Corrosion Science 63 (2012) 323–333

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Corrosion of simulated weld HAZ of API X-80 pipeline steel

Farzad Mohammadi ⇑, Faysal Fayez Eliyan, Akram Alfantazi
Dept. of Materials Engineering, The University of British Columbia, Vancouver, BC, Canada

a r t i c l e i n f o a b s t r a c t

Article history: Four peak temperatures and two cooling rates were used in a Gleeble thermomechanical processing
Received 13 January 2012 machine to simulate weld HAZ of API X-80 pipeline steel. Bainitic microstructures were observed at both
Accepted 15 June 2012 30 and 100 °C/s cooling rates. Bainite favoured higher passive current densities in alkaline solutions. The
Available online 23 June 2012
lowest peak temperature, 770 °C, produced the highest martensite-retained austenite (M–A) phase in the
microstructure. Presence of M–A phases in the microstructure extended the passive region to higher
Keywords: potentials in alkaline solutions. Corrosion current density of the as-received sample was higher in acidic
A. Low alloy steel
solutions and lower in alkaline solutions compared to the heat-treated ones.
C. Welding
B. Polarisation
Ó 2012 Elsevier Ltd. All rights reserved.
C. Acid corrosion
C. Alkaline corrosion

1. Introduction refinement [6,7]. API-X80 pipeline steel is a recent generation

In 2010, International Energy Outlook reported that an increase
of up to 40% is expected for the world gas consumption over the
2007 to 2035 period. This increase in demand means that a greater
supply of resources is required over long distances that typically
exist between the reservoirs and demand centres. Pipelines are
an important means of fuel transportation through which high
flow rates of hydrocarbons can be provided. In order to transport
a greater volume of resources through pipelines, higher operating
pressures are required. Simultaneously, there is always demand
from the industry to decrease pipeline construction and operating
costs. These were among the main motives for the development of
new pipeline steels [1,2].
Increasing carbon content up to 0.3 wt.%, as well as adding
alloying elements such as Mn, Cr, Mo, Cu, and Ni, can be used
to increase the strength of steel [3]. Increased hardenability of
the steel; however, causes the strength to increase at the expense
of manufacturing viability and cost. Also, the fusion and heat
affected zones (HAZ) of such steels are more prone to cracking
at operating conditions [4]. High strength low alloy (HSLA) steels
were developed to overcome such difficulties. They contain very
low amounts of carbon (0.05–0.10 wt.%), as well as total level of
microalloying elements, less than 1 wt.%. HSLA steels usually con-
tain Mn up to 2 wt.% [3,5]. Alloying elements such as Nb, B, V, Ti
and Mo are typically used for microalloying and the strengthen-
ing mechanisms are usually precipitation hardening and grain
⇑ Corresponding author. Address: Dept. of Materials Engineering, The University
of British Columbia, Vancouver, BC, Canada V6T 1Z4. Tel.: +1 778 855 3026; fax: +1
604 822 3619
E-mail address: farzadmoh@gmail.com (F. Mohammadi).
of HSLA steels with the minimum 800 ksi (550 MPa) yield
strength [8].
Approximately 20% of the entire pipeline construction costs is
due to welding, coating, and subsequent maintenance to confirm
their integrity [9]. Thus, increasing the welding efficiency without
losing the performance in the welded joints is of great importance.
Therefore, applications of steels become limited by their weldabil-
ity. Despite significant efforts for the development of alternative
welding methods, girth metal arc welding (GMAW) is still the
major technique used to join large diameter pipes [2,3]. In this
technique, the weld metal is usually deposited using a single torch
and the arc is typically protected and stabilized using a mixture of
an inert gas (He, Ar) and an active gas (CO2) [10]. Due to the high
temperature (higher than the melting point) experienced in the
fusion zone during the welding process, microstructural changes
are also observed in the HAZ that depend on both chemical
composition of the steel and the thermal cycle [4]. In the case of
API-X80 pipeline steel, depending on the thermal cycle experi-
enced by the HAZ, the microstructure may be a combination of
ferrite, bainite and martensite–austenite (M–A), which can initiate
fracture [11].
General and pitting corrosion of pipeline steels have been the
subject of previous studies [12–15]. The most severe pitting is usu-
ally reported for the welded area with different rates of pit growth
measured for the fusion zone, HAZ, and the base metal [12]. Corro-
sion resistance of the HAZ is reported to be highly dependent on
the thermal cycle experienced by the metal [13,14]. Huang et al.,
studied the microstructure of weldments and found that the coars-
ening of Widmanstatten ferrite in the HAZ increased the corrosion
resistance of carbon steel in acidic solutions containing NaCl [15].

0010-938X/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2012.06.014
324 F. Mohammadi et al. / Corrosion Science 63 (2012) 323–333
Pereda et al., reported that the thermal cycles experienced by the
HAZ of super martensitic welds in chloride-containing solutions
do not have a significant effect on the pitting potential [16]. Zhang
and Cheng used the scanning vibrating electrode technique and re-
ported that the corrosion mechanism of HAZ of welded API-X70
pipeline steel does not change upon hydrogen charging or stress-
ing; however, hydrogen charging enhanced the local anodic disso-
lution of the steel [17]. Liou et al., studied the effects of nitrogen
content and cooling rate on the microstructure and stress corrosion
cracking (SCC) of the HAZ of 2205 duplex stainless steel [18]. They
reported that Widmanstatten, intergranular and partially trans-
formed austenite have beneficial role in the SCC resistance of the
alloy since they deviate the crack propagation path.
Although several studies related to the effect of heat input and
thermal cycles on the microstructure of pipeline steels have been
performed, the effect of post welding microstructure on corrosion
behaviour of the HAZ, especially for HSLA steels, is still not very
well understood. Therefore, the objective of this study is to inves-
tigate the effect of heating/cooling cycles relevant to GMAW weld-
ing on corrosion behaviour of API X-80 pipeline steel in acidic and
alkaline solutions in the presence and absence of chloride.
2. Experimental
10 mm  1 mm  95 mm rectangular samples of API-X80 were
prepared. 95 mm was the maximum allowable length by the sam-
ple holder of the thermomechanical simulator device. Choosing
this length allowed a uniform temperature distribution across
the 15 mm middle part of the samples (four thermocouples at-
tached to this area), of which only 10 mm was used to perform
microstructural analysis and corrosion studies. 1 mm thickness of
the samples virtually eliminated temperature gradient across the
two faces of the samples.
Thermal processing of the samples was performed using the
Gleeble 3500 thermomechanical processing machine. This device
is capable of providing vacuum levels down to 109 atm, along
with rapid and programmable heating and cooling cycles. Heating
is provided by running an electric current through the samples.
Fig. 1. Microstructure of the sample heated up to 770 °C and cooled down at 100 °C/s using Le pera and 2% nital etchants (top left and top right) and results of Imaje J analysis
(buttom).
Table 1
Compositions of the etchants.
Etchant Nitric acid Sodium Water Picric Ethanol
(ml) metabisulfite acid (ml)
2% 2 – – – 98
nital
Le pera – 1g 100 ml 4g 100
Temperature is controlled by thermocouple readings at rates up
to 1000 Hz. Cooling of the samples can be performed using the
water-cooled sample holders (for low cooling rates) or gas (for
higher cooling rates). In this study, compressed He gas was used
to provide cooling rates of 30 and 100 °C/s. The heating rate was
identical for all experiments (250 °C/s). The heating and cooling
rates were selected based on the previous temperature readings
of different areas of the HAZ of API-X80 steel using GMAW [19].
Following the thermal cycles, 10 mm  10 mm sections were
cut from the middle part of heat-treated samples and were cold
mounted. Mounted samples were then ground using 320, 600
and 1200 grit silicon carbide sand papers followed by 6 and 1 lm
polishing using a diamond suspension abrasive. Samples were then
etched with the proper solution (Table 1) to reveal specific phases.
As shown in Table 1, for preparation of 2% nital, 2 ml of nitric acid
was mixed with 98 ml of ethanol. Preparation of Le Pera solution;
however, was more complicated. 4 g picric acid was dissolved in
100 ml ethanol and 1 g sodium metabisulfite was dissolved in
100 ml deionized water. The two solutions were mixed in a 1:1 ra-
tio immediately before etching. Each sample was etched with
freshly prepared Le pera solution. Etching time using 2% nital var-
ied between 15 and 30 s while with Le pera, this time varied be-
tween 35 and 60 s.
Microstructure studies were performed using the Nikon EPIP-
HOT 300 series optical microscope and the Clemex Vision PE image
analysing software. Le pera solution was used to identify the
amount of M–A phases in the microstructure. M–A phases tend
to turn white upon exposure to Le pera solution [20]. Fig. 1 shows
the results of Le pera etching and image analysis using ImajeJ.
 F. Mohammadi et al. / Corrosion Science 63 (2012) 323–333
Fig. 2. Differentiation criteria for ferrite and bainite phase quantification according to ASTM E562-08.
Phase quantification for the remaining ferrite and bainite was
performed using 2% nital as the etchant according to ASTM E562-
08. The differentiation criteria for the ferrite and bainite phases
in the microstructure are shown in Fig. 2. One of the differences be-
tween bainite and ferrite phases is that prior austenite grain
boundaries cannot be observed for ferritic structures, while in
bainitic structures these boundaries are noticeable. Depending on
the cooling rate, three bainite types or a combination of them
may occur. The image analysis procedures, both for Le pera and
2% nital etchants, were repeated on at least ten pictures captured
from each sample under identical imaging processes. Therefore,
each data point on the phase quantification graphs is the average
of at least ten individual measurements. The maximum deviation
observed from the average values plotted for phase contents was
7% using ASTM E562-08 while the value for the Le Pera procedure
was less than 3%.
Microhardness measurements were performed using the Micro-
metÒ3 microhardness tester by Buehler. The load was set to 500 g
and the loading time was adjusted to 15 s. Each experiment was re-
peated ten times to ensure accuracy and reproducibility of the
results.
A three-electrode cell was used to perform electrochemical
experiments. Graphite was used as the counter electrode (CE), sat-
urated calomel electrode (SCE, 0.242SHE) as the reference electrode
(RE), and API X-80 steel (Evraz Inc., chemical composition in Table
2) as the working electrode. Electrochemical experiments were
performed using a princeton applied research (PAR) Versastat 4
potetiostat/galvanostat. Before electrochemical experiments, sam-
ples were ground using 1200 grit SiC sand paper, cleaned ultrason-
ically, washed with deionized water, and air dried. Samples were
immediately immersed in solution for 24 h and open circuit poten-
tial (OCP) was recorded before electrochemical impedance spec-
troscopy (EIS) and potentiodynamic experiments. Following the
OCP, EIS tests were performed with RMS applied potential ampli-
tude of 10 mV at the OCP. The frequency range of 0.01–10000 Hz
Table 2
Chemical composition of the API X-80 steel used in this study (wt.%).
C Mn Nb Mo Ti
0.060 1.650 0.034 0.240 0.012
325
was used for EIS experiments with a sampling rate of 10 points
per decade. The potentiodynamic tests were performed with a scan
rate of 0.167 mV s1. All the potentials in this work are reported
versus the SCE reference electrode.
The test solution for the acidic conditions contained 0.1 M so-
dium sulphate under continuous CO2 purging with a pH of 4.2 that
did not change significantly over the 24 h of experiments. As for
the alkaline solutions, 0.1 M solution of sodium bicarbonate was
used, along with 0.17 M (1 wt.%) sodium chloride. In the prelimin-
ary experiments performed in alkaline solutions in the absence of
chloride ions, the alloys exhibited a passive-like behaviour at
potentials slightly more positive than the OCP. Therefore, sodium
chloride was added to the alkaline solution to investigate the pit-
ting behaviour of these alloys. The pH of the alkaline solution
was 8.4 that dropped to 8.2 over 24 h as the experiment pro-
gressed. All experiments were performed at room temperature.
The alkaline solutions were continuously purged with argon in or-
der to deaerate the solution. For both alkaline and acidic solutions
gas purging was started at least one hour prior to start of each
experiment. All the chemical agents were obtained from Fisher Sci-
entific and solutions were prepared with deionized water.
3. Results and discussion
3.1. Microstructural analysis
It is well known that the final phases present in the microstruc-
ture of steels depend highly on the applied thermal cycles. Three
factors have been frequently held responsible in formation of dif-
ferent phases in HSLA steels [21]. Prior austenite grain size is the
first factor, since grain boundaries provide preferable sites for
nucleation of new phases. Therefore, peak temperature affects
the final phase content by affecting the austenite grain size and,
consequently, the grain boundaries. The second factor that plays
an important role is the cooling rate. Transformation of austenite
to ferrite takes place through diffusion. Ferrite nucleates on the
austenite grain boundaries and grows into the grains [22] which,
like all diffusional transformations, is highly affected by the cooling
rate. The third factor, which is important in the case of HSLA steels,
N is the state of Nb, in solution or precipitated. It has been shown
that in the case of API X-80, presence of Nb in the precipitated form
0.005
generally results in higher austenite decomposition temperatures
326 F. Mohammadi et al. / Corrosion Science 63 (2012) 323–333
Fig. 3. Thermal cycle temperature recordings by Gleeble 3500 (arrows indicate the austenite decomposition plateau).
[23]. The higher the peak temperature, the higher the Nb present in
the solution.
Fig. 3 shows the temperature recordings made using a Gleeble
3500 thermomechanical processing device during the thermome-
chanical processing. It is apparent that the device is very well capa-
ble of following the designed experimental procedure. As observed
on the graphs for both cooling rates, the temperature at which aus-
tenite decomposition occurs through diffusional processes is re-
duced by increasing the peak temperature. This can be due to
both austenite grain size and Nb present in the solution. Increasing
the peak temperature (higher super heating) increases the grain
size of the austenite phase which, in turn, reduces the grain bound-
ary concentration. This reduces the number of preferred sites for
nucleation of the new phases and, therefore, a higher driving force
(larger undercooling) is required for the transformation to happen.
In addition, increasing the peak temperature may increase the Nb
content of the solution (austenite), which increases the transfor-
mation temperature [23].
The effect of the cooling rate can also be observed on the graphs
shown in Fig. 3. The transformation plateau shifts slightly to
lower temperatures (10–15 °C) by increasing the cooling rate from
30 °C/s to 100 °C/s. This may be due to the more favourable ferrite
transformation (nucleation) at lower temperatures [24]. According
to Enomoto et al., [25] the higher cooling rate (larger undercooling)
changes the mechanism and preferred sites for ferrite nucleation
from the prior austenite phase.
Fig. 4 shows the results of image analysis for ferrite and bainite
phase quantification. The highest ferrite percentage was observed
at 770 °C peak temperature with 30 °C/s cooling rate. This sample
also contained the lowest amount of bainite compared to others.
Increasing the peak temperature increased the bainite content of
the samples at 30 and 100 °C/s cooling rates. The ferrite content;
however, was continuously decreased with increasing tempera-
ture. This behaviour can be described by the effect of temperature
on grain size and, thus, grain boundary concentration. Increasing
peak temperature increases austenite grain size constantly. There-
fore, the number of preferred sites for ferrite nucleation is reduced
and austenite decomposition through diffusive processes becomes
more difficult. Therefore, at high temperatures, formation of bai-
nite is favoured and a higher percentage of bainite is detected.
The effect of the cooling rate on the percentage of ferrite and bai-
nite phases is not significant. However, except for the 770 °C peak
temperature, the 100 °C/s cooling rate resulted in slightly higher
bainite content in the samples. This means that both cooling rates
are high enough to favour formation of bainite, given the austenite
grain size becomes large enough to assist the transformation.
Fig. 5 shows the results of M–A phase quantification along with
measured hardness values. Interestingly, the highest M–A phase
was measured for the samples with the lowest peak temperature
(770 °C) with 30 °C/s producing more M–A than the 100 °C/s cool-
ing rate. This can be described based on the effect of cooling rate on
the ferrite formation. When the cooling rate is low, austenite can
first transform to ferrite and, therefore, become enriched with car-
bon due to rejection of carbon from ferrite. Therefore, the remain-
ing austenite has a higher chance of transforming to martensite as
the temperature is lowered. However, at higher cooling rates, con-
ditions are more suitable for bainite formation, which results in the
remaining austenite less enriched with carbon and less prone to
transform to martensite compared to the case of initial ferrite
formation.
The effect of peak temperature on the M–A content can be de-
scribed using a similar argument. At lower peak temperatures,
the austenite grains are small and the concentration of grain
boundaries is fairly high. Therefore, formation of ferrite from the
austenite is highly favourable enriching the remaining austenite
in carbon. Therefore, as the temperature is lowered, martensite
can form from the remaining austenite. On the contrary, when
the peak temperature is increased (large superheating), austenite
grains are enlarged and thus, the concentration of grain boundaries
is reduced, which favours formation of bainite. Therefore, higher
M–A contents are measures for the lowest peak temperature and
cooling rate.
As also apparent from Fig. 5, hardness of the samples is not a
function of their martensite content. However, if the results are
compared with their bainite contents shown in Fig. 4, it can be con-
cluded that the hardness of the samples increased as their bainite
content increased. The measured values for the hardness were in
the middle range of the previously reported values for hardness
of bainite and ferrite [26]. Between 1200 and 1350 °C, the bainite
contents of the samples were relatively similar to the 100 °C/s
 F. Mohammadi et al. / Corrosion Science 63 (2012) 323–333 327

Fig. 4. Ferrite and bainite contents of API X-80 steel samples as a function of peak temperature and cooling rate.

Fig. 5. Hardness and M–A content of API X-80 steel samples as a function of peak temperature and cooling rate.

cooling rate; however, the hardness values differ significantly. This
may be attributed to higher residual stresses in the sample rapidly
cooled from 1350 °C compared to the one cooled from 1200 °C.
Although the as-received sample contained a smaller percentage
of ferrite in its microstructure, its hardness value was similar to
samples heated to 770 and 950 °C.
Fig. 6 shows microstructures of the samples heated up to 770,
950, 1200, and 1350 °C and cooled down at 30 °C/s using 2% nital.
It is apparent that the primary austenite grain boundaries are
clearly visible at both 1200 and 1350 °C with the grain sizes being
larger for the 1350 °C. The microstructures of these samples
include mostly bainite with a small amount of ferrite (see Fig. 2
for differentiation criteria). At 950 °C, the structure is a mixture
of bainite and ferrite of relatively equal percentage, while at
770 °C, the microstructure appears to include mostly ferrite grains
with a small amount of bainite.
3.2. Electrochemical corrosion studies
3.2.1. OCP
The OCP values of as-received and heat treated samples after
24 h of exposure to the test solutions are presented in Table 3. It
is apparent that, in both acidic and alkaline solutions, OCP values
for the as-received samples were more positive than the ones for
328 F. Mohammadi et al. / Corrosion Science 63 (2012) 323–333

Fig. 6. Microstructures arising from application of different thermal cycles on API X-80 steel (etched with Le pera solution).

Moreover, several mechanisms have been proposed to describe

Table 3 the effect of carbonic species on the anodic reactions during corro-
OCP values for as-received and heat treated samples in both acidic (0.1 M sion of carbon steel in aqueous solutions [28,29]. In this study, the
Na2SO4 + continuous CO2 purging, pH 4.2) and alkaline (0.1 M NaHCO3 + 0.17 M Cl
OCP values for the as-received samples were more positive than
as NaCl) media.
the heat treated ones in both acidic and alkaline media. This may
As Rec. 770 °C 950 °C 1200 °C 1350 °C be interpreted as better corrosion resistance of these samples,
(VSCE) (VSCE) (VSCE) (VSCE) (VSCE)
meaning that for the as-received samples the anodic reactions be-
Acidic 30 °C/ 0.701 0.725 0.730 0.731 0.732 come dominant at higher potentials compared to those of heat
s
treated samples. However, commenting on the corrosion rates of
Acidic 0.701 0.730 0.729 0.727 0.729
100 °C/s the samples requires further experiments, which are presented in
Alkaline 0.775 0.821 0.824 0.814 0.820 the next section. The overall lower OCP values of the samples
30 °C/s in alkaline solutions indicate a greater share of reactions 1 and 2
Alkaline 0.775 0.815 0.822 0.817 0.820 in the net cathodic current density.
100 °C/s

3.2.2. Potentiodynamic polarisation

heat treated samples. However, the OCP values of heat treated
samples were not very different from each other. The OCP mea-
surements versus time in acidic solutions revealed very minor dif-
ference between the OCP after 1 h (not shown in Table 3) and after
24 h (always less than 7 mV). However, in the case of as-received
samples, this minor difference was in the form of a decrease in
OCP over the 24 h period, while for all heat treated samples, it
was an increase. The comparison between the results of acidic
and alkaline solutions also reveals that the OCP values in alkaline
media were always more negative compared to the acidic media.
It has been shown previously that addition of carbonic species
to aqueous solutions may enhance corrosion of carbon steel by
adding reactions 1 and 2 to the chain of cathodic reactions; how-
ever, Linter and Burstein showed that these reactions are thermo-
dynamically less favourable compared to reaction 3, hydrogen
evolution [27,28].
2H2 CO3 þ 2e ¼ H2 þ 2HCO3 ; E0 ¼ 0:622VSCE
2HCO3 þ 2e ¼ H2 þ CO2 0
E ¼ 0:856VSCE
3 ;
þ  0 cept for the corrosion current density of the as-received samples
2H þ 2e ¼ H2 ; E ¼ 0:242VSCE
Fig. 7 shows the results of potentiodynamic polarisation of sam-
ples in acidic solutions. The figure includes curves for the as-
received sample and four of the eight heat treated conditions.
The anodic and cathodic Tafel slopes, ba and bc, the corrosion cur-
rent density, icorr, and corrosion potential, Ecorr, were extracted
from potentiodynamic curves of all conditions and are presented
in Table 4. The corrosion parameters were calculated using a
Microsoft Excel code and the method (Tafel Curve Fitting) de-
scribed by Stansbury and Buchanan [30]. From Table 4 and the
magnified inset in Fig. 7, it can be understood that Ecorr was at its
most positive value for the as-received samples, which is consis-
tent with the OCP measurements. The anodic Tafel slopes did not
vary significantly between the as-received and the heat treated
samples. However, the cathodic Tafel slope for the as-received
sample was slightly higher than the ones cooled at 30 °C/s. The
cathodic Tafel slopes of the samples cooled at 100 °C/s were not
very different from the as-received samples. No clear correlation
ð1Þ was observed between the behaviour of the samples in acidic con-
ð2Þ ditions at corrosion potential and the microstructural studies, ex-
ð3Þ being higher than the rest.
 F. Mohammadi et al. / Corrosion Science 63 (2012) 323–333 329

Fig. 7. Select potentiodynamic polarisation curves of the heat treated samples along with as-received sample in acidic solution (0.1 M Na2SO4 + continuous CO2 purging, pH
4.2).

samples with higher anodic current densities in this region oc-

Table 4
curred at lower potentials. This implies that the reduction in cur-
Corrosion parameters and passive potential extracted from potentiodynamic curves
in acidic condition (0.1 M Na2SO4 + continuous CO2 purging, pH 4.2). rent density is probably a result of solution saturation near the
sample surface and corrosion product deposition [28]. Therefore,
Ecorr (VSCE) ba (V/dec) bc (V/dec) icorr (A/cm2) Ep (VSCE)
the higher the corrosion rate, the lower the protection potential.
As Rec. 0.687 0.048 0.082 1.51  1004 0.660 The reduction in current density above Ep was significantly larger
770–30 0.725 0.043 0.069 6.96  1005 none
for the as-received samples, which is likely a result of better adher-
950–30 0.718 0.038 0.071 7.81  1005 0.696
1200–30 0.700 0.043 0.069 8.09  1005 0.743 ence of the deposited products to the surface. The backward polar-
1350–30 0.718 0.033 0.072 5.42  1005 0.630 isation of the samples that exhibited passive-like behaviour
770–100 0.707 0.044 0.084 9.24  1005 none resulted in immediate repassivation of the surface after reversing
950–100 0.728 0.040 0.085 5.34  1005 0.642 the potential.
1200–100 0.705 0.043 0.082 8.12  1005 0.737
Figs. 8 and 9 show the results of potentiodynamic polarisation
1350–100 0.700 0.049 0.077 6.85  1005 0.710
in alkaline solutions of as-received and heat treated samples
cooled at 30 and 100 °C/s, respectively. The data extracted from
these curves is shown in Table 5. It is apparent from the data that
As shown in Fig. 7, except for the two samples heated up to the Ecorr of the as-received sample was more positive than the heat
770 °C, samples experienced a sudden decrease in current density treated samples, similar to the results of the acidic condition.
at high potentials. The potentials where this passive-like behaviour Therefore, it can be concluded that in both acidic and alkaline envi-
was observed for all samples, Ep, are reported in Table 4. The term ronments the base metal has the ability to act as cathode relative
‘‘passive-like’’ is used since the sudden decrease in the current to the heat affected zone. As shown in Table 5, although of the
density is similar to passive film formation; however, the surface same order of magnitude, the corrosion current density for the
is indeed not passive due to current densities significantly larger as-received sample is smaller than the rest of the samples. Unlike
than what is typically observed for a passive surface. Referring to the acidic conditions, polarisation of samples to potentials higher
Figs. 4 and 5, it is realised that the major difference between these than 0.1 VSCE did not result in passive-like behaviour. Therefore,
two samples and the rest of the samples is that they contained the only the potential range between 0.9 VSCE and 0.1 VSCE is pre-
highest amount of M–A phase in their microstructure (7% and 9% sented in Figs. 8 and 9. As can be observed, all samples exhibited
for 100 and 30°C/s cooling rates, respectively). Although the sam- a passive behaviour in this potential region. However, the passive
ple heated up to 770 °C and cooled at 100 °C/s also has a relatively region extended to higher potentials for the cases of 770 and
large amount of M–A phase in its microstructure, it exhibits the 950 °C peak temperatures cooled at 30 °C/s and sample heated to
passive-like behaviour. This shows that the passive-like behaviour 770 °C and cooled at 100 °C/s. As shown in Fig. 5, these samples
is not a function of M–A phase content; however, no clear correla- have higher M–A phase content in their microstructure. The
tion between the bainite and ferrite contents of the samples and extended passive region can therefore be said to depend on the
their passive-like behaviour and Ep was observed. The passive-like M–A content of the samples. As shown in Table 5, both anodic
behaviour was only stable in a small potential region and the cur- and cathodic Tafel slopes were larger for the heat treated samples
rent density started to increase as the potential was increased. In compared to the as-received ones. No clear correlation was found
the anodic potential region above corrosion potential and below between the Ep and microstructural studies of the samples. Both
Ep, the current density was the maximum for the as-received sam- Figs. 8 and 9 reveal that increasing the peak temperature increased
ple and was the minimum for the samples that did not experience the current density in the passive region of the potentiodynamic
the passive-like behaviour. The passive-like behaviour for the polarisation curves. This observation, along with Fig. 4, suggests
330 F. Mohammadi et al. / Corrosion Science 63 (2012) 323–333

Fig. 8. Cyclic potentiodynamic polarisation curves of the samples cooled down at 30°C/s along with the as-received sample in alkaline solution (0.1 M NaHCO3 + 0.17 M Cl as
NaCl) media.

Fig. 9. Cyclic potentiodynamic polarisation curves of the samples cooled down at 100 °C/s along with the as-received sample in alkaline solution (0.1 M NaHCO3 + 0.17 M Cl
as NaCl) media.

that the more bainitic the microstructure, the higher the passive
current density in alkaline solutions. Reverse polarisation of the
samples once the transpassive region was reached showed that
all samples were susceptible to pitting at potentials more positive
than 0.5 VSCE. In both Figs. 8 and 9, the potential where the re-
verse sweep curve coincides with the passive region curve is sim-
ilar for all samples and the difference is insignificant.
3.2.3. EIS
Fig. 10 shows the Nyquist and Bode plots for the EIS experi-
ments performed on as-received and heat treated samples at OCP
after 24 h of immersion in acidic solutions. Due to the similarity
of the results, the Nyquist plot of the samples cooled at 30 °C/s is
presented along with the bode plot of the samples cooled to
100 °C/s. One time-constant was observed on the bode plots of
all samples. It is apparent that the smallest semi-circle belongs
to the as-received samples. This corresponded to the results pre-
sented in Table 4 where as-received samples exhibited the largest
corrosion current density in acidic solutions. The results shown in
Fig. 10 suggest that at OCP in acidic media all samples experienced
active dissolution with the as-received sample having the maxi-
mum rate.
 F. Mohammadi et al. / Corrosion Science 63 (2012) 323–333 331

Table 5 Fig. 11 shows the results of EIS experiments in alkaline solu-

Corrosion parameters and passive potential extracted from potentiodynamic curves tions. As apparent from the plots, the as-received sample showed
in alkaline solution (0.1 M NaHCO3 + 0.17 M Cl as NaCl).
a semicircle in the Nyquist plot and only one time-constant in
Ecorr (VSCE) ba (V/dec) bc (V/dec) icorr (A/cm2) Ep (VSCE) the bode plot. However, mass transfer controlled behaviour was
As Rec. 0.773 0.044 0.037 1.29  1006 0.634 observed for all the heat treated samples. In the Nyquist plots of
770–30 0.825 0.066 0.052 4.53  1006 0.634 the heat treated samples, an incomplete semi-circle at high fre-
950–30 0.827 0.058 0.041 3.07  1006 0.637 quencies is followed by a linear region in lower frequencies. In
1200–30 0.817 0.059 0.051 4.46  1006 0.630
1350–30 0.812 0.067 0.047 3.37  1006 0.623
addition, the bode plot is the typical of circuits containing Warburg
770–100 0.813 0.069 0.054 6.98  1006 0.605 element. This suggests that the reaction rate for the heat treated
950–100 0.817 0.065 0.050 4.07  1006 0.657 samples at OCP is controlled by the diffusion of electroactive spe-
1200–100 0.824 0.065 0.051 5.54  1006 0.667 cies from or to the surface. This is in agreement with the findings of
1350–100 0.810 0.063 0.054 3.05  1006 0.593
Linter and Burstein suggesting that, in mildly alkaline solutions,

Fig. 10. Nyquist (top) and Bode (bottom) plots of samples cooled down at 30 and 100 °C/s along with as-received sample at OCP in acidic solution (0.1 M Na2SO4 + continuous
CO2 purging, pH 4.2).
332 F. Mohammadi et al. / Corrosion Science 63 (2012) 323–333

Fig. 11. Nyquist (top) and Bode (bottom) plots of samples cooled down at 30 and 100 °C/s along with as-received sample in at OCP alkaline solution (0.1 M NaHCO3 + 0.17 M
Cl as NaCl) media.

the corrosion rate of carbon steel is controlled by movement of the
complex ions away from the surface [27].
4. Conclusions
Samples of API X-80 pipeline steel were heated up to four peak
temperatures and cooled down at 30 °C/s and 100 °C/s using the
Gleeble thermomechanical processing machine to simulate weld
HAZ. Both cooling rates were high enough to produce bainitic
microstructures. The lowest peak temperature resulted in the most
M–A phase in the microstructure. OCP values were more negative
in alkaline solutions compared to acidic solutions; however, the
OCP values for the as-received samples were always more positive
than the heat treated samples. The corrosion rate of API X-80 pipe-
line steel is largely dependent on pH and oxidising power of the
electrolyte. In acidic solutions, the as-received samples had the
highest corrosion current density, while in alkaline solutions they
had the least. In acidic solutions, all samples exhibited passive-like
behaviour at high potentials except those heated up to 770 °C. In
alkaline solutions, the presence of M–A phase in the microstruc-
ture expanded the passive region to higher potentials. The struc-
tures with higher bainite content have higher current densities in
their passive regions in alkaline solutions.
Acknowledgements
Authors would like to thank Natural Sciences and Engineering
Research Council (NSERC) of Canada and Qatar National Research
Fund (QNRF) for providing the financial support for this project.
 F. Mohammadi et al. / Corrosion Science 63 (2012) 323–333 333

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