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

201206985 1

Passivation of HAZs of API‐X100 pipeline steel in

bicarbonate‐carbonate solutions at 298 K
F. F. Eliyan*, F. Icre and A. Alfantazi

This research explores electrochemical correlations between heat‐affected

zones (HAZs), produced by Gleeble© thermal simulation cycles, and their
passivation behavior in bicarbonate–carbonate solutions. The investigations
were carried out in comparison with the base API‐X100 steel in naturally
aerated 0.5 g/L chloride solutions, containing a matrix of bicarbonate and
carbonate concentrations at 298 K. The slow 0.05 mV/s potentiodynamic scans
revealed that the passivation onsets earlier in proportion with the bicarbonate
concentrations, possessing accordingly greater immunity against chloride ions
on HAZs cooled at 10 and 60 K/s from 1223 K peak temperature. The HAZs cooled
at 10 K/s, particularly in concentrated carbonate solutions, showed the most
stable passivation, and the HAZs cooled at 60 K/s showed the lowest cathodic
activity regardless of the chemical conditions.
0.1 V, versus saturated calomel
electrode, potentiostatic currents and the open‐circuit potentials decreased
and increased, respectively, with the carbonate concentration, confirming with
the main potentiodynamic polarization results, and a corresponding passivation
behavior of the HAZs, regardless of a bicarbonate–carbonate condition, was
relatively similar. In contrary to the 60 K/s HAZs, the 10 K/s HAZs showed
evidence of growing passive films with time and high charge‐transfer resistance,
as measured by the EIS tests.

1 Introduction
There are many new procedures of welding oil pipeline joints
being recently implemented with a wide variety of thermal inputs,
rates, and economically optimized parameters [1]. In association,
the metallurgy and chemical composition change from that of
candidate steel, at different extents, within a narrow region
containing distinct microstructures over the pipe circumference
[2]. And like many mega strategic structures, oil pipelines are
vulnerable to failures, but from a corrosion standpoint, welding‐
induced metallurgical changes, over each 150–200 m, render the
uncertainties with securing the pipeline integrity and safety quite
substantial. Typically, three microstructures, of the weldment,
the heat‐affected zone (HAZ) and the base steel react at different
rates with the corrosive flows. When analyzing the phenomenon,
two major complexities are encountered first with the intrinsic
degree of tendency of corrosion of the microstructures in the
F. F. Eliyan, F. Icre, A. Alfantazi
Corrosion Group, Department of Materials Engineering, The University
of British Columbia, Vancouver, British Columbia, V6T 1Z4 (Canada)
E-mail: faysal09@interchange.ubc.ca
F. Icre
Institut Catholique d’Arts et Métiers, Toulouse (France)
three zones, and the galvanic conductance among them [3,4].
The tendencies for the anodic and cathodic reactions to sustain
become as a result functions of location of certain micro-
structures. The corrosion rates become uneven, which over time,
accelerate on localized regions onto which preferential thinning
and cracks occur to lead eventually to oil spillages, and sometimes
catastrophic fires [5].
The problem is therefore highly microstructure‐dependent,
which this research aims to study taking into account the
microstructures in a zone that is most sensitive, and most difficult
to control in relation to a welding procedure; the HAZ. Two
HAZs were produced by thermal Gleeble© simulation cycles,
in an electrochemical study with an attempt to meet the need for
better correlations between the corrosion vulnerability and
welded steels’ microstructures as a whole, and the need for
more optimized welding parameters and procedures [6–8].
The experimental conditions were prepared to simulate,
relatively partially, the corrosion conditions the external pipeline
surfaces deteriorate because of being exposed to ground waters,
which contain mainly bicarbonate, carbonate, and chloride [9,10].
The influence of different concentrations of bicarbonate and
carbonate, in the presence of 0.5 g/L chloride, in naturally aerated
solutions at 298 K, on the HAZs corrosion in comparison with
that of the original API‐X100 steel, is investigated by electro-
chemical methods.

www.matcorr.com wileyonlinelibrary.com © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2 Eliyan, Icre and Alfantazi Materials and Corrosion 2013, XXX, No. XXX

In literature, it well seems that there is a lack of

electrochemical studies on the HAZ corrosion. Mostly, the new 1200
HSLA steels are still being considered in few studies on the
corrosion behavior in bicarbonate–carbonate solutions. In
addition, evaluating the conventional aspects of stress‐corrosion 1000
cracking remained the main objective to carry out the majority 10 K/s
of the available investigations [11,12]. At 23 8C (296 K), the

potentiodynamic polarization results, reported by Zhang and
Cheng [13] on spirally welded X70, indicated no sensible
difference in the corrosion behavior between the base steel, the
HAZ and weld metal in 1 M NaHCO3 þ 0.5 M Na2CO3 solutions.
The results of our slow‐scan potentiodynamic tests show,
however, that the HAZ microstructures, which are similar to
theirs, distinctly, from each other, reacted during dissolution and
passivation. In some studies, like that for instance reported by
Mitsui et al. [14] and by others, the significance of the dilute
bicarbonate–carbonate solutions with the reactions, and with the
cathodic currents did not particularly receive an interest.
With regard to the experimental techniques, the potentiostatic
polarization and electrochemical impedance spectroscopy are not
currently widely applied in the field of HAZ corrosion. In this
paper, a number of techniques are implemented along with a
large matrix of environmental conditions to develop, collectively,
a wider understanding on the HAZ corrosion behavior on an
electrochemical basis.
2 Experimental details
2.1 Corrosion test set‐up
A 1‐L‐glass jacketed cell was selected to carry out the experiments
in. It is multi‐port, through which the working, counter, and
reference electrodes are all fitted at the standard positions. A
working electrode, machined from API‐X100 pipeline steel, was a
rectangular coupon welded by conductive silver paste to copper
wires in which all were embedded in a cold‐cured epoxy resin. The
reference electrode was a saturated calomel electrode (SCE) of
0.240 V versus SHE, and the counter electrode was a graphite rod.
A VersStat 4© potentiostat was used to perform the experiments,
which was synchronized to a computer software to control the
experiments and analyze the results.
Temperature (K)
60 K/s
100 K/s
800
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 heating at 100 K/s to a peak 1223 K, followed by
cooling at 10 and 60 K/s
illustrated in Fig. 1, by thermo‐mechanical Gleeble© machine,
by heating at 100 K/s to a peak 1223 K, held for 0.5 s, and
then cooled to produce two different HAZs by cooling at 10
and 60 K/s.
The microstructural features were revealed by wet‐grinding
up to 1200 grit finish, polishing with 6 and 1 µm diamond
suspensions, and then by 10‐s immersion in Nital etchant
(2 ml of 70% nitric acid and 98 ml of anhydrous, denatured
ethyl alcohol). The metallurgical micrographs were produced
by a Hitachi© S3000N variable pressure scanning electron
microscope. The microstructure of the as‐received specimen
consists mainly of intergranular ferrite (F), pearlite, and bainitic
ferrite (BF), as shown in Fig. 2a. The 10 K/s HAZ consists of
polygonal ferrite (PF) and some dispersed pearlite, and the
microstructure of the 60 K/s HAZ was mainly martensitic, with
small prior retained austenite grains, as shown in Fig. 2b and c,
respectively.

2.2 Test material

The coupons were all wet ground in sequence by 120, 320, and
600 grit emery papers, degreased in ethyl alcohol, rinsed in
distilled water and dried with a hot air stream. The chemical
composition (shown in Table 1) of the test steel was analyzed by
inductive coupled plasma (ICP) and LECO carbon analysis. The
HAZ samples were prepared by thermal simulation cycles,
2.3 Test solutions
The solutions were naturally aerated of a matrix of bicarbonate
and carbonate concentrations of 5, 10, 15, and 20 g/L, kept at
298 K, containing 0.5 g/L chloride. The pH, which was kept
unbuffered, was between 8.2 and 8.7 in bicarbonate solutions,
and between 9.5 and 11.5 in bicarbonate–carbonate solutions.

Table 1. Chemical composition (wt%) and carbon equivalent of the test material

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

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

Materials and Corrosion 2013, XXX, No. XXX
Figure 2. Metallographic SEM images of the microstructures of (a) base
steel, (b) 10 K/s, and (c) 60 K/s HAZs
2.4 Electrochemical tests
The electrochemical tests, repeated three times to ensure
reproducibility, were preceded by cathodic conditioning for about
1000 s at
2 V versus SCE to eliminate the interference from any
air‐formed oxides. The potentiodynamic polarization experi-
www.matcorr.com
Passivation of HAZs in HCO3
/CO32
solutions 3
ments were carried out with a slow 0.05 mV/s scan, from
1.3 to
1.2 V versus SCE. The potentiostatic polarization tests were carried
out at
0.1 V versus SCE for 7200 s. At the open circuit potentials,
the influence of bicarbonate and carbonate on the charge transfer
resistance and the main interfacial processes over after 900, 1800,
and 5400 s were studied by EIS with a frequency range of from
10 000 to 0.1 Hz.
3 Results and discussion
3.1 Potentiodynamic polarization
The influence of bicarbonate concentration was first exclusively
investigated with slow‐scan potentiodynamic polarization, of
profiles shown in Fig. 3. With the upscan, the profiles revealed
the reduction of water and that of oxygen, two stable mixed
control regions at nearly
0.65 and
0.18 V versus SCE,
and relatively stable passivation regimes. Some important
changes, depending on the bicarbonate concentration, with
the cathodic and passivation regimes appeared. The small
internal peak at nearly
0.65 V versus SCE in 5 g/L solutions
turned to represent the more effective onset of passivation,
with anodic peaks increasing in size with the bicarbonate
concentration. And that could represent a clear indication on
bicarbonate being directly catalyzing the anodic reactions –
a notion receiving no wide agreement in many previous
studies [15–17], where FeCO3 precipitation (associated primarily
to the conditions of supersaturation [18]) can be a product of
that direct oxidation [19] as:
Fe þ HCO
þ

3 ! FeCO3 þ H þ 2e ;
ð1Þ
E o ¼
0:729 V versus SCE
The phenomena cannot be completely attributed to the
higher rate of the electrochemical (Equation 1) reaction, since the
kinetics and rate‐determining steps, in relation to the bicarbonate
concentration, first need special investigations. Second, some
products such as Fe(OH)2, whose earlier formation is indirectly
dependent on bicarbonate [20], might still have a role prior to the
active‐passive transition. Nernst equation was used to calculate
the potentials of Equation (1) in relation to the bicarbonate
concentration and pH at 298 K, which lied in a range between

0.965 and
0.945 V versus SCE. The oxygen reduction
intersected the anodic peaks at two locations to result in two,
anodic and cathodic peaks, above where the currents, summed
mainly of oxygen reduction, were between 0.5 and 1 mA/cm2,
and those corresponding to the charge‐transfer‐limited reduc-
tion of water were between 2 and 7 mA/cm2 for the as‐received
samples. Considering the cases of 10, 15, and 20 g/L solutions,
the onset‐of‐passivation potentials (Epass), of the anodic
peaks, were almost unaffected of being nearly
0.6 V versus
SCE, but whose critical current densities increased from
nearly 200 to 320 and 550 µA/cm2. The potentials of first
mixed‐control regions increased from nearly
0.67 to
0.64 V
versus SCE with the increased bicarbonate concentration.
Above the second intersection, at nearly
0.18 V versus SCE,
the passivation regimes notably depended on the bicarbonate
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
4 Eliyan, Icre and Alfantazi Materials and Corrosion 2013, XXX, No. XXX

1.0 Base steel 1.0 Base steel 1.0 Base steel 1.0 Base steel

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

5 g/L 10 g/L 15 g/L 20 g/L
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/cm2)

1.0 10 K/s HAZ 1.0 10 K/s HAZ 1.0 10 K/s HAZ 1.0 10 K/s HAZ

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

5 g/L 10 g/L 15 g/L 20 g/L
10-8 10-7 10-6 10-5 10-4 10-3 10-8 10-7 10-6 10-5 10-4 10-3 10-8 10-7 10-6 10-5 10-4 10-3 10-8 10-7 10-6 10-5 10-4 10-3

Current density (A/cm 2) Current density (A/cm2) Current density (A/cm2) Current density (A/cm2)

1.0 60 K/s HAZ 1.0 60 K/s HAZ 1.0 60 K/s HAZ 1.0 60 K/s HAZ

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

5 g/L 10 g/L 15 g/L 20 g/L
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/cm 2) Current density (A/cm 2)

Figure 3. The potentiodynamic polarization of the base steel, 10 K/s HAZ and 60 K/s HAZ in carbonate‐free solutions of 5, 10, 15, and 20 g/L bicarbonate
concentrations

concentration. In 5 and 10 g/L solutions, transpassivation oxygen concentration could considerably depend.
potentials were as low as 0.04 V versus SCE before pitting and
½CO2

3 
extensive dissolution occurred. In 15 and 20 g/L solutions, log ¼ ¼ pH
10:34 ð2Þ
however, the passivation ranges were almost as broad to up to ½HCO
3
0.8 V versus SCE of transpassivation, and with passive currents
of nearly 2 µA/cm2. It is not clear whether the passive films In the first place, if compared with carbonate‐free, 5 g/L
were intrinsically enhanced, or the competitive adsorption of bicarbonate solutions, the cathodic currents in 5 g/L bicarbonate–
the protective intermediates surpassed that of the aggressive 5 g/L carbonate solutions were almost an order of magnitude
chloride ions [21,22], to result in better passive films with the less across relatively a wide potential range. Moreover, the
increased bicarbonate concentrations. passive regime was notably broader, where carbonate seemed to
For the 10 and 60 K/s HAZs, the cathodic currents were less, facilitate a faster precipitation of FeCO3 into enhanced passive
and the same transformations with the
0.6 V versus SCE peaks films. Exclusively, in 5 and 10 g/L carbonate solutions, anodic
appeared in relation to the bicarbonate concentrations. Up to peaks appeared at nearly 0 V versus SCE, which were the largest
with 20 g/L bicarbonate, the passive regimes broadened, with with 15 g/L bicarbonate, below which the passive currents
considerable indications of instability at high potentials, as shown varied with the upscan. In these solutions, transpassivation
in Fig. 3, for the 10 K/s HAZs. Passivation of 60 K/s HAZs, as potentials were nearly 0.8 V versus SCE and the passive currents
shown in Fig. 3, seemed better, and its currents were lower were nearly 2 µA/cm2, during which a brown‐reddish film
and stable. formed, similar to observations reported in Refs. [24,25]. In
The combined influence of bicarbonate and carbonate addition, another peak sometimes appeared at nearly
0.3 V
introduced with a matrix of 5, 10, and 15 g/L on the polarization versus SCE, corresponding probably to an oxidation process
behavior of the as‐received samples is represented in Fig. 4. The on the passive films. In 15 and 20 g/L, carbonate solutions
0.5 g/L chloride concentration was the same, and the electro- the 0 V versus SCE peaks did not appear, and the passive
chemical results here represent the polarization of towards the currents were relatively higher but they decreased with the
interfacial concentrations of carbonate and bicarbonate, coex- bicarbonate concentration. The anodic peaks at
0.6 V versus
isting in an aqueous equilibrium (Equation 2 [23]), on which SCE, which were discussed at the beginning, appeared mostly

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

Materials and Corrosion 2013, XXX, No. XXX Passivation of HAZs in HCO3
/CO32
solutions 5

1.0 5 g/L CO2-

3
1.0 5 g/L CO2-
3
1.0 5 g/L CO2-
3

0.5 0.5 0.5

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

0.0 0.0 0.0

-0.5 -0.5 -0.5

15 g/L HCO-3
-1.0 -1.0 -1.0
5 g/L HCO-3 10 g/L HCO-3
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)

2- 2- 2-
1.0 10 g/L CO3 1.0 10 g/L CO3 1.0 10 g/L CO3

0.5 0.5 0.5

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

0.0 0.0 0.0

-0.5 -0.5 -0.5

15 g/L HCO-3
-1.0 -1.0 -1.0
5 g/L HCO-3 10 g/L HCO-3
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 )

2- 2- 2-
1.0 15 g/L CO3 1.0 15 g/L CO3 1.0 15 g/L CO3

0.5 0.5 0.5

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

0.0 0.0 0.0

-0.5 -0.5 -0.5

15 g/L HCO-3
-1.0 -1.0 -1.0
5 g/L HCO-3 10 g/L HCO-3
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

Current density (A/cm ) 2

Current density (A/cm2) Current density (A/cm2)

2- 2- 2-
1.0 20 g/L CO3 1.0 20 g/L CO3 1.0 20 g/L CO3

0.5 0.5 0.5

Potential (V vs. SCE)
Potential (V vs. SCE)

Potential (V vs. SCE)

0.0 0.0 0.0

-0.5 -0.5 -0.5

15 g/L HCO-3
-1.0 -1.0 -1.0
5 g/L HCO-3 10 g/L HCO-3
10-6 10-5 10-4 10-3 10-2 10-6 10-5 10-4 10-3 10-2 10-6 10-5 10-4 10-3 10-2

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

Figure 4. The potentiodynamic polarization of the base steel in 5, 10, 15, and 20 g/L carbonate solutions of 5, 10, and 15 g/L bicarbonate concentrations

when bicarbonate concentration was 15 g/L, regardless of the Transpassivation was at lower 0.7 V versus SCE potentials but
carbonate concentration. the lowest passive currents, among other samples, can be well
The polarization behavior of the 10 and 60 K/s HAZs was not associated to thicker passive films [26], where upon dissolution of
markedly different, and the results in Fig. 5 are selectively the big ferrite grains, Fe3C acted as an effective anchoring network
representing the major distinctions. For 10 K/s HAZ, the passive within which FeCO3 precipitated. For the 60 K/s HAZ, it exhibited
currents were the lowest, and increasing bicarbonate concentration notably the minimum cathodic current densities in all solutions.
up to 20 g/L, in the presence of low carbonate concentrations, Moreover, it showed considerable insensitivity towards the
seemed not to change the behavior. However, in the presence of bicarbonate concentration and, as shown in Fig. 5 for 5 g/L
20 g/L carbonate, the passive currents were as lowest as 0.1 µA/cm2. carbonate solutions, intense spikes appeared at 0.15 V versus SCE.

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

6 Eliyan, Icre and Alfantazi Materials and Corrosion 2013, XXX, No. XXX

1.0 10 K/s HAZ 1.0 10 K/s HAZ 1.0 10 K/s HAZ

0.5 0.5 0.5

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

0.0 0.0 0.0

-0.5 -0.5 -0.5

5 g/L HCO-3 5 g/L HCO-3 20 g/L HCO-3

-1.0 -1.0 -1.0
2-
5 g/L CO2-
3 20 g/L
2-
CO3 20 g/L CO3
10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-9 10-8 10-7 10-6 10-5 10-4 10-3

Current density (A/cm2) Current density (A/cm2) Current density (A/cm2)

1.0 60 K/s HAZ 1.0 60 K/s HAZ 1.0 60 K/s HAZ

0.5 0.5 0.5

Potential (V vs. SCE)

Potential (V vs. SCE)

Potential (V vs. SCE)

0.0 0.0 0.0

-0.5 -0.5 -0.5

5 g/L HCO-3 10 g/L HCO-3 15 g/L HCO-3

-1.0 -1.0 -1.0
5 g/L CO2-
3 5 g/L CO2-
3
5 g/L CO2-
3
10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-9 10-8 10-7 10-6 10-5 10-4 10-3

Current density (A/cm2) Current density (A/cm2) Current density (A/cm2)

Figure 5. The potentiodynamic polarization of the 10 K/s HAZ and 60 K/s HAZ in bicarbonate/carbonate solutions of different concentrations

3.2 Potentiostatic polarization studied by EIS over after 900, 1800, and 5400 s. The OCPs of
the base steel showed a change over time, and most possibly due
The potentiostatic polarization was applied at
0.1 V versus to the relative microstructural resemblance to the 10 K/s HAZ,
SCE, a potential at which all samples regardless of the chemical the OCPs of both samples in different conditions were
conditions showed evidence of a passive state. For the base steel, comparable, as shown in Fig. 7a and b. In carbonate‐free
whose profiles are shown in Fig. 6a, the currents showed a solutions, the OCPs were almost
0.5, increased to
0.3 in
continuous increase over time in the carbonate‐free solution to the presence of 5 g/L carbonate and to
0.25 V versus SCE with
become nearly 30 µA/cm2. In the presence of 5 g/L carbonate, the further increase of bicarbonate and carbonate to 15 g/L. That
average currents were nearly 10 µA/cm2 but they showed the trend, exhibited both for the base steel and the HAZs, suggests
same kind of current spikes that were followed by slow 100‐s a direct dependence of effectiveness/thickness of the passive
decays. But in solutions of 15 g/L of bicarbonate and carbonate, films on the carbonate concentration. The fluctuations in the
the currents were notably lower and highly stable indicating the concentrated solution for the base steel can be associated to a
high immunity of the passive films against chloride. Bicarbonate relative instability of the passive film during a short period of
seems to raise the currents of passivation, provided that they time. For the 60 K/s HAZ, the OCPs were lower in the
were in bicarbonate‐free carbonate solutions, in Ref. [24], an carbonate‐free solutions, being nearly
0.73 V versus SCE,
order of magnitude less. The potentiostatic currents of 10 which were, as the potentiodynamic polarization tests showed,
and 60 K/s HAZs were less than the base steel’s and the nature indicative of lower cathodic reaction rates, and as previously
of the spikes in carbonate‐free solutions were different as they reported about low cathodic activity of martentistic micro-
were followed by abrupt, not gradual, decrease. In carbonate‐ structures [6,27]. The OCPs were almost 50 mV higher than the
containing solutions the currents were lower and comparable of base steel and the 10 K/s HAZs’ in carbonate‐containing
being between 0.1 and 0.5 µA/cm2, and it seemed that the solutions without indications, as to be explained below on the
significance of the microstructures of 10 K/s and 60 K/s HAZs 60 K/s HAZ EIS results, of higher resistance of charge‐transfer
was not as significant on the passivation behavior – at least in or across the passive films.
its early stages. The EIS spectra, represented in Figs. 8 and 9, suggest
that the dissolution and growth of the passive films were
primarily influenced by the chemical conditions, not by
3.3 Electrochemical impedance spectroscopy and open the microstructures. In carbonate‐free 5 g/L bicarbonate
circuit potentials solutions, the interfaces showed evidence of adsorption‐
controlled processes, of Nyquist spectra similar to the reported
The influence of bicarbonate and carbonate concentrations at by other researchers, of two depressed, overlapped capacitive
the open circuit potentials on the interfacial interactions were arcs [28,29]. As a Nyquist spectrum size correlates qualitatively

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

Materials and Corrosion 2013, XXX, No. XXX Passivation of HAZs in HCO3
/CO32
solutions 7

-0.2
a 5 g/L : 0 g/L a
10 g/L : 5 g/L
30 15 g/L : 15 g/L

-0.3
Current density (μA/cm2)

Potenital (V vs. SCE)

20

-0.4

5 g/L : 0 g/L
10 g/L : 5 g/L
10 15 g/L : 15 g/L
-0.5

0 -0.6
0 2000 4000 6000 0 1000 2000 3000 4000 5000

Time (s) Time (s)

10 -0.25
b 5 g/L : 0 g/L b
10 g/L : 5 g/L
15 g/L : 15 g/L
-0.30
8
Current density (μA/cm2)

Potenital (V vs. SCE)

-0.35
6

-0.40

4
5 g/L : 0 g/L
-0.45 10 g/L : 5 g/L
15 g/L : 15 g/L

2
-0.50

0 -0.55
0 2000 4000 6000 0 1000 2000 3000 4000 5000

Time (s) Time (s)

30 -0.1
c 5 g/L : 0 g/L c
10 g/L : 5 g/L
15 g/L : 15 g/L -0.2
25

-0.3
Current density (μA/cm2)

Potenital (V vs. SCE)

20

-0.4

15
-0.5

10
-0.6 5 g/L : 0 g/L
10 g/L : 5 g/L
15 g/L : 15 g/L
5 -0.7

0 -0.8
0 2000 4000 6000 0 1000 2000 3000 4000 5000

Time (s) Time (s)

Figure 6. The potentiostatic polarization of (a) as‐received, (b) 10 K/s Figure 7. The open circuit potentials of (a) as‐received, (b) 10 K/s HAZ,
HAZ, and (c) 60 K/s HAZ in solutions of different bicarbonate:carbonate and (c) 60 K/s HAZ in solutions of different bicarbonate:carbonate
concentrations concentrations

to charge‐transfer resistance [30], the base steel was highly
resistant to corrode, but it is interesting to note the decrease and
then the increase of resistance over time, as shown in Fig. 8a,1.
Taking into account the sole, relatively narrow phase peaks in
Fig. 9a,1, that indicates higher rates of dissolution from ferrite
(becoming less rate‐determining), and the increased influence
of adsorption of reaction intermediates covering increased areas
onto which charge‐transfer occurs [31]. The 60 K/s HAZ
exhibited a similar phenomenon, but the 10 K/s HAZ, which
comprised of greater ferrite content showed a continuous

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

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

18000 50000
900 s a,1 105 900 s
1800 s
a,2 900 s a,3
16000 1800 s 1800 s
5400 s 5400 s 5400 s
40000
14000 8x104

12000

Zim (Ω.cm )
Zim (Ω.cm )

Zim (Ω.cm )
2
30000
2

2
6x104
10000

8000
4x104 20000
6000

4000
2x104 10000

2000
5g/L:0g/L 10g/L:5g/L 15g/L:15g/L
2000 4000 6000 8000 1000012000140001600018000 2x104 4x104 6x104 8x104 105 10000 20000 30000 40000 50000
2 2 2
Zre (Ω.cm ) Zre (Ω.cm ) Zre (Ω.cm )
6000
900 s
1800 s
b,1 50000
900 s
1800 s
b,2 40000 900 s
1800 s
b,3
5400 s 5400 s 5400 s
5000
40000
30000
4000
Zim (Ω.cm )
Zim (Ω.cm )

Zim (Ω.cm )
2
2

2
30000
3000 20000

20000
2000

10000
10000
1000

5g/L:0g/L 10g/L:5g/L 15g/L:15g/L

1000 2000 3000 4000 5000 6000 10000 20000 30000 40000 50000 10000 20000 30000 40000
2
Zre (Ω.cm ) Zre (Ω.cm2) Zre (Ω.cm )
2

4000
900 s
1800 s
c,1 900 s
1800 s
c,2 900 s
1800 s
c,3
5400 s 30000 5400 s 30000 5400 s

3000
Zim (Ω.cm )

Zim (Ω.cm )

Zim (Ω.cm )
2
2

20000 20000
2000

10000 10000
1000

5g/L:0g/L 10g/L:5g/L 15g/L:15g/L

1000 2000 3000 4000 10000 20000 30000 10000 20000 30000
2 2
Zre (Ω.cm ) Zre (Ω.cm ) Zre (Ω.cm2)

Figure 8. The EIS Nyquist profiles of (a) as‐received, (b) 10 K/s HAZ, and (c) 60 K/s HAZ in solutions of different bicarbonate:carbonate
concentrations

increase in the charge‐transfer resistance over time, where the 4 Conclusions

adsorption fields transformed into dispersed passivating films,
as discerned from the increased phase values at low frequencies The special vulnerability to external corrosion and the passivation
in Fig. 9b,1. behavior, for a new‐generation API‐X100 pipeline steel, at the
In the presence of carbonate evidence of a second‐time HAZs, were studied by electrochemical methods. Two types of
constant element that accounts for fully‐covering passive films HAZs were produced by Gleeble© thermal simulation cycles of
appeared, as the second Nyquist loops grew into tails to heating at 100 K/s, and cooling at 10 and 60 K/s from a 1223 K
represent diffusion‐controlled processes, similar to findings peak temperature. Their corrosion behavior was compared with
reported in Ref. [24]. Different from the carbonate‐free the base steel’s in naturally aerated, 0.5 g/L chloride solutions
solutions, the passive films increasingly blocked the active of a matrix of concentrations of bicarbonate and carbonate at
dissolving sites over time, especially for the as‐received 298 K. The onset of passivation was directly dependent on the
and 10 K/s HAZs, where the phase peaks broadened and bicarbonate concentration, as revealed by the potentiodynamic
shifted to higher frequencies, as shown in Fig. 9a,2 and b,2. polarization for both the base steel and the HAZs, and the
The interfaces of 60 K/s HAZs were insensitive to the passivation of the HAZs was more immune against chloride. In
increased carbonate concentrations, and the other samples 5 and 10 g/L carbonate solutions, special anodic peaks appeared at
reflected seemingly diverse effects of the increased bicarbonate nearly 0 V versus SCE, and in 15 and 20 g/L solutions the passive
and carbonate concentrations. currents were notably lower and transpassivation occurred at

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

Materials and Corrosion 2013, XXX, No. XXX Passivation of HAZs in HCO3
/CO32
solutions 9

105 80 105 80

104
a,1 60
a,2 a,3
900 s 900 s 900 s
50 1800 s
1800 s 60 1800 s 60
5400 s 5400 s 104 5400 s
104

Phase angle (deg)

Phase angle (deg)
Phase angle (deg)
40

IZI (Ω.cm )
2
IZI (Ω.cm )
IZI (Ω.cm )

2
2

30 40 40
103
103
103
20

20 20
10 102

102

102
5g/L:0g/L
0
10g/L:5g/L 0
15g/L:15g/L
10-2 10-1 100 101 102 103 104 105 10-2 10-1 100 101 102 103 104 105 10-2 10-1 100 101 102 103 104 105

Frequency (Hz) Frequency (Hz) Frequency (Hz)

70 105 105

b,1 b,2 70 b,3 70

60
900 s 900 s 900 s
1800 s 60 60
1800 s 1800 s
50 5400 s 104
5400 s 104 5400 s

Phase angle (deg)

Phase angle (deg)
Phase angle (deg)

50 50
40
103

IZI (Ω.cm )
IZI (Ω.cm )

IZI (Ω.cm )

2
2
2

40 40
30 103
103
30 30
20

20 102 20
10

102 102 10 10
0

5g/L:0g/L 10g/L:5g/L 15g/L:15g/L

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

Frequency (Hz) Frequency (Hz) Frequency (Hz)

80 80
c,1 60 c,2 c,3
900 s 900 s 900 s
1800 s 104 1800 s 104 1800 s
50
5400 s 5400 s 60 5400 s 60
103
Phase angle (deg)

Phase angle (deg)

Phase angle (deg)

40
IZI (Ω.cm )

IZI (Ω.cm )
IZI (Ω.cm )
2

2
2

103 103
30 40 40

20
102 102
102 20 20

10 a, 15-15
5g/L:0g/L 10g/L:5g/L 101
15g/L:15g/L
0 101 0 0
10-2 10-1 100 101 102 103 104 105 10-2 10-1 100 101 102 103 104 105 10-2 10-1 100 101 102 103 104 105

Frequency (Hz) Frequency (Hz) Frequency (Hz)

Figure 9. The EIS Bode profiles of (a) as‐received, (b) 10 K/s HAZ, and (c) 60 K/s HAZ in solutions of different bicarbonate:carbonate concentrations

higher potentials with the increased bicarbonate concentration. polarization, it seems that it might constitute the pipeline HAZ of
The 10 K/s HAZs exhibited the minimum passive currents, in the high tendency to sustain the anodic reactions, especially if
proportion with the bicarbonate and carbonate concentrations, exposed to ground waters concentrated with carbonate.
and the 60 K/s HAZs exhibited the minimum cathodic activity.
The potentiostatic currents of the HAZs, at
0.1 V versus SCE, Acknowledgements: This publication was made possible by
were lower and more stable than the base steel’s, and the nature of NPRP grant #09‐211‐2‐089 from the Qatar National Research
their current spikes in carbonate‐free solutions was accordingly Fund (a member of Qatar Foundation). The statements made
different. But with a given carbonate and bicarbonate concen- herein are solely the responsibility of the authors.
trations the behavior of either HAZs did not show, comparatively,
a significant difference. The OCP tests allowed for better 5 References
determination of carbonate concentration significance with
the growth of the passive films as the OCPs, although being [1] E. Shashi Menon, Pipeline Planning and Construction Field
comparable for all samples, were getting higher accordingly. Only Manual, Gulf Professional Publishing, Waltham, Massachu-
the base steel and the 10 K/s HAZs showed evidence of setts USA 2011.
continuous growth of the passive films over time, as revealed [2] Y. You, C. Shang, N. Wenjin, S. Subramanian, Mater. Sci.
by EIS, and in carbonate‐free solutions, the interactions were Eng. A 2012, 558, 692.
mainly controlled by adsorption. The 60 K/s HAZ showed the [3] G. Savva, G. Weatherly, K. Aust, Corrosion 1989, 45, 243.
minimum charge‐transfer resistance in all conditions, and given [4] E. Blasco‐Tamarit, D. García‐García, M. Ibáñez Ferrándiz,
the lowest cathodic activity revealed by the potentiodynamic J. García Antón, A. Guenbour, Corrosion 2011, 67, 035001‐1.

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

10 Eliyan, Icre and Alfantazi
[5] C. Manfredi, J. Otegui, Eng. Fail. Anal. 2002, 9, 495.
[6] F. Eliyan, A. Alfantazi, Corr. Sci. 2013, 74, 297.
[7] F. Mohammadi, F. Eliyan, A. Alfantazi, Corr. Sci. 2012, 63,
323.
[8] F. Eliyan, A. Alfantazi, Mater. Corros. 2012, DOI: 10.1002/
maco.201206984.
[9] S. Savoye, L. Legrand, G. Sagon, S. Lecomte, A. Chausse,
R. Messina, P. Toulhoat, Corr. Sci. 2001, 43, 2049.
[10] N. Smart, D. Blackwood, L. Werme, Corrosion 2002, 58,
547.
[11] R. Parkins, S. Zhou, Corr. Sci. 1997, 39, 159.
[12] A. Mustapha, E. Charles, D. Hardie, Corr. Sci. 2012, 54, 5.
[13] G. Zhang, Y. Cheng, Electrochim. Acta 2009, 55, 316.
[14] H. Mitsui, R. Takahashi, H. Asano, N. Taniguchi, M. Yui,
Corrosion 2008, 64, 939.
[15] A. Fu, Y. Cheng, Corr. Sci. 2010, 52, 612.
[16] S. Zhou, M. Stack, R. Newman, Corr. Sci. 1996, 38,
1071.
[17] F. Eliyan, E. Mahdi, A. Alfantazi, Corr. Sci. 2012, 58, 181.
[18] E. Castro, J. Vilche, A. Ariva, Corr. Sci. 1991, 32, 37.
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Materials and Corrosion 2013, XXX, No. XXX
[19] Z. Lu, C. Huang, D. Huang, W. Yang, Corr. Sci. 2006, 48,
3049.
[20] V. Alves, C. Brett, Electrochim. Acta 2002, 47, 2081.
[21] N. Pessall, C. Liu, Electrochim. Acta 1971, 16, 1987.
[22] M. El‐Naggar, Appl. Surf. Sci. 2006, 252, 6179.
[23] M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous
Solutions, Press‐CEBELCOR, Oxford 1966.
[24] F. Eliyan, E. Mahdi, A. Alfantazi, Int. J. Electrochem. Sci. 2013,
8, 578.
[25] J. Thomas, T. Nurse, R. Walker, Br. Corros. J. 1970, 5, 87.
[26] D. Li, Y. Feng, Z. Bai, J. Zhu, M. Zheng, Appl. Surf. Sci. 2008,
254, 2837.
[27] E. Ramírez, J. González‐Rodriguez, A. Torres‐Islas, S. Serna,
B. Campillo, G. Dominguez‐Patiño, J. Juárez‐Islas, Corr. Sci.
2008, 50, 3534.
[28] A. Shahriari, T. Shahrabi, A. Oskuie, J. Mater. Eng. Perform.
2012, 22, 1459.
[29] B. Kinsella, Y. Tan, S. Bailey, Corrosion 1998, 54, 835.
[30] D. Silverman, J. Carrico, Corrosion 1988, 44, 280.
[31] G. Zhang, Y. Cheng, Corr. Sci. 2009, 51, 1589.
(Received: December 14, 2012) W6985
(Accepted: May 20, 2013)
www.matcorr.com