E3S Web of Conferences 121, 04006 (2019) https://doi.org/10.

1051/e3sconf/201912104006
Corrosion in the Oil & Gas Industry 2019

Study of corrosion behavior of carbon and low-alloy steels in

CO2-containing environments
Irina Kostitsyna1*, Aleksey Shakhmatov2, and Artem Davydov2
1RN-BashNIPIneft, 450006 Ufa, Russia
2 St. Petersburg Polytechnical University, R&D center Weatherford-Polytechnic, 195251 St. Petersburg, Russia

Abstract. Carbon and low-alloy steels, which constitute the main volume of pipe production, are unstable
to the action of aggressive mineralized oil fields environments, which are often in the late stage of
development. Recently, attempts have been made to use steels with an economical alloying of chromium up
to 0.5% in CO2-containing media without application of the additional measures against corrosion. The
corrosion behaviour of carbon and low-alloy steels with a chromium content of up to 0.5% in CO2-
containing environments was investigated by electrochemical and metallographic studies. The results show
that the addition of 0.5 wt% Cr could not effectively improve the corrosion resistance of the low-Cr alloy
steel in CO2-containing environments.

1 Introduction and gas production and transportation, corrosion must

always be seen as a potential risk. The risk becomes real
Corrosion remains a major operational obstruction to once an aqueous phase is present and is able to contact
successful hydrocarbon production, and its optimum the steel, providing a ready electrolyte for the corrosion
control and management is regarded necessary for the reaction to occur.
cost-effective design of facilities and their safe In recent years, there has been an attempt to use low-
operations [1]. Carbon dioxide (CO2) is a constant Cr alloy steel (0.5% - 3% Cr) in CO2 environments
component in produced water of almost any oil field. without inhibitor injection because adding Cr to low
Typical corrosive damage on internal surfaces of alloy steel could enhance corrosion resistance [2-4]. It
pipelines caused by CO2-corrosion is shown in Fig.1. has been reported that the addition of Cr contributes to
the enrichment of Cr in the corrosion products, which
causes the corrosion product layers to be more
protective. In addition, an increase in Cr content could
lower both the uniform corrosion rate and susceptibility
to localized corrosion in CO2 environments. While some
authors have reported the beneficial effects of chromium
additions, there is not yet a consensus on the optimum
amount of Cr in the steel structure [1].
The objective of the present study was to evaluate the
effect of Cr content up to 0.5 wt.% on the corrosion
behavior of carbon and low alloy steels under different
combinations of pH and temperature.

Fig. 1. A typical example of corrosion damage on internal 2 Experimental

surfaces of pipeline transporting CO2-containing fluids

The industry continues to lean heavily on the 2.1 Material

extended use of carbon and low-alloy steels, which are
readily available in the volumes required and are able to The test specimens with different alloying systems were
meet many of the mechanical, structural, fabrication, and selected from steels, serially used to produce oil and gas
cost requirements. Their technology is well developed, pipes. The steels used in this study are melted in electric
and they represent an economical materials choice for arc furnaces with following ladle refining and final
many applications. However, a key issue for their aluminium deoxidation and calcium treatment. All
effective use is their poor general and CO2 corrosion materials were analysed for chemical composition using
performance. Given the conditions associated with oil

*
Corresponding author: [email protected]
© The Authors, published by EDP Sciences. This is an open access article distributed under the terms of the Creative Commons Attribution License 4.0
(http://creativecommons.org/licenses/by/4.0/).
E3S Web of Conferences 121, 04006 (2019) https://doi.org/10.1051/e3sconf/201912104006
Corrosion in the Oil & Gas Industry 2019

atomic emission spectroscopy. Table 1 shows chemical

compositions of steels used in the present study.
Table 1. Chemical compositions of steels

Steel C Si Mn P S Cr Mo
0.20C-Mn
0.18 0.23 0.51 0.009 0.015 0.08 0.01
(As rolled)
0.20C-Mn 0.19 0.22 0.54 0.009 0.003 0.08 0.02

0.15C-0.5Cr 0.15 0.23 0.53 0.008 0.002 0.64 0.01

0.10C-0.5Cr-
0.11 0.38 0.56 0.008 0.005 0.60 0.18
0.2Mo

According to Table 1 following steels samples were

investigated: (1) C-Mn steel in as rolled condition, (2) C-
Mn steel, (3) C-Mn-0.5Cr steel with 0.64 wt. % Cr
Fig. 2. External view of corrosion electrochemical tests setup
addition and (4) C-0.5Cr-Mo steel with the
relatively lowest carbon content and 0.60 wt. % Cr and Electrochemical corrosion tests were consisted of
0.18 wt. % Mo additions. Last three steels were open circuit potential (OCP) measurements and
heat treated according to commercial production potentiodynamic polarization with 0.16 mV/s scan rate
routes in order to obtain microstructures condition. in range of OCP ± 50 mV with followed corrosion rates
The microstructures details will be discussed further. (CR) calculations according to Tafel corrosion current
2.2 Electrochemical corrosion tests (icorr) extrapolation. Equivalent weights samples values
were in range 27.99 – 28.14 depending on actual steels
The flat ≈ 0.80 cm2 specimens were used for static chemistry. Materials density was set to 7.8 g/cm3.
electrochemical corrosion tests. Specimens were Knowing specimen area, density, equivalent weight it
sequentially ground with 180, 400, and then 600 grit was possible to calculate corrosion rates from corrosion
silicon carbide (SiC) paper with following cleaning, current measurements results [5]. Graphic representation
degreasing and drying. The test solution was prepared of electrochemical measurements procedure is shown in
from deionized water with 5 wt.% NaCl. There were two Fig. 3.
types of solution regarding pH range that were used at
different temperatures: 20, 40 and 60°C. Table 2
represents tests conditions. The pH range information
will be used as the test solution description in results and
discussion chapter.
Table 2. Corrosion electrochemical test conditions

Temperatures, pH
Solution
°C range
1.5 g/L NaHCO3 buffer,
5 wt.% NaCl static, 20; 40; 60 5.6-6.0
deaerated, CO2 saturated
5 wt.% NaCl static,
20; 40; 60 3.8-4.2
deaerated CO2 saturated

The solution was initially deaerated by 1 hour Fig. 3. Graphic representation of electrochemical tests
nitrogen bubbling. Corrosion tests were performed in a measurements
300 mL cell under atmospheric CO2 pressure. The cell OCP value corresponds to equilibrium corrosion potential and
setup consisted of: (1) three-electrode corrosion cell: will be referred as potential in further discussion.
Pt counter electrode, Ag/AgCl reference electrode,
working electrode); (2) oil thermostat system; (3) CO2
gas supply set (Fig. 2). 2.3 Metallography
Steel microstructure study was carried out with using
light optical microscopy. Microstructures that were
corresponded to transverse ¼ pipeline thickness were
revealed by 4% Nital etching. Hardness measurements
were performed by Vickers microhardness test with 180
g load.

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E3S Web of Conferences 121, 04006 (2019) https://doi.org/10.1051/e3sconf/201912104006
Corrosion in the Oil & Gas Industry 2019

3 Results and discussion

Prior the electrochemical test results discussion
microstructure investigation will be presented.
Investigated steels microstructures are shown in Fig. 4.

Fig. 5. 0.20C-Mn steel polarization curves evolution depending

on temperature and solution pH

According to Fig.5 lower pH in non-buffered CO2

saturated solution shifts OCP from ≈ 650 mV range to
≈550 mV with following increasing of cathodic and
Fig. 4. Microstructures of investigated steels, ×200, 4% Nital anodic reactions current densities. This fact is agreed
0.20 C-Mn (as-rolled) and 0.20C-0.5Cr-0.2Mo steels had with results of CO2 electrochemistry study [8]. Also, the
ferrite-pearlitic microstructures with relative hardness possible explanation of observed polarization curves
values equal to 175 and 198 HV. The C-Mn (As rolled) shifts is cathodic reaction evolution due carbonic acid
steel had not banded slightly coarse microstructure in dissociation dependence on pH. The overall
comparison with 0.20C-0.5Cr-0.2Mo steel that have fine, electrochemical corrosion tests results are presented in
but not homogeneous structure which is characterized by Table 3.
perlite and ferrite phase distribution. This type of Table 3. Electrochemical corrosion test results
inhomogeneity could be formed during annealing heat
treatment and solidification inheritance phenomena Temperature,
pH 5.6-6.0 pH 3.8-4.2
occurrence [6,7]. The 0.20C-Mn steel microstructure Steel OCP, CR, OCP, CR,
°С
mV mm/y mV mm/y
investigation revealed fine distributed ferrite and pearlite 20 -627 0.03 -562 0.33
phases. The revealed microstructure hardness is equal to 0.20C-Mn
40 -641 0.08 -577 1.25
186 HV. The microstructure of 0.15C-0.5Cr steel is (As rolled)
60 -660 0.13 -588 1.71
spheroidized annealed microstructure with uniform 20 -632 0.02 -543 0.26
carbides distribution in ferrite matrix. The hardness was 0.20C-Mn 40 -640 0.04 -564 0.61
equal to 184 HV. So, as overall investigation it could be 60 -664 0.05 -570 0.79
20 -652 0.06 -571 0.74
concluded that investigated steels are belong to similar 0.15C-
40 -662 0.10 -585 1.43
strength grade, but with different microstructure 0.5Cr
60 -677 0.13 -587 2.14
conditions as the result of production route technology. 0.10C- 20 -664 0.02 -541 0.36
The microstructure investigation will be used in 0.5Cr- 40 -677 0.04 -556 0.77
electrochemical corrosion tests results interpretation. 0.2Mo 60 -682 0.07 -567 1.29
As the results of electrochemical tests polarization
curves for investigated steels in different environments According to electrochemical results (Table 3) the OCP
were obtained and analyzed. For example, 0.20C-Mn from -682 to -627 were observed in solution with higher
steel polarization curves evolution depending on pH 5.6-6.0 and from -588 to -541 in non-buffered CO2
temperature and solution pH is presented in Fig. 5. saturated solution with lower pH 3.8-4.2. The corrosion
rates measurements results showed following variation:
0.02÷0.13 mm/y at pH 5.6-6.0 and 0.26÷2.14 mm/y at
pH 3.8-4.2, where increased rates correspond to
increased environment testing temperature. Graphical
comparative representation of obtained data (Table 3) is
presented in Figures 6 and 7.

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E3S Web of Conferences 121, 04006 (2019) https://doi.org/10.1051/e3sconf/201912104006
Corrosion in the Oil & Gas Industry 2019

Fig. 6. Investigated steels potentials comparison depending on

pH and temperature Fig. 9. Temperature influence on investigated steels corrosion
rates in CO2 environment with pH range 3.8-4.2
From corrosion rates point of view steels could be
Overall analysis environment parameters influence
ranged in following order from poor to best corrosion
has shown that by increasing temperature from 20 to
performance in CO2 environment: 0.15C-0.5Cr, 0.20C-
60°C and by decreasing pH from ≈ 6.0 to ≈ 4.0 corrosion
Mn (As rolled), 0.10C-0.5Cr-0.2Mo, 0.20C-Mn. In
rates were dramatically increased. The interpretation for
purpose of additional illustrations for this type of steel
this experimentally obtained fact is complex
comparison Figures 8 and 9 are presented below.
microstructure/chemistry effect and its interaction with
environment.
Corrosion rates measurements results show that there
was no benefit in 0.5Cr addition for 0.15C-0.5Cr steel as
the result of high carbon content chromium was tied up
in carbides and then was no more available to reduce
corrosion rate.
The next 0.20C-Mn (As-rolled) is slightly better in
comparison with previous example (0.15C-0.5Cr), due
to ferrite-perlite microstructure after hot rolling process.
The 0.10C-0.5Cr-0.2Mo has shown good performance
and it is due to ferrite-perlite microstructure and alloying
system but revealed ferrite-perlite microstructure
inhomogeneity did not let get CO2 corrosion benefit
from Cr and Mo additional alloying. The 0.20C-Mn steel
with relatively low sulphur content (Table 1) in
Fig. 7. Investigated steels corrosion rates in CO2 environment
comparison with as-rolled 0.20C-Mn steel and which is
depending on pH and temperature had fine well distributed ferrite-perlite microstructure
has shown best performance in CO2 containing
environment. It should be noticed that obtained data is
more likely corresponds to steel-environment interaction
in instantaneous context and it didn’t cover a complex
topic of CO2 corrosion products layer formation in time.
There was published data [9] that the more uniform the
distribution and the smaller the ferrite grain size, the
lower the corrosion rate.

4 Conclusions
1. The corrosion and metallography studies of
commercially available pipeline steels were
provided. It was shown that 0.20C-Mn steel with
fine homogenous microstructure had relatively
lowest corrosion rates in CO2 environment.
Fig. 8. Temperature influence on investigated steels corrosion 2. There is no clear evidence benefit significant
rates in CO2 environment with pH range 5.6-6.0 influence of Cr and Mo addition on corrosion rates.
The most possible reason is microstructure
condition. For example, the 0.15C-0.5Cr steel in
spheroidized microstructure condition have

4
E3S Web of Conferences 121, 04006 (2019) https://doi.org/10.1051/e3sconf/201912104006
Corrosion in the Oil & Gas Industry 2019

relatively high corrosion rates in comparison with

0.20C-Mn steels.
3. According to investigated environments conditions,
the temperature increasing and pH decreasing leads
to steels corrosion rates increasing in CO2 saturated
environment.

References
1. M.B. Kermani, A. Morshed, Corrosion – Vol.59,
no.8 (2003)
2. M. Ueda, H. Takabe, P.I. Nice, CORROSION 2000,
NACE International 2000
3. T. Muraki, T. Hara, K. Nose, H. Asahi,
CORROSION 2002, paper no. 272 (Houston, TX:
NACE, 2002)
4. Y.S. Choi, S. Nešic, H.G. Jung, Corrosion – Vol.59,
№8 (2003)
5. ASTM G102-89 (2015) e1., Standard Practice for
Calculation of Corrosion Rates and Related
Information from Electrochemical Measurements,
ASTM International, West Conshohocken, PA,
2015, www.astm.org
6. Krauss, G, Solidification, Segregation, and Banding
in Carbon and Alloy Steels, Metallurgical and
Materials Transactions B: Process Metallurgy and
Materials Processing Science, Volume 34, Issue 6,
December 2003, Pages 781-792
7. Kazakov, A., Daniil Kiselev, Elena Kazakova,
George F. Vander Voort, and Lev Chigintsev.
"Quantitative Description of Microstructural
Banding in Steels." Materials Performance and
Characterization 6, no. 3 (2017): 224-236. doi:
https://doi.org/10.1520/MPC20160009
8. Aria Kahyarian, Bruce Brown, Srdjan Nesic,
Electrochemistry of CO2 corrosion of mild steel:
Effect of CO2 on iron dissolution reaction,
Corrosion Science, Volume 129, 2017, Pages 146-
151
9. Guenter, S., Hörstemeier, M., Fundamental aspects
of CO2 metal loss corrosion – Part II Influence of
different parameters on CO2 corrosion mechanisms,
Paper 06112, CORROSION/2006, NACE
International, 2006