Engineering Failure Analysis 60 (2016) 307–315

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Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal

Electrochemical polarization study on crude oil pipeline

corrosion by the produced water with high salinity
Yucheng Liu a, Bo Zhang b, Yinlong Zhang b, Lili Ma b, Ping Yang a,⁎
a
College of Architecture and Environment, Sichuan University, Chengdu 610065, China
b
School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China

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

Article history: The effects of chloride ion, temperature, pH value, CO2 and O2 on the corrosion induced leakage
Received 30 June 2015 of the inner wall of crude oil pipeline with the produced water were investigated by electro-
Received in revised form 7 October 2015 chemical polarization. The results showed that chloride ion corrosion would gradually
Accepted 17 November 2015
experience the smooth invariant stage, the slow rise stage, and the rapid rise stage which
Available online 18 November 2015
due to the chloride ion destroy the corrosion product film. The corrosion rate would reach a
maximum when the temperature was 65 °C or the pH value was 3.5. O2 was the dominant
Keywords: factor induced the increase of corrosion rate when compared with the effect of CO2. Moreover,
Crude oil pipeline
long term and periodic (30 consecutive days) electrochemical CO2 corrosion tests suggested
Corrosion induced leakage
that the CO2 corrosion rate reached a maximum at 4 days. The obtained results would facilitate
Electrochemical polarization
Produced water the formulation of control measures for pipeline corrosion in the oil field.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction

Corrosion induced leakage of oil pipeline in the oil field can affect the normal production, cause enormous economic loss, and
even result in huge security risk [1–3]. Using new composite materials, improving corrosion media, adding coating on metal
surface, electrochemical protection, and adding corrosion inhibitor are commonly used for corrosion protection [4–6]. Corrosion
inhibitors with high efficiency, low-cost, and no changes in media are widely applied in the oil transmission pipeline [7,8]. On
the other hand, corrosion inhibitors have strong selectivity, a series of experiments is essential for evaluating their efficacy
[9,10]. In order to prevent the corrosion of oil pipeline, the first priority is to find the factors induced corrosion. The pipe corrosion
is generally divided into outer wall corrosion and inner wall corrosion, which occur in different media. The sulfate reducing
bacteria, dissolved oxygen, carbon dioxide, hydrogen sulfide, salinity, pH value and chloride ion in the produced water all can
cause the corrosion failure of pipe [4,11–13], while the factors induced corrosion may be varied when the pipe exists in different
environment. In the previous work, the effect of different factors on the corrosion of the outer wall of pipe had been fully
discussed [14–16]. However, corrosion environment of the inner wall was more complex in real situation, and only certain factors
had been discussed separately [17,18]. Therefore, it is necessary to carry on a systematic study of effective factors on the corrosion
of the inner wall of pipe in the oil field. In this work, the effective factors of produced water on the corrosion of pipe steel of Tuha
oil field were analyzed, and the corrosion reasons of every factor were also discussed. The obtained results could facilitate the
formulation of measures for corrosion control of pipeline in the oil field.

⁎ Corresponding author.
E-mail addresses: [email protected] (Y. Liu), [email protected] (P. Yang).

http://dx.doi.org/10.1016/j.engfailanal.2015.11.049
1350-6307/© 2015 Elsevier Ltd. All rights reserved.
308 Y. Liu et al. / Engineering Failure Analysis 60 (2016) 307–315

Table 1
Chemical compositions of pipeline.

Elements C Si Mn P S Cr Ni Fe

AISI 1020 steel (wt.%) 0.18 0.17 0.37 0.026 0.028 0.08 0.10 99.046

2. Materials and methods

2.1. Compositions of produced water and pipe

The selected pipe for the experiment was AISI 1020 steel from crude oil transmission pipeline in Tuha oil field. The composi-
tion of pipe was analyzed by direct-reading spectrograph (spectrovuc-100), and the result was reported by mass percent
(Table 1). It showed that the pipeline met the national standard (GB/T 8163-1999).
The produced water was obtained from the outlet of three-phase separator of crude oil. And the parameters of produced water
were shown in Table 2. The produced water was low-acid and high salinity.

2.2. Preparation of the working electrode

Electrochemical polarization test of corrosion of pipe steel was carried out by the working electrode. In fact, the working
electrode was the pipe steel connected a copper wire, which was given in Fig. 1. Firstly, 160 mm copper wire was prepared,
and the insulation sheath of the front and rear end of which were removed and meanwhile the exposed part was burnished
by abrasive paper. Then, the polished and cleaned steel (AISI 1020 steel) was placed on the glass disc, and the surface of
which was coated by melted solder wire through electric soldering iron, and the end of the copper wire was quickly inserted
into the melted solder wire for 30 s to a fixed state. Finally, the no-welding side of sheet steel was fixed on the double-sided
adhesive tape and then surrounded by the PVC pipe, which was poured by the prepared hardener, solidification for 7 days. The
used hardener was epoxy hardener, which consisted of epoxy, dimethyl phthalate and ethylenediamine, and the ratio of
epoxy/dimethyl phthalate/ethylenediamine was 10:2:0.8 by mass.

2.3. Electrochemical polarization method

Polarization curve method is an important means of electrochemical corrosion studies. The spectrogram of polarization curves
can describe the relationship between electrode potential and electric current in the process of polarization. The corrosion rate can
be determined by Tafel extrapolation of either the cathode or anode polarization curve alone. Moreover, the electrochemical
mechanism of the effective factor on corrosion is analyzed according to the different changes of polarization curve.

2.4. Experimental procedures

Polarization curve test using a three-electrode system, which includes the platinum electrode (auxiliary electrode), saturated
calomel electrode (reference electrode), and working electrode. As the schematic diagram of electrolytic cell is given in Fig. 1,
which constituted a platinum electrode, a reference electrode, a working electrode with the area of 1.0 cm2 and packaged by
epoxy hardener, a gas inlet ans a gas outlet. Before each test, the working face of the working electrode was polished with
400#, 600#, 800# and 1000# abrasive paper, in turn. First rinsed with deionized water, and then swabbed with petroleum
ether to remove the oil, and finally cleaned the stains with anhydrous ethanol, the surface of the sheet steels was dried by
hair dryer. After three electrodes were immersed in the produced water for 60 min, polarization curve was obtained from the
electrochemical workstation.
Potentiodynamic scanning of electrochemical workstation was employed to determine the polarization curve of pipe steel in
the produced water, which scanned from − 1.0 to 0 V with a 2.0 mV/s scanning rate. After testing, the cathode and anode
polarization curves of the strong polarization area were fitting and calculated to get the corrosion current density (icorr) by the
analysis software, which could be further converted into the corrosion rate. In addition, the morphologies of corrosion products
under different conditions were observed by Scanning Electron Microscopy (SEM, America, QUANTA450). The reasons of corrosion
and trends of corrosion rate at different conditions were analyzed.

Table 2
Parameters of produced water from Tuha oilfield.

pH Fe Ni Cu V Na Sulfur concentration DO (mg/L) Cl− (mg/L) CO2

(wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (mg/L) (mg/L)
×10−4 ×10−4 ×10−4 ×10−4 ×10−4

6.59 4.13 6.19 0.06 6.12 9.96 129.68 2.2551 44,000 26.9
 Y. Liu et al. / Engineering Failure Analysis 60 (2016) 307–315 309

Fig. 1. Schematic diagram of electrolytic cell for polarization curves tests.

3. Results and discussion

3.1. Effect of chloride ion on steel corrosion

The effects of different concentrations of chloride ions in the produced water on the corrosion of steel were investigated.
According to the parameters of produced water and the method of electrochemical test, the initial conditions used for the
polarization curves test were as follows: pH value was 6.5, test time was 1 h and test temperature was 20 °C. The polarization
curves of AISI 1020 steel were determined in different chloride ions, which were presented in Fig. 2. And the calculation results
of corrosion rate are shown in Table 3.
The concentration of chloride ion of produced water from the outlet of three-phase separator in Tuha oilfield was 44,000 mg/L,
and so detected the corrosion rate when the content of chloride ion was lower than 44,000 mg/L had little meaning. Therefore, it
was necessary to increase the concentration of chloride ion of produced water to test the polarization curve of working electrode.
Table 3 showed that the corrosion rate of working electrode gradually enlarged with the increase of the content of chloride ion,
but presented a little change in 84,000–104,000 mg/L. Furthermore, the corrosion rate rapidly increased when the concentration
of chloride ion increased to 144,000 mg/L. Taken as a whole, the corrosion rate would gradually experience the smooth invariant
stage, the slow rise stage, and the rapid rise stage, which were seen in Fig. 3.
As shown in Fig. 4, the surface morphology of steel specimen was observed by SEM photograph when the concentration of
chloride ion was 144,000 mg/L, which showed that the corrosion products were dense and homogeneous, but they were finally
destroyed. This phenomenon could be explained that the chloride ion was attached to the surface of the sheet steel in the smooth

Fig. 2. Polarization curves of AISI 1020 steel of different chloride ion concentration.
310 Y. Liu et al. / Engineering Failure Analysis 60 (2016) 307–315

Table 3
Electrochemical corrosion rates of AISI 1020 steel in different chloride ion concentration.

Chloride ion(mg/L) 44,000 64,000 84,000 104,000 144,000

icorr (×10−5) 1.404 1.466 2.083 1.975 5.885
Corrosion rate (mm/y) 0.1637 0.1709 0.2429 0.2303 0.6862

invariant stage, and then they began to work slightly and caused the slow rise of the corrosion rate. As the corrosion progressed,
the corrosion product film was formed on the steel surface, which could prevent the further increase of the corrosion rate.
However, the ionic radius of chloride ion was small, penetration ability was strong, and could permeate to the metal surface
and enrichment from the weakest part of the corrosion product film, and finally destroyed the corrosion product film [19].
Therefore, the chloride ion aggravated steel corrosion.

3.2. Effect of temperature on steel corrosion

When the pH was 6.5, stabilization time was 1 h and the concentration of chloride ion was 44,000 mg/L, the polarization
curves of AISI 1020 steel in the produced water were obtained at 20 °C, 35 °C, 50 °C, 65 °C, and 80 °C, respectively (Fig. 5).
The calculation results of corrosion rate were presented in Table 4.
As shown in Table 4, the results suggested that the corrosion rate of the working electrode gradually increased with the rise of
temperature, and reached a maximum at 65 °C, when the temperature over 65 °C, the corrosion rate reduced. Seen from the SEM
of corrosion morphology of steel specimen at 65 °C (Fig. 6), it suggested that the porous and loose structure of corrosion products
emerged on the surface of specimen. When the temperature was less than 65 °C, the molecular energy enlarged with the increase
of temperature, which could result in the increase of the contact probability of ions and steel surface. Meanwhile, the formed
corrosion products were loose and unstable, and then fell off naturally, and therefore the corrosion rate increased. However, as
the corrosion progressed, the corrosion product film was formed on the steel surface, as when the film-forming rate exceeded
the critical value, the steel surface can form an effective protective film to reduce the area of the steel surface in direct contact

Fig. 3. Effect of chloride ions with different concentrations on the corrosion rate.

Fig. 4. SEM morphology result for AISI 1020 steel when chloride ion concentration was 144,000 mg/L.
 Y. Liu et al. / Engineering Failure Analysis 60 (2016) 307–315 311

Fig. 5. Polarization curves of AISI 1020 steel at different temperatures.

Table 4
Electrochemical corrosion rates of AISI 1020 steel at different temperatures.

Temperature (°C) 20 35 50 65 80
icorr (×10−5) 1.404 2.986 4.452 5.213 2.300
Corrosion rate (mm/y) 0.1637 0.3482 0.5191 0.6078 0.2682

with the solution, which played a slowing effect on corrosion [19,20]. Therefore, the corrosion would be greatly reduced when the
reaction temperature was higher than 65 °C.

3.3. Effect of pH on steel corrosion

The produced water of Tuha oilfield was acidic solution through the on-site survey, and the pH of produced water in this
experiment was 6.5. Therefore, in order to investigate the effect of pH, the produced water was adjusted under acidic conditions.
Under the stabilization time was 1 h, test temperature was 20 °C and the concentration of chloride ion was 44,000 mg/L, the
polarization curves of AISI 1020 steel in the produced water were got when the pH were 6.5, 5.5, 4.5, and 3.5, respectively.
The results were reported in Fig. 7 and Table 5.
It illustrated that the corrosion rate of working electrode would increase with the decrease of pH value of produced water.
However, when the pH values reduced to the range of 6.5–5.5, the corrosion rate was nearly unchanged, which might be due
to the acidity increase of produced water was not high enough, and the reaction time was short. Because the acidity of solution
was enhanced, the reaction rate of steel and acid media was accelerated, and therefore, the corrosion rate enlarged rapidly when
the pH value was lowered from 5.5 to 4.5. As the corrosion progressed, the corrosion product was formed and accumulated on the
steel surface of working electrode, which could be observed by the SEM of corrosion morphology of steel specimen when pH
value was 4.5 (Fig. 8), and meanwhile could reduce the area of the steel surface in direct contact with the solution. Therefore,
the corrosion rate emerged the smooth invariant stage again when the pH value range was 4.5–3.5, which had almost no change.

Fig. 6. SEM of corrosion morphology of AISI 1020 steel specimen at 65 °C.

312 Y. Liu et al. / Engineering Failure Analysis 60 (2016) 307–315

Fig. 7. Polarization curves of AISI 1020 steel at different pH values.

Table 5
Electrochemical corrosion rates of AISI 1020 steel at different pH values.

pH value 6.5 5.5 4.5 3.5

icorr (×10−5) 1.404 1.513 2.236 2.373
Corrosion rate (mm/y) 0.1637 0.1764 0.2607 0.2767

3.4. Effect of CO2 and O2 on steel corrosion

In order to study the effect of CO2 and O2 on the corrosion of sheet steel, CO2, O2, and the mixed gas of CO2 and O2 were
introduced into the electrolytic cell according to a certain flow rate, respectively. The temperature was 20 °C, pH was 6.5,
stabilization time was 1 h and concentration of chloride ion was 44,000 mg/L, the polarization curves of AISI 1020 steel in the
produced water were detected when CO2 and O2 were introduced with the flow rate of 300 mL/min, 600 mL/min, respectively.
Meanwhile, the test was carried on when the mixed gas of CO2 and O2 was introduced, which prepared by the proportion of
CO2 and O2 of 1:1 by flow rate (300 mL/min). The results were shown in Fig. 9 and Table 6.
As seen in Table 6, when CO2 was introduced into the produced water at flow rate of 300 mL/min, the corrosion rate of
working electrode fell slightly, but decreased significantly under the flow rate of 600 mL/min. CO2 could cover the most surface
of working electrode, which played a role in isolating the sheet steel from the solution and made the corrosion rate greatly
reduced. The corrosion rate increases significantly when O2 was introduced at a flow rate of 300 mL/min, which suggested that
the oxygen might be an important factor affecting corrosion. However, when O2 was introduced at a higher flow rate of
600 mL/min, the corrosion product film was rapidly formed on the surface of steel and prevented the steel surface further contact
with O2, and therefore, the corrosion rate lowered. Moreover, when CO2 and O2 were introduced simultaneously with the flow
rate of 300 mL/min, the corrosion rate was between the separate rate of CO2 and O2, and it was closer to the corrosion rate of
O2, which demonstrated that the effect of O2 on the corrosion rate was dominant.

Fig. 8. SEM morphology of AISI 1020 steel specimen when pH value was 4.5.
 Y. Liu et al. / Engineering Failure Analysis 60 (2016) 307–315 313

Fig. 9. Polarization curves of AISI 1020 steel when different gases were introduced.

Table 6
Electrochemical corrosion rates of AISI 1020 steel when different gases were introduced.

Gas Blank CO2 CO2 Mixed O2 O2

(300 mL/min) (600 mL/min) (300 mL/min) (300 mL/min) (600 mL/min)

icorr (×10−5) 1.404 1.216 0.3309 3.665 5.453 2.751

Corrosion rate (mm/y) 0.1637 0.1419 0.0386 0.4273 0.6466 0.3208

However, CO2 corrosion is a time dependent phenomena because protective or non-protective corrosion induced layer forma-
tion can affect corrosion rate. Long term and periodic electrochemical corrosion test was used for this investigation. Under the
conditions of pH was 6.5, test temperature was 20 °C, the concentration of chloride ion was 44,000 mg/L and the flow rate of
CO2 was 300 mL/min, the polarization curves of AISI 1020 steel in the produced water were determined from 1 h to 30 days.
The CO2 corrosion rates at different corrosion time points according to the polarization curves were presented in Fig. 10.
Fig. 10 showed that the CO2 corrosion rate decreased to a minimum after being corroded for 12 h. Then, the CO2 corrosion rate
began to rise, and reached a maximum at 4 days. After being corroded for 4 days, the corrosion rate decreased again, and
gradually got to a constant value which was close to the blank value. Seen from the SEM of CO2 corrosion morphology of steel
specimens at 1 h (Fig. 11), it showed that the steel surface was relatively flat and few corrosion products were formed, which
could be due to CO2 that covers the surface of steel and isolates the steel from the solution, and causes the decrease of corrosion
rate. Combined with the CO2 corrosion mechanism, CO2 could be dissolved in water and resulted in the formation of H2CO3 which

Fig. 10. Electrochemical CO2 corrosion rates of AISI 1020 steel at different corrosion time points.
314 Y. Liu et al. / Engineering Failure Analysis 60 (2016) 307–315

Fig. 11. SEM of CO2 corrosion morphology of AISI 1020 steel specimens at (a) 1 h and (b) 5 days.

could accelerate the corrosion of steel. However, this process would take some time. Therefore, from 12 h to 4 days, the CO2
corrosion rate increased as a result of the existence of H2CO3. As presented in Fig. 11, a large number of the porous structure
of corrosion products were formed and accumulated on the steel surface at 5 days, which could be acted as the protection film
to prevent the corrosion of steel. In addition, the solubility of CO2 in the water reached the saturation state. Eventually, the
CO2 corrosion rate gradually decreased to a stable value and was close to the blank value.

3.5. Effect of time on steel corrosion

As pH was 6.5, test temperature was 20 °C and the concentration of chloride ion was 44,000 mg/L, the polarization curves of
AISI 1020 steel in the produced water were gained when the corrosion time was 1 h, 18 h, 36 h, and 72 h, respectively (Fig. 12),
and got the calculation results of corrosion rate (Table 7).
It was observed that the corrosion rate of the working electrode had barely budged after being corroded for 18 h when
compared with 1 h. The corrosion rate decreased significantly when the corrosion time was over 36 h, and emerged a significant
increase after being corroded for 72 h, but presented a downward trend with respect to the corrosion rate that was soaked when
compared with 1 h and 18 h. That was, the corrosion rate decreased to a minimum when steel had been corroded for 36 h. From
the SEM morphology result for AISI 1020 steel after being corroded for 36 h (Fig. 13), it showed that the corrosion products were
formed on the steel surface, and they were dense and inhomogeneous, which could be acted as the protection film to play an
effective slowing role in a short time. Therefore, it explained the phenomenon that the corrosion rate decreased to a minimum
at 36 h. However, the corrosion product protection film was unstable and even fell down, which accounted for the re-increase
of the corrosion rate after 72 h.

Fig. 12. Polarization curves of AISI 1020 steel at different corrosion time points.

Table 7
Electrochemical corrosion rates of AISI 1020 steel at different corrosion time points.

Corrosion time (hour) 1 18 36 72

icorr (×10−5) 1.404 1.410 0.5463 1.286
Corrosion rate (mm/y) 0.1637 0.1644 0.0637 0.1499
 Y. Liu et al. / Engineering Failure Analysis 60 (2016) 307–315 315

Fig. 13. SEM morphology for AISI 1020 steel after being corroded for 36 h.

4. Conclusions

The results showed that the corrosion induced leakage of pipeline was due to the co-operation of high content of chloride ions
in produced water with other factors. With the increase of chloride ion content, the corrosion rate would gradually experience
three stages: the smooth invariant stage when ion content was less than 6.4 × 104 mg/L, the slow rise stage when ion content
was between 6.4 × 104 mg/L and 1.04 × 105 mg/L, and the rapid rise stage when ion content was more than 1.04 × 105 mg/L.
The rapid rise stage of chloride ion corrosion mainly due to the chloride ion could destroy the formed corrosion product film.
The corrosion rate would reach a maximum at 65 °C with the increase of temperature, while would also reach a maximum
when pH value decreased to 3.5. When the mixed gas prepared by the proportion of CO2 and O2 of 1:1 was introduced into
the media with high flow velocity, O2 was the dominant factor induced the increase of corrosion rate. In addition, the results
of electrochemical CO2 corrosion tests for 30 consecutive days showed that the CO2 corrosion would reach a maximum at
4 days because of the formation of H2CO3. After being corroded for 4 days, the corrosion rate decreased, and gradually got to a
constant value which was close to the blank value, which could be due to the formation of corrosion product film and the
solubility of CO2 in the water reached the saturation state.

Acknowledgments

This study gained the financial support from SWPU Pollution Control of Oil & Gas Fields Science & Technology Innovation
Youth Team (No. 2013XJZT003).

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