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Materials and Corrosion 2013, XXX, No.

XXX

DOI: 10.1002/maco.201206984

Sensitivity of the passive lms on APIX100 steel heataffected zones (HAZs) towards trace chloride concentrations in bicarbonate solutions at high temperature
F. F. Eliyan* and A. Alfantazi
This paper investigates the stability and growth of the passive lms on the heat affected zones (HAZs), of APIX100 pipeline steel, in dilute bicarbonate solutions containing 100 and 300 ppm chloride ions at 363 K. The investigations were carried out by electrochemical methods, and the kinetics and corrosion rates were evaluated. The HAZs were simulated by thermal Gleeble cycles of heating up to 1223 K peak temperature, followed by cooling at 10, 30, and 60 K/s. The 30 and 60 K/s HAZs showed evidence of thin, highly sensitive passive lms towards the increased chloride concentration, and evidence of increased chargetransfer resistance over immersion time at the OCP conditions. The corrosion rates of the 30 K/s HAZs, of which acicular ferrite is the main constituent, were the lowest, among other samples, as revealed by the slow 0.05 mV/s potentiodynamic polarization and EIS. The passive lms of the 10 K/s HAZ, at the open circuit potentials, were of the highest resistance to deteriorate/facilitate for mass transport.

1 Introduction
Corrosion of the heataffected zones (HAZs) is a special, critical type of problems that oil and gas pipelines are highly prone to at the welded regions [1,2]. Its criticality lies mainly in the microstructure, location, and size of the HAZs factors that all contribute to localized penetration of uneven, signicantly high corrosion rates. The microstructures of the HAZs are different from the base pipeline steel microstructures at extents primarily pertaining to a welding procedure [3] like that of the pulsed gas metal arc welding (PGMAW), a mechanized procedure of high operation efciency. Such a procedure is executed with slow rates to facilitate appreciably for complete phase transformation from austenite to ferrite and pearlite, or to mixtures of ferrite, bainite, and martensite [4] during a thermal cycle before another one starts. An incomplete ferritetoaustenite transformation, during a dualtorch PGMAW of interrupted cooling cycles, for instance, makes the corrosion vulnerability of a HAZ a strong function of its microstructures and size. A HAZ is between the weldment and the base pipeline zones, a narrow zone over a pipe circumference, of microstructures that are the highest sensitive to the thermal inputs and dissipations during a welding process. A broad variety
F. F. Eliyan, A. Alfantazi Department of Materials Engineering, The University of British Columbia, Vancouver, British Columbia V6T 1Z4 (Canada) E-mail: faysal09@interchange.ubc.ca

of HAZ microstructures is expected, and that makes selection and control of a welding procedure highly more important to optimize. Corrosion at a welding region simultaneously sustains on the three adjacent zones to constitute segregated active micro galvanic cells [5]. The attack as a result becomes preferential and localized, and of accelerated rates to lead, over time, to premature thinnings, leakages, and catastrophic res [6]. Research on simulated HAZs corrosion is actually useful to evaluate and identify the most susceptible HAZs to deteriorate, and to better prediction of the overall corrosion behavior in the eld. Most of the available HAZ corrosion studies do not address the electrochemical aspects of the problem, and they are mostly emphasizing on the stress endurance and the environmentally assisted cracking resistance in bicarbonatebased solutions [79]. The natures of the interfacial interactions between a HAZ microstructure and the main corrosive carboncarrying species, with respect to an environmental condition, did not receive specic or sufcient investigations. In some studies, like the one published by Mustapha et al. [10], the HAZs were made by ordinary heat treatments, compromising relatively the signicance of a real HAZ on the corrosion behavior in the eld. In this paper, the inuence of the chloride ions, introduced with trace 100 and 300 ppm concentrations, on the stability and the growth of the passive lms is investigated in dilute bicarbonate solutions at 363 K. The measurements investigate the behavior of the passive lms from specic electrochemical

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Materials and Corrosion 2013, XXX, No. XXX

aspects in reference to three types of HAZs made of APIX100 pipeline steel. The main objectives, and implications, of this research were explained in two previous efforts [11,12], in a pursuit devoted for evaluating the corrosion behavior of the HAZs of the newgeneration HSLA pipeline steels.
Temperature (K)

1200

1000

10 K/s

2 Experimental details
2.1 Corrosion test setup The experiments were carried out in a 1 L, threeelectrode, multi port jacketed cell. The working electrodes were machined from APIX100 steel sheet into at disks and mounted in hard epoxy resins of hightemperature reliability. The potentials were measured against the saturated calomel electrode (SCE) of 240 mV versus SHE, and the counter electrode was a graphite rod. The jacketed chamber was a part of a loop in which a 368 K constantvelocity water stream was circulated by a ColeParmer heater. The experiments were carried out by VersaStat 4 potentiostat, and with a synchronized software program, the experiments were controlled and the results were analyzed. 2.2 Test material The specimens were wet ground in sequence by 120, 320, and 600 grit emery papers, and then degreased in ethyl alcohol for 10 min, rinsed with distilled water and dried in a hot air stream. The chemical composition, presented in Table 1, of the test APIX100 steel was analyzed by inductive coupled plasma (ICP) and LECO carbon analysis. The SEM micrographs of the as received and the HAZ microstructures were produced by a variablepressure Hitachi S300N SEM. To reveal the microstructures, selected samples were wetground up to 1200 grit nish, polished with 6 and 1 m diamond suspensions, immersed in a Nital etchant (2 ml of 70% nitric acid and 98 ml of anhydrous, denatured ethyl alcohol), treated with alcohol swapping and nally dried in an air stream. As shown in Fig. 2a, the microstructure of the asreceived specimen consisted of a mixture of intergranular ferrite (F), pearlite, and bainitic ferrite (BF). A Gleeble thermal simulation machine was set to execute thermal cycles, presented in Fig. 1, on specimens to be of microstructures resembling three typical pipeline HAZs. The samples were heated up to a peak 1223 K at a rate of 100 K/s, and then cooled with different rates of 10, 30, and 60 K/s. The 10 K/s HAZ microstructure consisted, as shown in Fig. 2b, of equiaxed polygonal ferrite (PF) of large grain sizes, and few amounts of bainitic ferrite and pearlite. In 30 K/s HAZ, acicular ferrite and martensite were the main constituents, and the microstructure of 60 K/s HAZ was martentistic (M) with some prior austenite grains, as shown in Fig. 2c and d, respectively.

100 K/s
800

30 K/s

60 K/s
600

400

200 0 20 40 60 80 100 120

Time (s)

Figure 1. The Gleeble thermal simulation cycles set to simulate the HAZ microstructures by cooling at 10, 30, and 60 K/s from 1223 K peak temperature

2.3 Test solutions The tests were carried out in dilute 5 g/L bicarbonate solutions of 100 and 300 ppm Cl. The temperature was maintained at 363 K, and the pH was between 8.3 and 8.6. 2.4 Electrochemical tests The specimens were subjected to a cathodic conditioning at 2 V versus SCE for about 10 min before commencing the experiments which were repeated for many times to ensure the reproducibility of the results. The cyclic potentiodynamic polarization was scanned from 1.3 V to a vertex 1.2 V versus SCE, and scanned downward to the open circuit potentials, at a rate of 0.05 and 0.5 mV/s. At 0.5 V versus SCE for 4000 s, the potentiostatic polarization tests were carried out. The growth of the passive lms and the change in the transport interactions at the open circuit potentials over after 1000, 2000, and 3000 s were investigated by electrochemical impedance spectroscopy with a sampling rate of 10 points per decade from 10 000 to 0.1 Hz.

3 Results and discussion


3.1 Cyclic potentiodynamic polarization The proles representing the 0.05 mV/s polarization in 100 and 300 ppm Cl solutions are shown in Fig. 3. They show high

Table 1. Chemical composition (wt%) of the test API-X100 steel

C
0.1

Mn
1.66

Mo
0.19

Ni
0.13

Al
0.02

Cu
0.25

Ti
0.02

Nb
0.043

Cr
0.016

V
0.003

C.E.
0.45

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Materials and Corrosion 2013, XXX, No. XXX

Passivation on HAZs

Figure 2. Metallographic SEM images of the microstructures of (a) the base steel, (b) 10 K/s, (c) 30 K/s, and (d) 60 K/s HAZs

cathodic current densities of nearly 24 mA/cm2 at 1.3 V versus SCE, notably broad peaks, stable mixedcontrol regions at 0.2 V versus SCE, passivation of a range of nearly 700 mV and second peaks at between 0.8 and 0.9 V versus SCE. Exclusively, the 30 K/s
Base steel
1.0 1.0

HAZ, of which acicular ferrite is the main constituent, showed the minimum cathodic activity and multiple anodic peaks. The passivation behavior was notably dependent on the microstructure type and the chloride concentration. The active dissolution,
30 K/s HAZ
1.0 1.0

10 K/s HAZ

60 K/s HAZ

0.5

0.5

0.5

0.5

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE )

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0.0

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100 ppm Cl10-8 10-7 10-6 10-5 10-4 10-3 10-2

100 ppm Cl10-8 10-7 10-6 10-5 10-4 10-3 10-2

100 ppm Cl10-8 10-7 10-6 10-5 10-4 10-3 10-2

100 ppm Cl10-8 10-7 10-6 10-5 10-4 10-3 10-2

Current density (A/cm 2)

Current density (A/cm2)

Current density (A/cm2)

Current density (A/cm2)

Base steel
1.0 1.0

10 K/s HAZ
1.0

30 K/s HAZ
1.0

60 K/s HAZ

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Potential (V vs. SCE)

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300 ppm Cl10-8 10-7 10-6 10-5 10-4


2

300 ppm Cl10-3 10-2 10-8 10-7 10-6 10-5 10-4


2

300 ppm Cl10-3 10-2 10-8 10-7 10-6 10-5 10-4


2

300 ppm Cl10-3 10-2 10-8 10-7 10-6 10-5 10-4 10-3 10-2

Current density (A/cm )

Current density (A/cm )

Current density (A/cm )

Current density (A/cm2)

Figure 3. 0.05 mV/s cyclic potentiodynamic polarization for the base steel and the HAZs in 5 g/L NaHCO3 solutions containing 100 and 300 ppm Cl at 363 K

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Materials and Corrosion 2013, XXX, No. XXX

which mainly incorporates hydroxyl and bicarbonate [13,14], seemed to be decelerated by a more rapid passivation than that at lower temperatures [15,16] where small, sharp anodic peaks sometimes appeared right below the alwaysreproducible broad peaks. That encourages to analyze the inuence of temperature on the nature of the prepassive or lowvalence Fe(OH)2 oxide and its interference with the dissolution reactions. Its formation (Equation 1) in bicarbonate solutions was reported and discussed in many papers [17,18].

bicarbonate and chloride, mentioned that Fe(OH) results in Fe(OH) in a rate determining step (Equation 2), whom El Naggar [20] mentioned it transforms, depending on the applied potential, to a protective adsorbent oxygen complex.

FeOHads $ FeOH e

Fe 2OH ! FeOH2 2e

Similar to previous observations in Ref. [11], the cathodic reduction of oxygen (Equation 3), in the subject mildly alkaline solutions, interfered with the passivation currents to result in 300 mVbroad peaks.

It is preceded by adsorptionbased steps that involve adorbent complexes such as FeO2 2 , HFeO2 , and Fe(OH). Lu et al. [19], who carried out potentiodynamic polarization tests on pure iron at 30 8C (303 K) in solutions of different concentrations of

O2 2H2 O 4e 4OH

Their size was independent from the microstructure type, and they can be interpreted as a coalescence between
0

a
a
-200

Corrosion potential (mV vs. SCE)

-200

Passivation potential (mV vs. SCE )

-400

-400

-600 100 ppm Cl300 ppm Cl-

-600

100 ppm Cl 300 ppm Cl-

-800 As-received 10 C/s 30K/s C/s HAZ HAZ 60 60K/s C/s HAZ HAZ 10 K/sHAZ HAZ 30 As-received

-800 As-received 10 C/s 30K/s C/s HAZ HAZ 60K/s C/s HAZ HAZ 60 10 K/sHAZ HAZ 30 As-received

API-X100 test samples


140

API-X100 test samples


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b
120

Transpassivation potential (mV vs. SCE)

Corrosion current density (A/cm )

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40 100 ppm Cl 300 ppm Cl 20

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100 ppm Cl300 ppm Cl

0 As-received 10 C/s 30K/s C/s HAZ HAZ 60 60K/s C/s HAZ HAZ 10 K/sHAZ HAZ 30 As-received

0 As-received 10 C/s 30K/s C/s HAZ HAZ 60K/s C/s HAZ HAZ 60 As-received 10 K/sHAZ HAZ 30

API-X100 test samples


Figure 4. (a) Corrosion potentials (Ecorr) and (b) corrosion current densities (icorr) of the asreceived and the HAZ samples in 5 g/L NaHCO3 solutions containing 100 and 300 ppm Cl at 363 K

API-X100 test samples


Figure 5. (a) Passivation potentials (Epass) and (b) Transpassivation potentials (Etranspass) of the asreceived and the HAZ samples in 5 g/L NaHCO3 solutions containing 100 and 300 ppm Cl at 363 K

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Passivation on HAZs

the anodic peaks, which appear during the polarization of iron and steels in bicarbonate solutions [21,22], and the cathodic peaks of the O2 reduction. At low potentials slightly below the rst anodic peaks bicarbonate functions as an active adsorbent to form carboncarrying complexes, such as FeHCO 3 , to drive, in a series of reactions, FeCO3 precipitation. Alternatively, as reported by Simard et al. [23], the passive lms can more probably grow multilayered of Fe(OH)2 and FeCO3 in a process Fe(OH)2 is reacting with HCO 3. The passive regimes were broad and comparable, and they revealed the signicance of the microstructure type. The current densities were as the lowest as nearly 1 A/cm2 for the as received and the 10 K/s HAZ, of microstructures mainly composed of ferrite which upon dissolution cementite (Fe3C) becomes the conductive, effective, anchoring network for thick passive lms to precipitate/grow within [24]. For the 30 and 60 K/s HAZs, the passive current densities were nearly as great as 40 and 10 A/cm2, respectively. The higher current densities indicate thinner/less stable passive lms to have formed on the lowtemperaturetransformation phases of the acicular and bainitic ferrite, and martensite phases of high residual stresses and high density of lattice defects [5,25]. FeCO3 oxidizes to gFe2O3 at higher potentials, as reported by Castro et al. [17] who carried out voltammetric studies in carbonate/bicarbonate solutions:
2FeCO3 3H2 O ! g Fe2 O3 2CO2 3 6H 2e

4
A brief discussion (to refer to) was previously made on the reactivity of the dissolved O2 and OH with FeCO3 to generate Fe2O3 and/or Fe3O4 [11,15]. After transpassivation, which
Base steel
1.0 1.0

occurred at comparable potentials, second anodic peaks of various sizes appeared below the vertex potentials. If the inuence of O2 is discounted, these peaks which were seldom reproducible in chloridefree solutions [11] can be linked to repassivated pits onto ruptured lms, as proposed by Jelinek and Neufeld [26] on similar observations in bicarbonatechloride solutions, but at lower potentials. It should be noted that only the 10 K/s HAZ exhibited a positive hysteresis loop in the 100 and 300 ppm Cl solutions. Increasing the chloride concentration to 300 ppm made the passive currents markedly higher to nearly 320 A/cm2 for the asreceived samples. It destabilized the passive lms on the 30 and 60 K/s HAZs, whose passivation regimes exhibited many intense spikes. To explain, the Cl ions adsorb between the adsorbed ontothesurface H2O molecules and the sites where the lm is thinner or more permeable to initiate, consequently, the lm pitting and the increase in the substrate dissolution rates [27] a phenomenon that causes the intense repetitive spikes with the thin passive lms that formed on the 30 and 60 K/s HAZs. As Fig. 4 shows, the corrosion potentials are between 780 and 760 mV versus SCE, and the corrosion rates were between 80 and 120 A/cm2. But except for the 30 K/s HAZs, the corrosion potentials were nearly 820 mV versus SCE and the corrosion rates were between 20 and 30 A/cm2. That is very attributed to the slower cathodic reactions on the 30 K/s HAZs, given that the proportion between the acicular and grain boundary ferrites of a similar HAZ was reported to be a strong factor in affecting the rate of the cathodic reactions [28]. The corrosion rates showed sensitivity towards chloride, but the onset of passivation, as shown in Fig. 5, did not, and it is interesting to note the delayed, of 570 mV versus SCE, onset of passivation of the 30 K/s HAZ. While it is difcult to articulate on the discrepancy of the transpassivation potentials of the asreceived and the 10 K/s HAZ with the chloride concentrations, the potentials of the 30 and
30 K/s HAZ
1.0 1.0

10 K/s HAZ

60 K/s HAZ

0.5

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Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

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100 ppm Cl10-7 10-6 10-5 10-4


2

100 ppm Cl10-3 10-2 10-7 10-6 10-5 10-4


2

100 ppm Cl10-3 10-2 10-7 10-6 10-5 10-4


2

100 ppm Cl10-3 10-2 10-7 10-6 10-5 10-4 10-3 10-2

Current density (A/cm )

Current density (A/cm )

Current density (A/cm )

Current density (A/cm 2)

Base steel
1.0

10 K/s HAZ
1.0 1.0

30 K/s HAZ
1.0

60 K/s HAZ

0.5

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Potential (V vs. SCE)

Potential (V vs. SCE)

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300 ppm Cl10-8 10-7 10-6 10-5 10-4 10-3 10-2

300 ppm Cl10-8 10-7 10-6 10-5 10-4 10-3 10-2

300 ppm Cl10-8 10-7 10-6 10-5 10-4 10-3 10-2

300 ppm Cl10-8 10-7 10-6 10-5 10-4 10-3 10-2

Current density (A/cm2)

Current density (A/cm2)

Current density (A/cm2)

Current density (A/cm 2)

Figure 6. 0.5 mV/s cyclic potentiodynamic polarization for the base steel and the HAZs in 5 g/L NaHCO3 solutions containing 100 and 300 ppm Cl at 363 K

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Materials and Corrosion 2013, XXX, No. XXX

60 K/s HAZs in 300 ppm solutions were less than the 100 ppm solutions. That can be attributed to the lesser resistance of the passive lms to deteriorate upon the adsorption of chloride ions, with greater concentrations, counteracting the competitive adsorption of O2, of H2O, to make the passive lms deteriorate at lower potentials. The equilibrium between O2 and Cl species adsorbing on a passive lm was reported by

Kolotyrkin [29] as:

M O

H H

x x Cl $ MCl x mH2 O

The polarization carried out at a higher 0.5 mV/s scan rate is represented in Fig. 6. The current densities during the cathodic

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Base steel

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0 0 1000 2000 3000 4000

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Time (s)

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Current density (A/cm )

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0 0 1000 2000 3000 4000

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Time (s)

Base steel [11]


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0 0 1000 2000 3000 4000

Time (s)

Figure 7. The potentiostatic polarization proles at 0.5 V versus SCE for the base steel and the HAZs in 5 g/L NaHCO3 solutions containing 100 ppm Cl, and for the base steel in a chloridefree solution [11], at 363 K

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Passivation on HAZs

reduction and passivation were higher than those of 0.05 mV/s and they generally imply, as previously reported by Mitsui et al. [7] from 20 mV/min polarization scans on a number of HAZs, no sensible signicance of a specic HAZ microstructure with the polarization behavior. Regardless of the chloride concentration, negative hysteresis loops resulted for all samples. 3.2 Potentiostatic polarization

the currents were nally nearly 1 mA/cm2. Increasing the chloride concentration to 300 ppm did not impose quite different effects with respect to a HAZ microstructure. It is interesting to note the continuously decreasing, and slightly uctuating, currents over time for the asreceived sample to become nally nearly 0.2 mA/cm2 currents higher than the asreceiveds in chloridefree solutions [11] whose prole is shown in Fig. 7. 3.3 Electrochemical impedance spectroscopy

The potentiostatic proles generated at 0.5 V versus SCE in 100 ppm solutions are shown in Fig. 7. The currents showed a considerably fast decrease over the rst 300 s. The currents of the 30 and 60 K/s HAZs were the lowest, being nearly 10 and 50 A/cm2, respectively, and they showed limited spikes. Their currents were almost of an order of magnitude different from the potentiodynamic currents at the same potential. The currents of the10 K/s HAZ and asreceived samples were higher, and their nal values and pattern of change over time were not reproducible. For the 10 K/s HAZ, the spikes, corresponding to repetitive ruptures of the passive lms, intensied over time and

The Nyquist spectra generated over 3000 s of immersion in 100 ppm Cl solutions at the open circuit potentials are represented in Fig. 8. They reect the two timeconstant nature of interactions being sustained on passivated interfaces [30] with no indications, across relatively these short EIS frequency ranges, to considerable dependence on a HAZ microstructure. All samples developed relatively transparent, brownish passive lms with quite minimal pitting. As shown in Fig. 9, for the asreceived sample, the semitransparent passive lm shows evidence of a spread of starlike shallow attacks, but not penetrating through to

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Figure 8. EIS Nyquist spectra of (a) the base steel, (b) 10 K/s, (c) 30 K/s, and (d) 60 K/s HAZs, monitored over after 1000, 2000, and 3000 s of immersion in 5 g/L NaHCO3 solutions containing 100 ppm Cl

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Materials and Corrosion 2013, XXX, No. XXX

Figure 9. The brownish passive lm formed on the base steel after 3000 s of immersion, at the OCP conditions, in 5 g/L NaHCO3 solutions containing 100 ppm Cl. It shows the starlike spread of shallow attacks on the semitransparent passive lm

the substrate. The twotimeconstant tting for the interactions sustained through the passive lms to the substrate, therefore, well complies with the physical observation. The small high frequency capacitive arcs overlapped with long diffusion tails, to show that the chargetransfer resistance increased over time for the 30 and 60 K/s HAZs. The inuence of bicarbonate in our case, at high temperature, on the resistance at the double layers and of the passive lms is similar to that reported from the 0.1 M NaHCO3 to 0.17 M NaCl solutions at 25 8C (298 K) [12]. The chargetransfer resistance, proportionally corresponds to the size of a Nyquist plot, was the highest for the 30 K/s HAZs, conrming with the potentiodynamic polarization results that showed the lowest corrosion rates for those HAZs. Agreeably, Huang et al. [31] reported an increased chargetransfer resistance of HAZs of large Widmansttten ferrite fractions (the acicular ferrite of our 30 K/s HAZ can be considered as a ne Widmansttten ferrite) in harsher corrosion conditions, without proposing relevant reasons. Increasing the chloride concentration did not induce signicant changes, but the time of immersion needs to be considerably longer, especially for the asreceived and 10 K/s HAZ, in future studies, to better understand the correlations between the growth of the passive lms and the charge transfer resistance, in relation to chloride concentration. The phase peaks, which are shown in Fig. 10,
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Phase angle (deg) 2 IZI (.cm )

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Figure 10. EIS Bode spectra of (a) the base steel, (b) 10 K/s, (c) 30 K/s, and (d) 60 K/s HAZs, monitored over after 1000, 2000, and 3000 s of immersion in 5 g/L NaHCO3 solutions containing 100 ppm Cl

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Phase angle (deg)

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IZI (.cm )

IZI (.cm )

Phase angle (deg)

IZI (.cm )

Materials and Corrosion 2013, XXX, No. XXX

Passivation on HAZs

Metal surface

Double layer
Ydl

Passivation
Yf

Solution

constant type of interactions on/across passivated interfaces, and they showed a continuous increase of charge transferresistance over time for the 30 and 60 K/s HAZs at the open circuit potentials. Acknowledgements: This publication was made possible by NPRP grant #092112089 from the Qatar National Research Fund (a member of Qatar Foundation). The statements made herein are solely the responsibility of the authors.

RS

Rch

Rf

YW

Figure 11. The twotimeconstant equivalent circuit tting the experimental EIS data

5 References
[1] A. Palmer, R. King, Subsea Pipeline Engineering, PennWell corporation, Tulsa, OK 2008. [2] P. Rhodes, Corrosion 2001, 57, 923. [3] G. Goodall, J. Gianetto, J. Bowker, M. Brochu, Can. Metall. Q. 2012, 51, 58. [4] W. Xu, Q. Wang, T. Pan, H. Su, C. Yang, J. Iron Steel Res Int. 2007, 14, 234. [5] T. Hemmingsen, H. Hovdan, P. Sanni, N. Aagotnes, Electrochim. Acta 2002, 47, 3949. [6] F. Khan, T. Husain, S. Abbasi, J. Loss Prevent. Proc. 2002, 15, 129. [7] H. Mitsui, R. Takahashi, H. Asano, N. Taniguchi, M. Yui, Corrosion 2008, 64, 939. [8] B. Fang, E. Han, J. Wang, W. Ke, Corrosion 2007, 63, 419. [9] B. Lu, J. Luo, Corrosion 2005, 62, 129. [10] A. Mustapha, E. Charles, D. Hardie, Corr. Sci. 2012, 54, 5. [11] F. Eliyan, A. Alfantazi, Corr. Sci. 2013, 74, 297. [12] F. Mohammadi, F. Eliyan, A. Alfantazi, Corr. Sci. 2012, 63, 323. [13] D. Davies, G. Burstein, Corrosion 1980, 36, 416. [14] M. ElNaggar, J. Appl. Electrochem. 2004, 34, 911. [15] F. Eliyan, E. Mahdi, A. Alfantazi, Corr. Sci. 2012, 58, 181. [16] F. Eliyan, Z. Farhat, A. Alfantazi, Int. J. Electrochem. Sci. 2013, 8, 3026. [17] E. Castro, J. Vilche, A. Ariva, Corr. Sci. 1991, 32, 37. [18] D. Li, Y. Feng, Z. Bai, J. Zhu, M. Zheng, Appl. Surf. Sci. 2008, 254, 2837. [19] Z. Lu, C. Huang, D. Huang, W. Yang, Corr. Sci. 2006, 48, 3049. [20] M. ElNaggar, Appl. Surf. Sci. 2006, 252, 6179. [21] J. GonzalezRodriguez, M. Casales, V. SalinasBravo, J. Albarran, L. Martinez, Corrosion 2002, 58, 584. [22] X. Mao, X. Liu, R. Revie, Corrosion 1994, 50, 651. [23] S. Simard, M. Drogowska, H. Menard, J. Appl. Electrochem. 1997, 27, 317. [24] A. Dugstad, H. Hemmer, M. Seiersten, presented at CORROSION/2000, Orlando, Florida, March 2631, 2000, Paper no. 24. [25] J. Jelinek, P. Neufeld, Corr. Sci. 1980, 20, 489. [26] K. Rajagopalan, K. Venu, M. Viswanathan, Corr. Sci. 1969, 9, 169. [27] H. Huang, W. Tsai, J. Lee, Corr. Sci. 1994, 36, 1027. [28] Ja. Kolotyrkin, Corrosion 1963, 19, 261t. [29] R. Cottis, S. Turgoose, R. Newman, Corrosion Testing Made Easy: Electrochemical Impedance and Noise, NACE International, Houston, TX 1999. [30] H. Huang, W. Tsai, J. Lee, Electrochim. Acta 1996, 41, 1191. [31] B. Boukamp, Equivalent Circuit Users Manual, University of Twente, Einshede 1989. (Received: December 14, 2012) (Accepted: May 29, 2013) W6984

tended to shift to higher frequencies of between 10 and 30 Hz with time. They were notably wide for the 30 K/s HAZ, and the peaks of the 60 K/s HAZ, at low frequencies, were more clearly indicating the increased chargetransfer resistance with time. The equivalent circuit, shown in Fig. 11, achieved a good tting with the experimental data. A constant phase element, whose admittance [32] is expressed in Equation (6), was used for the double layer and across the passive lm, and it was mostly capacitive.

n p n p jYQ vn sin Y Y Q vn cos 2 2

v is the angular frequency and n is the CPE exponent. The average solution resistance (Rs) was almost 15 V cm2, and the 30 K/s HAZ was of the highest 16 750 V cm2 charge transfer resistance (Rch) and the 10 K/s HAZ was of the highest 486 V cm2 passive lm resistance.

4 Conclusions
A number of electrochemical corrosion aspects were employed to analyze the inuence of 100 and 300 ppm chloride ions on the growth and the stability of the passive lms, of the APIX100 HAZs, in dilute bicarbonate solutions at 363 K. For an industrial relevance, the results emphasize the necessity of welding the pipeline steels to cool at high rates so that the HAZs become reliably more corrosion resistant when exposed to mildly alkaline ows at high temperature. The HAZs cooled at 30 K/s showed evidence for thin, highly sensitivetowardschloride passive lms, and they showed the lowest cathodic activity and corrosion rates, and multiple anodic peaks. During the slow 0.05 mV/s potentiodynamic polarization, the reduction of O2 resulted in broad peaks, coalesced with the anodic peaks, below stable mixed control regions at almost 0.2 V versus SCE. The corrosion rates showed a slight increase with higher chloride concentration, with which, accordingly, transpassivation occurred at lower potentials. Revealing the virtues of the slow 0.05 mV/s potentiodynamic polarization scans, the signicance of a microstructure type during the 0.5 mV/s potentiodynamic scans was not, on contrary, as clear to identify. The potentiostatic currents, of values and modes of change with time, did not depend on the chloride concentration, and for the 30 and 60 K/s HAZs, they were almost one order of magnitude different from the potentiodynamic currents at the same 0.5 V versus SCE. The EIS experiments indicated a twotime

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