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Acta Metall. Sin.(Engl. Lett.)Vol.23 No.4 pp301-311 August 2010

Electrochemical corrosion behavior of 300M ultra high strength steel in chloride containing environment
Min SUN, Kui XIAO, Chaofang DONG and Xiaogang LI

Corrosion and Protection Center, School of Material and Engineering, University of Science and Technology Beijing, Beijing 100083, China Manuscript received 26 February 2010; in revised form 23 April 2010

The electrochemical corrosion behavior of 300M ultra high strength steel in chloride containing environment was investigated by potentiodynamic polarization technique, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The results show that uniform corrosion occurs on 300M steel during the electrochemical measurements because no anodic passivation phenomenon is observed on polarization curves within the measurement range. The tests also show that 300M steel is highly susceptible to chloride containing solution, which is characterized by corrosion current density increasing with the addition of chlorides, and corrosion potential shifting towards positive direction and corrosion resistance decreasing, positively suggesting that chloride ions speed up the corrosion rate of 300M steel. Meanwhile corrosion products on the 300M steel surface formed during the salt spray test are too loose and porous to eectively slow down the corrosion rate. Additionally, a schematic structure of uniform corrosion mechanism can explain that 300M steel has better property of stress corrosion cracking (SCC) resistance than stainless steels. KEY WORDS 300M ultra high strength steel; Electrochemical corrosion; Chloride

1 Introduction 300M steel, as a kind of ultra high strength steel, is always used as high rate of loading[1,2] , i.e., the airplane landing gear and pressure vessel because of possessing a desirable combination of high tensile strength and fatigue strength, high hardness, and therefore it is always faced with the chloride containing environment during the service life, which can cause corrosion, especially SCC. Corrosion is one of the most important failures which threaten the safe usage of 300M steels, especially the SCC and failure cracking (FC). Graca et al.[1] have studied that the rupture occurred suddenly at a pressure level lower than expected for the proof pressure when 300M steel pressure vessel failed during hydrotest, and hydrogen assisted SCC was the mechanism responsible for the failure. Up to date, most studies have been focused on microstructure and the mechanical properties of 300M steel[35] , while very few papers

Corresponding author. Professor, PhD; Tel.: +86 10 62333975-509; Fax: +86 10 62334005.

E-mail address: lixiaogang99@263.net (Xiaogang LI)

 302 studied about the corrosion behavior in bulk solutions by electrochemical technique. It is well known that some aggressive ions, like chloride ions, can be adsorbed on the surface and increase corrosion rate[6,7] . The corrosion rate of steels is enhanced by chloride ions, and the eects of chloride ions on stainless steel and magnesium alloy have been studied and mature mechanisms have been summarized[8] . Chloride ions can be adsorbed on the passive surface and penetrate the oxide lm through pores or defects easier than other ions, such as SO2 . Through ow 4 of current[9,10] chloride ions can transfer into the pits, forming concentrated solutions of Fe2+ , Ni2+ , and Cr3+ chlorides, which, by hydrolysis, account for an acid solution. D et al.[11] have studied the eect of the chloride content on high strength steel az wires in NaOH solutions and found that the typical feature corresponding to chloride adsorption can be seen in the passivity domain, because the passivity current decreases as the chloride increases. In the absence of chlorides, the steel surface remains passive at 70% of the ultimate tensile strength, and no pitting potential and the zero current potential in the reverse curve dened by the reduction product -Fe2 O3 /Fe3 O4 . However, in the presence of very small amounts of chlorides, pitting occurs under this aerated condition. The pitting potential decreases as the [Cl ]/[OH ] ratio increases. In fact, deep selective corrosion patterns have been measured by AFM proling in 0.05 M NaCl solution[12] . Jegdic et al.[13] have studied the inuence of chloride ions on austenitic 304 stainless steel in aqueous sulphuric acid solution and found that, addition of NaCl accelerates the hydrogen evolution reaction on the passive surface, while the same reaction on the bare surface is somewhat inhibited by NaCl. On the other hand, presence of NaCl accelerates the anodic reaction on the bare surface, and it activates the dissolution of the passive layer, so that the passivation currents increase with addition of NaCl. However, few investigations on the inuence of chlorides have been focused on ultra high strength steels. The present paper studied the corrosion behaviors of 300M ultra high strength martensite steels in chloride containing environment by polarization curve measurement and EIS. In addition, the inuences of chloride concentration on the corrosion form, corrosion rate and morphology of 300M were also investigated. 2 Experimental 2.1 Material and test solutions The working electrodes for electrochemical measurement were cut from a bulk of 300M ultra high strength steel. The chemical composition (wt pct) of the steel is C 0.40, Mn 0.64, Si 1.66, S 0.0013, P 0.009, Ni 1.90, Cr 0.71, Mo 0.37, V 0.008 and Fe balanced. Fig.1 is the metallographic microstructure of the 300M ultra high strength steel. The microstructure of the steel contains martensite, lower bainite and retained austenite, which seems to be in agreement with the above reference literature ndings[9] . The specimens were embedded in epoxy resin leaving a working area of 1.0 cm2 . The specimen preparation was carefully controlled to ensure that there was no grooving and bubble at the epoxy/steel interface. Prior to the tests, all the working surfaces were subsequently polished to 1200grade emery paper, and rinsed with deionized water and methanol. Solutions were prepared from deionized water with 0, 0.1, 0.3, 0.5 mol/L NaCl concentrations, respectively, and used to simulate the atmospheric environment. All the tests

 303 were carried out at room temperature. The value of pH for the testing solution can remarkably inuence the corrosion rate and corrosion form. In this paper, all of the NaCl solution is near-neutral, with a pH value of 6.8. 2.2 Electrochemical measurements The conventional electrochemical measurements, including corrosion potential, potentiodynamic polarization curves and EIS, were performed in a three-electrode cell Fig.1 Metallographic microstructure of the through a PAR 2273 workstation. 300M steel 300M ultra high strength steel. was used as the working electrode, a platinum sheet as the counter electrode and a saturated calomel electrode (SCE) as the reference electrode. Prior to the electrochemical measurements, the working electrode was cathodically polarized at 1.3 V vs. SCE for 3 min to remove the air-formed oxides on the surface of electrode. The corrosion potential was then recorded for 1 h. EIS technique was used to study the corrosion behavior of 300M steel in NaCl solutions, which was measured at the open-circuit potential and frequency was ranged from 100 kHz to 0.01 Hz with an applied ac perturbation of 10 mV. The impedance data were analyzed by a commercial ZSimpWin software package. After that, the polarization curve was measured at a potential scan rate of 0.5 mV/s. The potential was ranged from 0.25 mV (vs. the open potential EOC ) to 0.3 mV (vs. the reference potential ER ). 2.3 Salt spray test Corrosion resistance of 300M ultra high strength steel was evaluated by salt spray test, which was used to simulate the atmospheric environment. Salt spray test was followed by Standard ASTM B117-97. Working materials were tested under (352) C temperature, 5 wt pct neutral sodium chloride solution and continuous spraying 4, 8, 12, 16, 20 days. All the electrode samples were tested by electrochemical techniques, including potentiodynamic polarization curves and EIS, which were used to study the electrochemical behavior of 300M with corrosion products. Solutions were prepared from deionized water with 0.2 wt pct NaCl concentrations. 3 Results and Discussion 3.1 Eect of chloride on electrochemical corrosion for 300M steel 3.1.1 Open circuit potential Fig.2 shows the variations of open circuit potential with immersion time of 300M steel electrodes in NaCl solutions with dierent concentrations at the room temperature. Observe that open circuit potentials of the electrodes in deionized water and 0.1 mol/L NaCl solution shift positively rst and then decrease to reach a relatively steady value of about 0.58 V vs. SCE and 0.61 V vs. SCE, meanwhile open circuit potentials of electrodes in 0.3 mol/L and 0.5 mol/L NaCl solutions slowly reach a steady-state value of 0.62 V

 304 vs. SCE and 0.64 V vs. SCE. With the increase of Cl content, there is a slight change of open circuit potential, less than 15 mV. The open circuit potentials shift toward negative direction, implying that the working electrodes are electrochemically unstable and susceptible to anodic dissolution with increase of Cl content. 3.1.2 Polarization curve After measurements of open circuit potential on the 300M steel electrodes for 1 h, the potentiodynamic polarization technique was used to investigate the electrochemical behavior of 300M steel in NaCl solutions with dierent concentrations. Fig.3 shows the potentiodynamic polarization curves of 300M steel in NaCl solutions.
-0.4
Deionized water

0.15 0.00 -0.15 -0.30 -0.45 -0.60 -0.75 -0.90

Deionized water

Potential / V vs. SCE

0.1 mol/L NaCl

0.5 mol/L NaCl

Potential / V vs. SCE

-0.5

0.3 mol/L NaCl

0.1 mol/L NaCl 0.3 mol/L NaCl 0.5 mol/L NaCl

-0.6

-0.7

-0.8

500

1000

1500

2000

2500

-8

-7

-6

-5
lg(i /A

-4
cm )
-2

-3

-2

-1

Time / s

Fig.2 Time dependence of open circuit potentials of the 300M steel in NaCl solutions.

Fig.3 Polarization curves of the 300M electrodes measured in NaCl solutions.

The polarization curve was scanned from cathodic to anodic potentials. Notice from the anodic polarization curves that, the current density increases rapidly with the potential. At low current densities, the cathodic reaction is a predominantly charge transfer controlled process. All electrodes are in active state and unable to be passivated in the measured potential range. It is conformed that the anodic reaction is controlled by activated dissolution process. Furthermore, with the increase of chloride concentration, the polarization curves shift toward the right-down direction and the anodic current density increase. On the cathodic branch of the polarization curve, the cathodic current density of the corrosion system should be attributed to the reduction of oxygen dissolved in the solution, and the cathodic current density decreases with the chloride concentration increasing. The presence of cathodic limiting diusion current means that all the cathodic reactions are oxygen diusion-controlled processes. When the potential is below 0.85 V, the cathodic current density shifts towards right obviously, because hydrogen reduction occurs beside the oxygen reduction. The anodic dissolution of 300M ultra high strength steel can be expressed as Fe Fe2+ + 2e (1) This work shows that diusion and reduction of oxygen dominate the cathodic process, as demonstrated by the presence of cathodic limiting diusive current density. So the cathodic reaction can be expressed as O2 + 2H2 O + 4e 4OH (2)

 305 When the corrosion potential is below 0.85 V, the reduction of hydrogen occurs. In neutral solutions hydrogen evolution occurs predominantly through the reduction of H2 O rather than hydrogen ions: 2H2 O + 2e H2 + 2OH (3) The values of the electrochemical parameters corrosion potential Ecorr , corrosion current density icorr , anodic tafel slope ba and cathodic tafel slope bc in NaCl solution are shown in Table 1. Notice that with the increase of chloride concentration, the corrosion potential Ecorr decreases from 0.448 V vs. SCE to 0.637 V vs. SCE and this result is remarkable at higher chloride concentration. Meanwhile the chloride ions can induce the increase of the corrosion current density icorr and the decrease of anodic Tafel slope ba . In deionized water icorr is only 7.24 A, which is remarkably lower than the values in NaCl solutions. 300M steel has the lowest corrosion rate in deionized water, because there is no accelerating eect of chloride ions. It is thus reasonable to assume that chloride ions accelerate corrosion rate of 300M steel obviously.
Table 1 Solutions Deionized water 0.1 mol/L NaCl 0.3 mol/L NaCl 0.5 mol/L NaCl Values of parameters observed from polarization curves Ecorr /V vs. SCE 0.448 0.552 0.587 0.637 icorr /A 7.24 10.4 11.5 14.8 ba /V vs. SCE 0.2141 0.0607 0.0564 0.0480 bc /V vs. SCE 0.4078 0.7488 0.5940 0.8718

After measurement of polarization curves, the surface morphologies of electrodes were observed visually. It is found that there are trace amounts of dark corrosion products on surface of the 300M electrodes. No evidence of localized attack is observed after corrosion products removed. 3.1.3 EIS The EIS results are presented in the form of Nyquist plots, in which the imaginary impedance Zim is plotted against the real impedance Zre . Fig.4a shows the Nyquist plots obtained on electrodes in deionized water and NaCl solutions with dierent concentrations at the open circuit potential. Notice that there is a similar impedance feature for all the electrodes, i.e., one depressed semicircle over the whole frequency range, and they are all characteristic of a capacitive behavior, indicating that there is one interfacial reaction process occurring over the measurement frequency range.

2000 1750
cm

(a)

De 0.

ionized water 1 M NaCl 5 M NaCl

1500 1250 1000 750 500 250 0 0 500 1000

0.3 M NaCl 0.

Zi

1500
cm

2000

2500

re

Fig.4 Nyquist plots of impedance in NaCl solutions with dierent concentrations and electrochemical equivalent circuits.

 306 In the monitoring technique based on the theory of electrochemical impedance, the solution resistance Rs is estimated from impedance measured in the high frequency range, while the sum of polarization resistance and the solution resistance are estimated from the impedance in the low frequency range. It is well known that the polarization resistance is inversely proportional to the corrosion rate in aqueous solutions. Thus this technique is very useful for monitoring the atmospheric corrosion rates. Notice from Fig.4a that the Nyquist impedance semicircles decrease with the increase of chloride concentration. While for electrode in deionized water, the semicircle size is much larger than that in NaCl solutions, implying that the polarization resistance also decreases with addition of chloride ions, which in turn increases the corrosion rate. This agrees with the previous polarization work. The electrochemical equivalent circuit for a simple corroding electrode is represented by a semi-circle, with the parallel connection of the charge-transfer resistance Rct and the double-layer capacitance Cdl . When potential E is the only status variable during electrode process, the charge-transfer resistance Rct is equal to linear polarization resistance Rp . The simple linear relation that denes the corrosion current density forms, icorr is estimated from Rp using the Stern-Geary relationship icorr = B 2.303Rp (4)

where B=f (a , c ), and Tafel anodic a and cathodic c slopes are taken as positive kinetic parameters for determining icorr of a corroding or oxidizing metallic material. The value of B is less than 1 V. Rp is the linear polarization resistance, which can be evaluated from polarization curves. Eq.(4) predicts that the corrosion current density is very sensitive to changes in the polarization resistance. This icorr expression is simple but essential in corrosion measurement, since icorr can be converted to corrosion rate in units of mm/y, which are more convenient for engineering purposes[17] . The electrochemical equivalent circuit for 300M electrodes in NaCl solutions with dierent concentrations are shown in Fig.4b with the parallel connection of Rct and Q. Electroelements in Fig.4b have the following meanings[17] : Rs is the electrolyte resistance between the working and reference electrodes; Rct is the polarization resistance and in inversely proportional to icorr , and Rct is equal to Rp because there is only one time constant; Q is the constant phase angle element (CPE) in place of the interfacial capacitance Cdl when the dispersion eect exists, which is caused by the roughness of working electrode surface. The parameters observed from Fig.4 are shown in Table 2. Observe that in deionized water Rs is thousands of times of that in NaCl solutions, and Rct decreases with the increase of chloride concentration, indicating that the corrosion rate increases according to the Eq.(4). It agrees with previous potentiodynamic polarization studies.
Table 2 Values of parameters observed from Nyquist plots Solutions Deionized water 0.1 mol/L NaCl 0.3 mol/L NaCl 0.5 mol/L NaCl Rs /cm2 192.3 27.48 5.476 2.592 Q Y0 /1 cm2 sn 0.000473 0.001594 0.002695 0.001186 n 0.7012 0.7684 0.6611 0.7742 Rct /cm2 2244 1263 1257 1019

 307 3.2 Electrochemical behavior of 300M steel with corrosion products after salt spray test After the salt spray test with dierent days, the polarization curves of 300M steel were measured in 0.2 wt pct NaCl solutions, as shown in Fig.5. Notice that with the processing of salt spray test, polarization curves move to the right-down side. Additionally, comparing Fig.3 with Fig.5, it can be seen that the corrosion current in Fig.5 is 23 orders of magnitudes than that in Fig.3, even the polarization curves are measured in lower chloride concentration solutions. The corrosion potentials shift towards negative and the corrosion currents become larger, meaning that the corrosion rate of 300M steel is speeded up after salt spray test. But the dierences between all of the polarization curves are small. It can be concluded that corrosion products have formed and adhered to the metal surface, acting as the function of passive lm on the stainless steel. But the protection of the corrosion products against chloride ions is not eective as passive lm, so the corrosion rate is accelerated with the processing of the salt spray test. Fig.6 shows the Nyquist plots of 300M steel after the salt spray test with dierent time. For all the Nyquist plots, there is a depressed semicircle at the high frequency which is characterized by a capacitive behavior, and another incomplete semicircle is present at the low frequency which is related with the corrosion products on the metal surface.
0.6 4 days
8 days

0.4
Potential / V vs. SCE

0.2

12 days 16 days 20 days

0.0

-0.2

-0.4

-0.6 -5 -4 -3 -2
lg(i /A

-1
cm )
-2

Fig.5 Polarization curves of 300M ultra high strength steel in 0.2 wt pct NaCl after salt spray test.
200 175 150
2
(a) 4 days

125 100 75 50 25 0 0 50 100

-Z

im

cm

12 days 16 days 20 days

8 days

150
Z
re

200
cm

250
2

300

350

Fig.6 Nyquist plots of impedance for 300M ultra high strength steel in 2 wt pct NaCl after salt spray test and electrochemical equivalent circuits.

The electrochemical equivalent circuit for the 300M electrodes after salt spray test in 0.2 wt pct NaCl solutions is shown in Fig.6b, Qf is the CPE and Rf is resistance caused by the lm of corrosion products. The other electro elements in Fig.6b have the same meanings as described in Fig.4b. With the processing of the salt spray test, the diameters of capacitive semicircles decrease. Corrosion products formed on the metal surface during the salt spray test have two eects: one is that the corrosion products can slow down the exchange of reaction ions to some extent, for example, chloride ions permeates into the substrate/corrosion products interface and the iron ions permeate out of the corrosion products into the solutions. The

 308 other one is that corrosion products are too loose to stop the permeation of chloride ions into the iron/corrosion products interface. Chloride ions continue to destroy the substrate integrity and aggravate the corrosion rate. 3.3 Analysis of corrosion mechanism for 300M ultra high strength steel Morphologies of 300M steels after anodic polarization in NaCl solutions with dierent concentrations are shown in Fig.7. It is obviously seen that corrosion morphologies become more serious with increasing concentrations of chloride ions. As shown in Fig.7a, little corrosion product has formed on the whole surface in deionized water. After polarization in 0.1 mol/L NaCl solutions, a thin layer of corrosion products covers the whole surface and a number of ne cracks lie among them, shown in Fig.7b. Block corrosion products can be seen in Figs.7c and 7d, and the sizes of them are approximately close to each other. From the even micrograph in Fig.7, it can be calculated that uniform corrosion occurs on 300M steel in NaCl solutions. The SEM results show that the presence of chloride ions increases corrosion rate of 300M steel, and this phenomenon is in complete agreement with the results obtained from electrochemical measurements. In the environment containing appreciable concentrations of Cl , corrosion products are formed on 300M steels surface and block the diusion of corrosion media containing Cl , which act as the eective barriers against diusion of matters through the lm and hence decreases the active dissolution current. When the oxide-lm is present, corrosion occurs through outward diusion of cations and inward diusion of ions. But it can be seen that, from the corrosion morphologies of 300M shown in Fig.7, corrosion products are too loose and porous to eectively block the chloride ions penetrating into the interface

Fig.7 Morphologies of 300M steels after anodic polarization in NaCl solutions with dierent concentrations: (a) deionized water; (b) 0.1 mol/L; (c) 0.3 mol/L; (d) 0.5 mol/L.

 309 of corrosion products/substrate, so Cl penetrates the oxide lm through pores or defects easier than do that in stainless steel; hence more corrosion pits initiate on the interface of the corrosion products/metal and evenly distribute on the surface, so the corrosion form is uniform corrosion macroscopically. There is more evidence that uniform corrosion occurs on 300M ultra high strength steel during dynamic polarization test and salt spray test. Fig.8 shows the lateral morphology of 300M steel after salt spray test and corrosion products removed. Notice that the lateral side is irregularity, with many low holes. According to dene of pitting, all the holes are not deep enough to be dened pits. The schematic structure of uniform corrosion of the 300M steel exposed to chloride solution is shown in Fig.9.

Fig.8 Lateral morphology of 300M steel after salt spray test.

Fig.9 Schematic structure of uniform corrosion mechanism for 300M steel exposed to chloride solution.

From the lateral morphology and schematic structure of uniform corrosion for 300M steel, it can explain that the diameters of Nyquist diagrams for 300M steels after salt spray test dramatically decrease. Comparing the dierence of the corrosion morphologies between 300M steel and stainless steels, stainless steels remain essentially passive in environments containing Cl . From the perspective of the oxide-lm theory, breakdown of passivity by Cl occurs locally rather than generally. It is evident, because of the possibility of passive-active cell formation, that deep pitting is much more common with passive metals than with nonpassive metals[10,18,19] . Once a pit initiates, a passive-active cell is set up of 0.50.6 V potential dierence. Minute anode of active metal is formed and surrounded by large cathodic areas of passive metal. The resultant high current density accompanies a high corrosion rate of the anode (pit) and, at the same time, polarizes the alloy surface immediately surrounding the pit to values below the critical potential. High current densities at the anode cause high rates of metal penetration. Through ow of current, Cl transfer into the pit forming concentrated solutions of Fe2+ , Ni2+ , and Cr3+ chlorides, which, by hydrolysis, account for an acid solution, as shown in Fig.10. A pit stops growing only if the surface within the pit is again passivated[20,21] . It has been well known that pits and defects play a role in SCC initiation. In general, SCC is observed in alloy-environment combinations that result in the formation of a lm

 310 on the metal surface, making the alloy desirable for resistance to uniform corrosion. SCC can initiate at pits that form during exposure to the service environment by a breakdown in the protective lm. The pit geometry is important in determining the stress and strain rate at the base of the pit. Generally, the aspect ratio between the penetration and the lateral corrosion of a pit must be greater than about 10 before a pit acts as a crack initiation site. A penetration to lateral corrosion ratio of 1 Fig.10 Schematic structure of passive-active corresponds to uniform corrosion, and a racell responsible for pit growth in staintio of about 1000 is generally observed for less steel exposed to chloride solution. a growing stress-corrosion crack. As in the case of a growing crack, the pit walls must exhibit some passive lm forming capability in order for the corrosion ratio to exceed 1[22] . Comparing Fig.9 and Fig.10, the stainless steel is more susceptive to SCC. Considering the 300M steel in NaCl solutions, it can be calculated that, even though passive lm can not form and 300M steel are less corrosion resistance than stainless steels, it has a better property desirable for resistance to SCC. In this aspect, 300M steel is suitable for applying in the aggressive environment with corrosive media and tensile stress where SCC tends to occur. 4 Conclusions Uniform corrosion occurs on 300M steel during electrochemical measurement in NaCl solutions with dierent concentrations. There is no anodic passive potential region on the polarization curves. It is clear that the 300M steel is highly susceptible to NaCl solutions, which is characterized by corrosion current density increasing with addition of chloride ions, and the increase of chloride concentration shifts corrosion potential towards positive direction and decreases the corrosion resistances, positively suggesting that the chloride ions speed up the corrosion rate of 300M steel. Meanwhile the corrosion rate of 300M steel with corrosion products are accelerated after salt spray test, and corrosion products on the 300M steel surface formed during the salt spray test are too loose and porous to eectively slow down the corrosion rate. The schematic structure of uniform corrosion mechanism can well explain that the 300M steel has better property of SCC resistance than stainless steels.
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