Materials and Corrosion 2013, XXX, No. XXX DOI: 10.1002/maco.

201206984 1

Sensitivity of the passive films on API‐X100 steel

heat‐affected 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 films on the heat‐
affected zones (HAZs), of API‐X100 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 films towards
the increased chloride concentration, and evidence of increased charge‐transfer
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 films of the 10 K/s HAZ, at the open circuit
potentials, were of the highest resistance to deteriorate/facilitate for mass
transport.

1 Introduction of HAZ microstructures is expected, and that makes selection and

Corrosion of the heat‐affected 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, significantly 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 (P‐GMAW), a mechanized procedure of high
operation efficiency. 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 ferrite‐to‐austenite transformation, during
a dual‐torch P‐GMAW 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
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 fires [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 field. 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 bicarbonate‐based solutions [7–9].
The natures of the interfacial interactions between a HAZ
microstructure and the main corrosive carbon‐carrying species,
with respect to an environmental condition, did not receive
specific or sufficient investigations. In some studies, like the one
published by Mustapha et al. [10], the HAZs were made by
ordinary heat treatments, compromising relatively the signifi-
cance of a real HAZ on the corrosion behavior in the field.
In this paper, the influence of the chloride ions, introduced
with trace 100 and 300 ppm concentrations, on the stability
and the growth of the passive films is investigated in dilute
bicarbonate solutions at 363 K. The measurements investigate
the behavior of the passive films from specific electrochemical

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2 Eliyan and Alfantazi Materials and Corrosion 2013, XXX, No. XXX

aspects in reference to three types of HAZs made of API‐X100

pipeline steel. The main objectives, and implications, of this 1200
research were explained in two previous efforts [11,12], in a
pursuit devoted for evaluating the corrosion behavior of the HAZs
of the new‐generation HSLA pipeline steels. 1000
10 K/s

2 Experimental details

Temperature (K)
100 K/s 30 K/s
800
2.1 Corrosion test set‐up
60 K/s
The experiments were carried out in a 1 L, three‐electrode, multi‐
600
port jacketed cell. The working electrodes were machined from
API‐X100 steel sheet into flat disks and mounted in hard epoxy
resins of high‐temperature reliability. The potentials were
400
measured against the saturated calomel electrode (SCE) of
þ240 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‐
200
constant‐velocity water stream was circulated by a Cole‐Parmer 0 20 40 60 80 100 120
heater. The experiments were carried out by VersaStat 4 Time (s)
potentiostat, and with a synchronized software program, the
experiments were controlled and the results were analyzed. 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
2.2 Test material
2.3 Test solutions
The specimens were wet ground in sequence by 120, 320, and 600
grit emery papers, and then degreased in ethyl alcohol for 10 min, The tests were carried out in dilute 5 g/L bicarbonate solutions of
rinsed with distilled water and dried in a hot air stream. The 100 and 300 ppm Cl. The temperature was maintained at 363 K,
chemical composition, presented in Table 1, of the test API‐X100 and the pH was between 8.3 and 8.6.
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 variable‐pressure 2.4 Electrochemical tests
Hitachi S300N© SEM. To reveal the microstructures, selected
samples were wet‐ground up to 1200 grit finish, polished with 6 The specimens were subjected to a cathodic conditioning at 2 V
and 1 µm diamond suspensions, immersed in a Nital etchant versus SCE for about 10 min before commencing the experiments –
(2 ml of 70% nitric acid and 98 ml of anhydrous, denatured ethyl which were repeated for many times to ensure the reproducibility of
alcohol), treated with alcohol swapping and finally dried in an air the results. The cyclic potentiodynamic polarization was scanned
stream. As shown in Fig. 2a, the microstructure of the as‐received from 1.3 V to a vertex 1.2 V versus SCE, and scanned downward to
specimen consisted of a mixture of intergranular ferrite (F), the open circuit potentials, at a rate of 0.05 and 0.5 mV/s. At 0.5 V
pearlite, and bainitic ferrite (BF). versus SCE for 4000 s, the potentiostatic polarization tests were carried
A Gleeble© thermal simulation machine was set to execute out. The growth of the passive films and the change in the transport
thermal cycles, presented in Fig. 1, on specimens to be of interactions at the open circuit potentials over after 1000, 2000, and
microstructures resembling three typical pipeline HAZs. The 3000 s were investigated by electrochemical impedance spectroscopy
samples were heated up to a peak 1223 K at a rate of 100 K/s, and with a sampling rate of 10 points per decade from 10 000 to 0.1 Hz.
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 3 Results and discussion
polygonal ferrite (PF) of large grain sizes, and few amounts of
bainitic ferrite and pearlite. In 30 K/s HAZ, acicular ferrite and 3.1 Cyclic potentiodynamic polarization
martensite were the main constituents, and the microstructure of
60 K/s HAZ was martentistic (M) with some prior austenite The profiles representing the 0.05 mV/s polarization in 100 and
grains, as shown in Fig. 2c and d, respectively. 300 ppm Cl solutions are shown in Fig. 3. They show high

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

C Mn Mo Ni Al Cu Ti Nb Cr V C.E.

0.1 1.66 0.19 0.13 0.02 0.25 0.02 0.043 0.016 0.003 0.45

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Materials and Corrosion 2013, XXX, No. XXX Passivation on HAZs 3

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 HAZ, of which acicular ferrite is the main constituent, showed
SCE, notably broad peaks, stable mixed‐control regions at 0.2 V the minimum cathodic activity and multiple anodic peaks. The
versus SCE, passivation of a range of nearly 700 mV and second passivation behavior was notably dependent on the microstruc-
peaks at between 0.8 and 0.9 V versus SCE. Exclusively, the 30 K/s ture type and the chloride concentration. The active dissolution,

Base steel 10 K/s HAZ 30 K/s HAZ 60 K/s HAZ

1.0 1.0 1.0 1.0

0.5 0.5 0.5 0.5

Potential (V vs. SCE )

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

0.0 0.0 0.0 0.0

-0.5 -0.5 -0.5 -0.5

-1.0 -1.0 -1.0 -1.0

100 ppm Cl- 100 ppm Cl- 100 ppm Cl- 100 ppm Cl-
10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-8 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 10 K/s HAZ 30 K/s HAZ 60 K/s HAZ

1.0 1.0 1.0 1.0

0.5 0.5 0.5 0.5

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

0.0 0.0 0.0 0.0

-0.5 -0.5 -0.5 -0.5

-1.0 -1.0 -1.0 -1.0

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

2 2 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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4 Eliyan and Alfantazi 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 always‐reproducible broad
peaks. That encourages to analyze the influence of temperature
on the nature of the pre‐passive or “low‐valence” 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].
Fe þ 2OH ! FeðOHÞ2 þ 2e
bicarbonate and chloride, mentioned that Fe(OH) results in
Fe(OHþ) 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.
FeðOHÞads $ FeðOHþ Þ þ e ð2Þ
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
ð1Þ 300 mV‐broad peaks.

It is preceded by adsorption‐based steps that involve adorbent


O2 þ 2H2 O þ 4e þ 4OH ð3Þ
complexes such as FeO22 , HFeO 2 , and Fe(OH). Lu et al. [19],
who carried out potentiodynamic polarization tests on pure iron Their size was independent from the microstructure
at 30 8C (303 K) in solutions of different concentrations of type, and they can be interpreted as a coalescence between

0
0 a
a

-200
-200 Passivation potential (mV vs. SCE )
Corrosion potential (mV vs. SCE)

-400
-400

-600 -600 100 ppm Cl

-

100 ppm Cl- 300 ppm Cl-

300 ppm Cl-

-800 -800
As-received
As-received 10 C/s
10 K/sHAZ 30K/s
HAZ 30 C/s HAZ
HAZ 60K/s
60 C/s HAZ
HAZ
As-received
As-received 10 C/s
10 K/sHAZ 30K/s
HAZ 30 C/s HAZ
HAZ 60
60K/s
C/s HAZ
HAZ
API-X100 test samples
API-X100 test samples
800
140
b
b
120
Transpassivation potential (mV vs. SCE)

600
Corrosion current density (μA/cm )
2

100

80

400

60

40
200 100 ppm Cl-
100 ppm Cl -
-
300 ppm Cl - 300 ppm Cl

20

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

API-X100 test samples API-X100 test samples

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

© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.matcorr.com

Materials and Corrosion 2013, XXX, No. XXX Passivation on HAZs 5

the anodic peaks, which appear during the polarization occurred at comparable potentials, second anodic peaks of
of iron and steels in bicarbonate solutions [21,22], and various sizes appeared below the vertex potentials. If the
the cathodic peaks of the O2 reduction. At low potentials – influence of O2 is discounted, these peaks – which were seldom
slightly below the first anodic peaks – bicarbonate functions reproducible in chloride‐free solutions [11] – can be linked to
as an active adsorbent to form carbon‐carrying complexes, repassivated pits onto ruptured films, as proposed by Jelinek and
such as FeðHCO 3 Þ, to drive, in a series of reactions, Neufeld [26] on similar observations in bicarbonate‐chloride
FeCO3 precipitation. Alternatively, as reported by Simard solutions, but at lower potentials. It should be noted that only
et al. [23], the passive films can more probably grow the 10 K/s HAZ exhibited a positive hysteresis loop in the 100
multilayered of Fe(OH)2 and FeCO3 in a process Fe(OH)2 is and 300 ppm Cl solutions.
reacting with HCO 3. Increasing the chloride concentration to 300 ppm made
The passive regimes were broad and comparable, and they the passive currents markedly higher to nearly 320 µA/cm2
revealed the significance of the microstructure type. The current for the as‐received samples. It destabilized the passive films on
densities were as the lowest as nearly 1 µA/cm2 for the as‐ the 30 and 60 K/s HAZs, whose passivation regimes exhibited
received and the 10 K/s HAZ, of microstructures mainly many intense spikes. To explain, the Cl ions adsorb between
composed of ferrite which upon dissolution cementite (Fe3C) the adsorbed onto‐the‐surface H2O molecules and the sites where
becomes the conductive, effective, anchoring network for the film is thinner or more permeable to initiate, consequently, the
thick passive films to precipitate/grow within [24]. For the 30 film pitting and the increase in the substrate dissolution rates [27] –
and 60 K/s HAZs, the passive current densities were nearly a phenomenon that causes the intense repetitive spikes with
as great as 40 and 10 µA/cm2, respectively. The higher current the thin passive films that formed on the 30 and 60 K/s HAZs.
densities indicate thinner/less stable passive films to have As Fig. 4 shows, the corrosion potentials are between 780
formed on the low‐temperature‐transformation phases of the and 760 mV versus SCE, and the corrosion rates were between
acicular and bainitic ferrite, and martensite – phases of high 80 and 120 µA/cm2. But except for the 30 K/s HAZs, the corrosion
residual stresses and high density of lattice defects [5,25]. FeCO3 potentials were nearly 820 mV versus SCE and the corrosion
oxidizes to g‐Fe2O3 at higher potentials, as reported by rates were between 20 and 30 µA/cm2. That is very attributed to
Castro et al. [17] who carried out voltammetric studies in the slower cathodic reactions on the 30 K/s HAZs, given that the
carbonate/bicarbonate solutions: proportion between the acicular and grain boundary ferrites of a
similar HAZ was reported to be a strong factor in affecting the rate
þ 
2FeCO3 þ 3H2 O ! g  Fe2 O3 þ 2CO2
3 þ 6H þ 2e
of the cathodic reactions [28]. The corrosion rates showed
sensitivity towards chloride, but the onset of passivation, as
ð4Þ
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.
A brief discussion (to refer to) was previously made on the While it is difficult to articulate on the discrepancy of the
reactivity of the dissolved O2 and OH with FeCO3 to generate transpassivation potentials of the as‐received and the 10 K/s HAZ
Fe2O3 and/or Fe3O4 [11,15]. After transpassivation, which with the chloride concentrations, the potentials of the 30 and

Base steel 10 K/s HAZ 30 K/s HAZ 60 K/s HAZ

1.0 1.0 1.0 1.0

0.5 0.5 0.5 0.5

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

0.0 0.0 0.0 0.0

-0.5 -0.5 -0.5 -0.5

-1.0 -1.0 -1.0 -1.0

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

2 2 2
Current density (A/cm ) Current density (A/cm ) Current density (A/cm ) Current density (A/cm 2)

Base steel 10 K/s HAZ 30 K/s HAZ 60 K/s HAZ

1.0 1.0 1.0 1.0

0.5 0.5 0.5 0.5

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

0.0 0.0 0.0 0.0

-0.5 -0.5 -0.5 -0.5

-1.0 -1.0 -1.0 -1.0

300 ppm Cl- 300 ppm Cl- 300 ppm Cl- 300 ppm Cl-
10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-8 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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6 Eliyan and Alfantazi Materials and Corrosion 2013, XXX, No. XXX

60 K/s HAZs in 300 ppm solutions were less than the 100 ppm Kolotyrkin [29] as:
solutions’. That can be attributed to the lesser resistance !
of the passive films to deteriorate upon the adsorption of 2 Hþ
M O þ xCl $ MðClÞx
x þ mH2 O ð5Þ
chloride ions, with greater concentrations, counteracting the Hþ
competitive adsorption of O2, of H2O, to make the passive films
deteriorate at lower potentials. The equilibrium between O2 The polarization carried out at a higher 0.5 mV/s scan rate is
and Cl species adsorbing on a passive film was reported by represented in Fig. 6. The current densities during the cathodic

1600 1600
Base steel 10 K/s HAZ
1400 1400

1200 1200
Current density (μA/cm )

Current density (μA/cm )

2

2
1000 1000

800 800

600 600

400 400

200 200

0 0
0 1000 2000 3000 4000 0 1000 2000 3000 4000

Time (s) Time (s)

300 300
30 K/s HAZ 60 K/s HAZ

250 250
Current density (μA/cm )

Current density (μA/cm )

2

200 200

150 150

100 100

50 50

0 0
0 1000 2000 3000 4000 0 1000 2000 3000 4000

Time (s) Time (s)

600
Base steel [11]

500
Current density (μA/cm )
2

400

300

200

100

0
0 1000 2000 3000 4000

Time (s)

Figure 7. The potentiostatic polarization profiles 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 chloride‐free solution [11], at 363 K

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Materials and Corrosion 2013, XXX, No. XXX Passivation on HAZs 7

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 significance of a specific HAZ microstructure with the
polarization behavior. Regardless of the chloride concentration,
negative hysteresis loops resulted for all samples.
3.2 Potentiostatic polarization
The potentiostatic profiles 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 first 300 s. The currents of
the 30 and 60 K/s HAZs were the lowest, being nearly 10 and
50 µA/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 as‐received samples were higher, and
their final 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 films, intensified over time and
the currents were finally 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 fluctuating,
currents over time for the as‐received sample to become finally
nearly 0.2 mA/cm2 – currents higher than the as‐received’s in
chloride‐free solutions [11] whose profile is shown in Fig. 7.
3.3 Electrochemical impedance spectroscopy
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 reflect the two time‐constant 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 films
with quite minimal pitting. As shown in Fig. 9, for the as‐received
sample, the semi‐transparent passive film shows evidence of a
spread of star‐like shallow attacks, but not penetrating through to

100
1000 s 1000 s
2000 s a 400 2000 s b
3000 s 3000 s
80

300
Zim (Ω.cm )

Zim (Ω.cm )
2

60

200
40

100
20

20 40 60 80 100 100 200 300 400

2 2
Zre (Ω.cm ) Zre (Ω.cm )

5000 1000 s 1000 s

2000 s c 600 2000 s d
3000 s 3000 s

4000 500
Zim (Ω.cm )
Zim (Ω.cm )

400
2
2

3000

300
2000

200

1000
100

0
0 1000 2000 3000 4000 5000 100 200 300 400 500 600
2 2
Zre (Ω.cm ) Zre (Ω.cm )

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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8 Eliyan and Alfantazi Materials and Corrosion 2013, XXX, No. XXX

the substrate. The two‐time‐constant fitting for the interactions

sustained through the passive films 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 charge‐transfer resistance increased over time for
the 30 and 60 K/s HAZs. The influence of bicarbonate in our case,
at high temperature, on the resistance at the double layers and
of the passive films is similar to that reported from the 0.1 M
NaHCO3 to 0.17 M NaCl solutions at 25 8C (298 K) [12]. The
charge‐transfer resistance, proportionally corresponds to the
size of a Nyquist plot, was the highest for the 30 K/s HAZs,
confirming with the potentiodynamic polarization results that
showed the lowest corrosion rates for those HAZs. Agreeably,
Huang et al. [31] reported an increased charge‐transfer resistance
of HAZs of large Widmanstätten ferrite fractions (the acicular
ferrite of our 30 K/s HAZ can be considered as a fine
Widmanstätten ferrite) – in harsher corrosion conditions, without
Figure 9.The brownish passive film formed on the base steel after 3000 s proposing relevant reasons. Increasing the chloride concentra-
of immersion, at the OCP conditions, in 5 g/L NaHCO3 solutions tion did not induce significant changes, but the time of
containing 100 ppm Cl. It shows the star‐like spread of shallow attacks
immersion needs to be considerably longer, especially for the
on the semi‐transparent passive film
as‐received and 10 K/s HAZ, in future studies, to better
understand the correlations between the growth of the passive
films and the charge transfer resistance, in relation to chloride
concentration. The phase peaks, which are shown in Fig. 10,

50 103 60
a 1000 s b 1000 s
102 2000 s 2000 s
3000 s 3000 s 50
40

Phase angle (deg)

Phase angle (deg)

30 40
IZI (Ω.cm )
IZI (Ω.cm )

2
2

102
20 30

101
10 20

0 10

101
0
10-2 10-1 100 101 102 103 104 105 10-2 10-1 100 101 102 103 104 105

Frequency (Hz) Frequency (Hz)

80 103
Frequency (Hz)1000 s
c 1000 s d
2000 s 2000 s 50
3000 s 3000 s

60
40
103
Phase angle (deg)
Phase angle (deg)

Phase angle (deg)

IZI (Ω.cm )
IZI (Ω.cm )

2
2

30
40 102

102 20

20
10

101 0 101 0
10-2 10-1 100 101 102 103 104 105 10-2 10-1 100 101 102 103 104 105

Frequency (Hz) Frequency (Hz)

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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Materials and Corrosion 2013, XXX, No. XXX
Metal surface Double layer Passivation Solution
Ydl Yf
RS
Rch Rf YW
Figure 11. The two‐time‐constant equivalent circuit fitting the
experimental EIS data
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 charge‐transfer resistance with time. The equivalent
circuit, shown in Fig. 11, achieved a good fitting 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 film, and it was mostly capacitive.
np np
Y ¼ Y Q vn cos þ jYQ vn sin
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 film resistance.
4 Conclusions
A number of electrochemical corrosion aspects were employed to
analyze the influence of 100 and 300 ppm chloride ions on the
growth and the stability of the passive films, of the API‐X100
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
flows at high temperature. The HAZs cooled at 30 K/s showed
evidence for thin, highly sensitive‐towards‐chloride passive films,
and they showed the lowest cathodic activity and corrosion rates,
and multiple anodic peaks. During the slow 0.05 mV/s potentio-
dynamic 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. Reveal-
ing the virtues of the slow 0.05 mV/s potentiodynamic polarization
scans, the significance 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 two‐time‐
www.matcorr.com
Passivation on HAZs 9
constant type of interactions on/across passivated interfaces, and
they showed a continuous increase of charge transfer‐resistance
over time for the 30 and 60 K/s HAZs at the open circuit potentials.
Acknowledgements: This publication was made possible by
NPRP grant #09‐211‐2‐089 from the Qatar National Research
Fund (a member of Qatar Foundation). The statements made
herein are solely the responsibility of the authors.
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(Received: December 14, 2012) W6984
(Accepted: May 29, 2013)
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim