was more severe than that on skyward surface. SEM observation of the rusted steel surface (Fig. 2) fur- ther confirmed the above conclusion. Compared with that on the skyward rust layer, the surface on the field-ward rust layer was rougher and contained more cavities. EDX analysis was carried out on more than five differ- ent positions of the rust layer and the average contents of elements contained in the rust layer were obtained (Table 2). The foreign elements O, Mg, Al, Si, Cl, K, and Ca were detected in both field-ward and skyward rust layers. And their contents in the rust of skyward surface were lower than that of field-ward surface. Generally, skyward surface favored deposition of pollutant particles. However, com- paring with field-ward surface, the skyward surface was subjected to more radiation by sun and more removal by rain and wind. This resulted in the lower content of con- taminations retained in the skyward rust. Based on the above results, more severe corrosion of field-ward surface can be explained as the following fac- tors. First factor is that the rust layer on field-ward surface is rougher and more porous than that on skyward surface. Such phenomenon was also found in Refs. [12,13]. More porous structure of field-ward rust layers lead to less bar- rier against the ingress of precipitation and chlorides pollu- tants and higher corrosion rate. Second factor is the larger amounts of polluted particles retained in the field-ward rust. The pollutants diffused through the rust to the metal/rust interface (confirmed by EPMA in Fig. 3) and accelerated steel corrosion during wetting. Third is the for- mation of amorphous d-FeOOH only in the skyward rust (see Fig. 5). Amorphous d-FeOOH is helpful to inhibit the corrosion of weathering steel [14]. To determine the distributions of elements in the rust on the steel, the EPMA analysis was performed. The results are shown in Fig. 3. A large amount of Cl and a little S were detected in the rust and Cl had diffused to the inter- face between the rust and substrate. Therefore, it can be postulated that Cl played an important role in the corro- sion of weathering steel in the salt lake atmosphere. Si, Al,

Q.X. Li et al. / Corrosion Science 50 (2008) 365–371 367 Anodic and cathodic polarization measurements

Fig. 2. Scanning electron micrograph of the rust layer on weathering steel exposed to the salt lake atmosphere: (a) the skyward surface and (b) the field- ward surface.

  • 368 Q.X. Li et al. / Corrosion Science 50 (2008) 365–371

Table 2 Average contents (wt.%) of elements containing in corrosion product

Element

Content

Skyward surface

Field-ward surface

O

4.51

5.74

Mg

1.15

2.07

Al

0.87

3.47

Si

2.13

8.34

Cl

1.58

3.60

K

0.76

1.72

Ca

0.81

0.97

Fe

88.50

75.60

Mg, and Ca were distributed in the whole rust layer. It is worth noting that much Mg was found in this study. Few papers had reported the presence of Mg in the rust. This may be because the salt lake air contains an amount of MgCl 2 particles. The values of the critical relative humidity (RH) of MgCl 2 and NaCl are 35% and 75%, respectively [15]. Evans demonstrated that the presence of hygroscopic magnesium chloride in sea-salt or sea mist enables corrosion to take place on iron and steel at much lower relative humidity than if only sodium chloride is present [16]. P element was not detected in the rust by EPMA because the amount of P contained in the original weather- ing steel was little [8,17]. Ni, Cr and Cu existed in the rust. However, they did not show any characteristic distribution. Ni, Cr and Cu are beneficial to the formation of the uni- form protective rust layer on the surface of weathering steel, whereas in this work, these elements did not display their functions, which may be because of the short expo- sure time [8].

Fig. 4 shows the X-ray diffraction patterns of the pow- dered rust formed on the weathering steels. The rust layers

on both surfaces were mainly composed of akaganeite (b-

FeOOH; JCPDS card # 34-1266), complex compound

Fe 8 (O,OH) 16 Cl 1.3 (JCPDS card # 42-1315), and a little lep- idocrocite (c-FeOOH; JCPDS card # 44-1415). In addi- tion, the quartz was also found in the rust layers. IR spectra were used to analyze the composition of the powered rust (shown in Fig. 5). The main absorb peaks were characterized according to the reported spectra of iron oxides [8,18,19]. The main compositions of the rust on both surfaces were b-FeOOH and c-FeOOH. Amor- phous d-FeOOH was found only in the skyward rust. Fe 8 (O,OH) 16 Cl 1.3 was not examined because no IR data

368 Q.X. Li et al. / Corrosion Science 50 (2008) 365–371 Table 2 Average contents (wt.%)

Fig. 4. X-ray diffraction patterns of the powdered rust formed on the weathering steels.

368 Q.X. Li et al. / Corrosion Science 50 (2008) 365–371 Table 2 Average contents (wt.%)

Fig. 3. The distribution of O, Cl, S, Si, Ca, Mg, Fe, Cr, Ni and Cu in the rust formed on skyward surface of 12 months old weathering steel. Back scatter electron image (BSEI) of the analyzed portion is shown in (a).

Q.X. Li et al. / Corrosion Science 50 (2008) 365–371

369

Q.X. Li et al. / Corrosion Science 50 (2008) 365–371 369 Fig. 5. IR spectra of

Fig. 5. IR spectra of the powdered rust formed on the weathering steels.

for Fe 8 (O,OH) 16 Cl 1.3 can be obtained in the public litera- tures. Compared with that of the field-ward rust, the peaks of the skyward rust were broader and weaker, indicating that the skyward rust was poorly crystallized. The absorp- tion band at the vicinity of 1630 cm 1 demonstrated that all corrosion products contained a considerable amount of bound water [8,19]. The results of XRD and IR indicated that a large amount of b-FeOOH was present in the rust, which is asso- ciated with the high concentration of Cl in the Qinghai salt lake atmosphere. This is due to the facts that the for- mation of b-FeOOH needs halogen ions such as Cl and F , which stabilize the tunnel structure of b-FeOOH crys- tals [6,9,14]. b-FeOOH is considered to be the most detri- mental to corrosion resistance of steel among the ferric oxyhydroxides [2]. Generally, a-FeOOH is present in the rust of weathering steel. However, in this work, no a-FeOOH was detected in the XRD and IR spectra of rusts. This may be associated with the chlorides-rich atmosphere of salt lake region. It is well established that the content of b-FeOOH in rust increased with increasing the concentration of Cl in the environment [6,9,14]. Therefore, most Fe involved in the corrosion reaction may be transformed into b-FeOOH, resulting in the little amount of a-FeOOH in rusts. In addi- tion, the transformation from c-FeOOH to a-FeOOH requires several years [7,8]. In present work, the exposure time is one year, which is not sufficient for the formation of a-FeOOH. To determine the protective characteristics of the rust layers, electrochemical measurements were performed on bare and rusted electrodes. Polarization results are shown in Fig. 6. Compared with that of naked steel, the corrosion potential of the rusted sample became more positive. And its anodic currents decreased. In addition, with the increase of potential, the current density of the rusted sample increased and then decreased at about 0.034 V. When the potential further increased to the range of 0.40– 0.75 V. the current density almost kept stable indicating

Q.X. Li et al. / Corrosion Science 50 (2008) 365–371 369 Fig. 5. IR spectra of

Fig. 6. Polarization curves of weathering steel in 0.5 M Na 2 SO 4 electrolyte.

the passivation occurred on the rusted steel. Based on the above results, it can be postulated that anodic reaction was suppressed by the rust layer on the steel [9]. It also can be seen from Fig. 6 that cathodic currents of the rusted steel became much larger than that of bare steel. This was mainly attributed to the reduction of ferric rust, not dis- solved O 2 [5,9,20,21]. Figs. 7 and 8 show the Nyquist and Bode plots of naked and rusted steel, respectively. For rusted steel, the Nyquist plot was composed of a capacitive arc in high frequency, and a line in medium and low frequency region represent- ing typical Warburg impedance. This indicated that the electrochemical reaction was controlled by the diffusion process. The construction of rust layer can be described using the equivalent circuit in Fig. 9 [11]. For naked steel, only one double-layer capacitive semicircle was observed in the Nyquist plot and its equivalent circuit is shown in Fig. 10. In Figs. 9 and 10, R s represents the electrolyte resistance, C rust the rust capacitance, R r the rust resistance, C dl the double-layer capacitance, R t the charge-transfer

Q.X. Li et al. / Corrosion Science 50 (2008) 365–371 369 Fig. 5. IR spectra of

Fig. 7. Nyquist plots of weathering steel in 0.5 M Na 2 SO 4 electrolyte.

  • 370 Q.X. Li et al. / Corrosion Science 50 (2008) 365–371

370 Q.X. Li et al. / Corrosion Science 50 (2008) 365–371 Fig. 8. Bode plots of

Fig. 8. Bode plots of weathering steel in 0.5 M Na 2 SO 4 electrolyte.

370 Q.X. Li et al. / Corrosion Science 50 (2008) 365–371 Fig. 8. Bode plots of

Fig. 9. Equivalent circuit for rusted steel.

370 Q.X. Li et al. / Corrosion Science 50 (2008) 365–371 Fig. 8. Bode plots of

Fig. 10. Equivalent circuit for naked steel.

resistance, W the Warburg resistance. As the dispersion effect is considered, a constant phase angle element (CPE) Q is introduced to describe the element C dl and C rust in the fitting procedure.

Table 3 Fitting data of impedance parameters in equivalent circuits

The electrochemical impedance for the circuit of Fig. 9 can be expressed by the following equation:

Z ¼ R s þ

  • 1 ð1Þ

1

1 R r þ
1
R r þ

Y dl ðjxÞ n dl þ1=ðR t þZ w Þ

Y rust ðjxÞ n rust þ

where Y rust and n rust , Y dl and n dl are constants representing the elements Q rust and Q dl , respectively, Z w is the Warburg resistance. Z w is represented as follows [22]:

Z w ¼ A w ðjxÞ 0:5

ð2Þ

where A w is the modulus of Z w . The total impedance for the circuit of Fig. 10 can be expressed by the following equation:

Z ¼ R s þ

1

Y dl ðjxÞ n dl þ 1=R t

ð3Þ

The equivalent circuits of Figs. 9 and 10 are used to fit the Nyquist and Bode plots of rusted and naked steel, respectively. A very good fitting was obtained and the results are listed in Table 3. Compared with that of the naked steel, R t of the rusted steel is much smaller, which is attributed to the reduction of the rust accelerating the cathodic reaction. It is worth noting that the values of R r and A w are much smaller than those in the published liter- atures [4,9]. R r is usually used to evaluate the corrosion resistance of the rust. Therefore, it can be concluded that the rust layer had poor barrier function and it can not effec- tively prevent the corrosion of weathering steel, which is in good agreement with the porous structure of the rust layer. Based on the all above results and the views furnished by Misawa et al. [14], Nishimura et al. [9] and Allam et al. [23], a model can be proposed to describe the initial corrosion process of weathering steel in salt lake atmosphere (Fig. 11). At the beginning of exposure, many hygroscopic saline particles (MgCl 2 , NaCl and KCl) were deposited on the steel surface. When environmental RH reached the critical relative humidity (RH) of the salts, deliquescence of the

Samples

R s (X cm 2 )

Y dl (mF cm 2 s n )

n dl

R t (X cm 2 )

R r (X cm 2 )

Y rust (mF cm 2 s n )

n rust

A w (X cm 2 s 1/2 )

Naked

Rusted

23.34

38.59

0.90

1.17

0.81

0.51

891.4

23.34

6.57

9.106

0.53

0.018

Fe-2e Fe 2+ H 2 O+O 2 +4e 4OH - FeCl 2 and FeCl 3 Oxidation
Fe-2e
Fe 2+
H 2 O+O 2 +4e
4OH -
FeCl 2 and FeCl 3
Oxidation without
elimination of Cl -
β -FeOOH
deliquescence
-
Fe 8 (O,OH) 16 Cl 1.3
(Mg,Na,K)Cl
Cl
n
Air oxidation
GRI(Fe(OH,Cl) 2.55 )
γ -FeOOH.
Rapid oxidation
and dehydration
δ -FeOOH
amorphous

Fig. 11. Model of initial rusting process for weathering steel in salt lake atmosphere.

Q.X. Li et al. / Corrosion Science 50 (2008) 365–371

371

saline particles took place and a thin electrolyte film was formed around the deposited position [15]. When chloride ions were released from the deliquescent saline particles, they were more readily adsorbed than oxygen in competi- tion for surface sites and could cause local breakdown of the oxide/oxyhydroxide protective film on the steel surface, especially at discontinuities and surface heterogeneities [17,23]. The area covered by electrolyte layer lacked oxygen and served as anodic site. And in the anodic area iron was oxidized into ferrous ions. The region free of pollutant par- ticles and rich in oxygen acted as cathodic site. And in the cathodic region oxygen was reduced into hydroxyl ions. The excess positive charge at anodic sites would be bal- anced by migration of Cl and OH ions. In this way, countless electrochemical cells involving cathodic and ano- dic areas were formed and scattered on the steel surface. The corrosion of weathering steel was accelerated. Under open exposure conditions, in the presence of moisture and oxygen, the corrosion would be facilitated by the del- iquescence and/or oxidation of iron chlorides FeCl 2 and FeCl 3 , accompanied with the formation of hydrochloric acid [23,24]. A neutral or slightly acidic environment was created and intermediate oxyhydoxychlorides ‘‘green rust I(GRI(Fe(OH,Cl) 2.55 )) was formed on the metal surface [9,14]. Most GRI was further oxidized into b-FeOOH and Fe 8 (O,OH) 16 Cl 1.3 and a small part of GRI was trans- formed into c-FeOOH and amorphous d-FeOOH. Once b- FeOOH and Fe 8 (O,OH) 16 Cl 1.3 were formed, they would work as a reservoir of Cl . In the wetting condition, chlo- ride ion in rust was easily separated, resulting in the forma- tion of pore in rust [6].

4. Conclusions

(1) The corrosion on field-ward surface was more severe than that on skyward surface. The corrosion prod- ucts on both surfaces were mainly composed of b- FeOOH, Fe 8 (O,OH) 16 Cl 1.3 and a little c-FeOOH. Amorphous d-FeOOH was found only on skyward surface. (2) The rust layer suppressed the anodic reaction and facilitated the cathodic reaction. The very small value of rust resistance R r indicated that the rust layer as a poor barrier could not prevent the corrosion of steel. (3) Cl has an important influence on the corrosion of weathering steel in the salt lake atmosphere.

Acknowledgement

This work was funded by the National Natural Science foundation of China under the Contract 50499331.

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