Caspian Journal of Applied Sciences Research, 1(11), pp.

1-10, 2012
Available online at http://www.cjasr.com
ISSN: 2251-9114, 2012 CJASR

Corrosion Investigation of A516-Gr70 and API 5LX70 Steels in H2S Containing

Solution
Saeid Kakooei1*, Hossein Taheri2, Mokhtar Che Ismail1, Abolghasem Dolati3
1 Center For Corrosion Research, Mechanical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri
Iskandar, 31750 Tronoh, Perak, Malaysia.
2 Corrosion Engineering Group, Engineering Faculty, Kish University, Kish Island, Iran.
3Department of Materials Engineering, Sharif University of Technology, Tehran, Iran

*Corresponding Author: skakooei59@hotmail.com

Environmental cracking in the presence of wet hydrogen sulfide (H2S) is a serious problem in the chemical or
petrochemical industries. This phenomenon causes major failure for pipeline steels transmitting sour gas/oil and
steel tanks storing liquefied petroleum gas (LPG). The effect of environmental parameters was studied for HSLA
steels (X70, A516) in sour simulated solution. The dissolved H2S was created by chemical reactions in solution.
Na2S9H2O was chosen as test material to replace H2S because of the toxicity of H2S. The specimens were
immersed into synthetic seawater saturated with H2S where corrosion behavior was evaluated by
potentiodynamic polarization, weight loss, and scanning electron microscopy (SEM). The results showed that
the presence of alloying elements can change the corrosion rate in inspecting steels.
Key words: Hydrogen sulfide; Corrosion; Hydrogen induced cracking; Sour environment

1. INTRODUCTION
Oilfield systems experience pipeline failures due
to presence of
aqueous H2S which cause
aggressive damage to the steels used in the
transport and processing of petroleum products.
Inspection studies on pipeline failures in the
petroleum refining industry indicate that 25% of
failures are associated by hydrogen diffusion. The
wet H2S reacts with steel will lead to generation of
atomic hydrogen. A part of atomic hydrogen will
be absorbed and penetrated into the steel(Carneiro
et al., 2003; Kittel et al., 2008). The diffused
hydrogen could be a reason of blistering or
hydrogen induced cracking (HIC) (Nasirpouri et
al., 2011).
Cathodic polarization of molecular surface
complex (Fe H-S-H) results in the release of
hydrogen atoms when aqueous H2S reacts with
steel. Some of the released hydrogen atoms will
diffuse into steel and others will recombine
(Elboujdaini et al., 2003). The mechanism is
shown below from equations.(1)-(4).
Fe + H2S + H2O FeSH ads +H3O+
FeSH ads FeSH+ads +2eFeSH+ads FeS + H+
FeSH+ads + H3O+ Fe2+ +H2S +H2O

value due to welding and cooling, the crack

initiation happens (Rogante et al., 2006). When
the concentration of hydrogen sulfide is low in a
CO2 dominated system, it is reported that the iron
sulfide (FeS) film interferes with the formation of
the iron carbonate scale (FeCO3). Although, the
FeS film is believed to have a protective effect at
about 60C (Brown et al., 2003).
Corrosion behaviors of two common pipeline
steels (X70 and A516) in different H2S
concentration brine solution are investigated in the
present study.
2. MATERIALS AND METHODS
Experiments were carried out at 50C in a glass
cell (Figure 1). Two common pipeline steel A516Gr70 and API 5LX70 were investigated in this
study. Elemental composition of two inspected
steels is shown in Table 1. A typical threeelectrode setup was used with a saturated calomel
electrode (SCE) as the reference electrode, a
platinum counter electrode, and X70 and A516
steel specimens as the working electrodes. Steel
specimens were connected to copper wire and
covered with epoxy resin with an exposed area of
1cm2. The specimens were polished, degreased
with acetone and rinsed with distilled water before
conducting experiments.

(1)
(2)
(3)
(4)

Hydrogen diffuses shift stress gradients from

regions of lower to higher concentration. When
the concentration of hydrogen reaches a critical

Kakooei et al.
Corrosion Investigation of A516-Gr70 and API 5LX70 Steels in H2S Containing Solution

Different concentrations of H2S containing

solution were made by using different
concentration of Na2S.9H2O , acetic acid, and

distilled water as shown in Table 2 (Taheri et al.,

2012). The base solution was 3% NaCl solution.

Fig. 1: Schematic of the experimental test cell: 1-platinum counter electrode 2- temperature probe 3reference electrode, 4-Chemical in, 5- sample holder (working electrode) 6-gas out.
Table 1: Elemental composition of X70 and A516 steels (in wt %).
Elements
Chemical Composition
(wt%)
X70
A516
C
0.08
0.2
Si
0.29
0.3
Mn
1.59
1.05
P
0.013
0.035
S
0.002
0.04
Cu
0.08
-Ni
0.1
-Cr
0.02
-Mo
0.11
-V
0.047
-Al
0.023
-Nb
0.034
-Ti
0.016
-Fe
Balance
Balance

Caspian Journal of Applied Sciences Research, 1(11), pp. 1-10, 2012

Table 2: Different concentration of chemicals for test matrix

Material
Concentration of Solution (mol/Lit)

Na2S.9H2O
CH3COOH

C1
0.015

C2
0.035

C3
0.055

C4
0.075

0.035

0.082

0.128

0.175

slop and redox potential, as shown in equations 5

and 6 (Fatah et al., 2011):

Corrosion rates in weight loss experiment were

measured by using the following equation [6]:
C .R

Na2S+H2
2Na++HS +OH
(5)
2HS +2e 2S (ads)+2H(ads)
(6)
Figures 4 and 5 demonstrate the results of the
weight-loss experiment for the X70 and A516
steel types, respectively. The variations in the
corrosion rate are due to the role of the FeS film
in surface passivation. The A516 steel samples
dipped in critical concentration (C2) exhibited a
high corrosion rate under different exposure times
because the FeS protective layer was detached
from the surface, thereby increasing the corrosion
rate.
For the X70 steel, by contrast, the protective
layer was apparently unstable under all
concentrations, and the average corrosion rate
increased with increasing H2S concentration. A
layer of the black corrosion film was detected on
the surfaces of all specimens after exposure to the
test solution.
The EDAX analysis of the corrosion product
indicates a high sulfur content due to the FeS film
on the sample surface (Figure 6).
Table 1 shows the chemical composition of the
steel specimens. The Nb, Cu, and Mo present in
X70 steel produced carbon nitride during its
manufacture. Thus, the corrosion rate of this steel
is lesser than that of the A516 steel.Furthermore,
the susceptible area for the initiation of cracking
in the X70 steel is reduced. In contrast, the A516
steel is more susceptible to corrosion because of
the high MnS content, which is another causative
factor of the high corrosion rate of this steel.
Decreasing the sulfur and manganese contents can
decrease the corrosion rate of the A516 steel.

534 W
DAT

(5)
Where C.R. is corrosion rate (mpy), W is the
weight loss (mg), D is specimen density (g/cm3),
A is specimen exposure surface (in2), and T is
exposure time (hr).
The corrosion morphology of specimens and
hydrogen induce cracking were characterized by
SEM (Vega Tescan, USA). Corrosion products on
the corroded samples were analyzed using Energy
dispersive X-ray spectroscopy (EDAX).
3. RESULTS AND DISCUSSION
The potentiodynamic polarization curves for X70
and A516 steels under different H2S solution
concentrations at 50 C are shown in Figures 2
and 3, respectively. The corrosion potential
becomes increasingly positive with increasing
H2S concentration. Two factors that influence the
value of the corrosion potential are the cathodic
and anodic processes. Although the individual
contribution of each process is not very
significant, a positive shift in the corrosion
potential occurred because the cathodic process on
the metal surfaces was promoted, and the anodic
process was retained. The combined effect of
these processes can be clearly observed in Figures
2 and 3. However, Tang et al. (2010) showed that
under a high H2S concentration at 90 C, the
cathodic hydrogen evolution process on a metal
surface increasingly influenced the cathodic
branches with increasing H2S concentration,
thereby positively shifting the potential. However,
the anodic branches remained nearly the same in
all solutions..
Fatah et al. (2011) indicated that a change in
the nature of the cathodic reaction in the presence
of S2- ions is the main causative factor of the
changes in the cathodic reaction of both the Tafel

Kakooei et al.
Corrosion Investigation of A516-Gr70 and API 5LX70 Steels in H2S Containing Solution

Fig. 2: Potentiodynamic polarization curves of X70 steel in the 3% NaCl solution with different concentration of H2S(C1, C2, C3, and C4) for different exposure times a) 24, b) 48,
c) 72, d) 96 hr at 50C

Caspian Journal of Applied Sciences Research, 1(11), pp. 1-10, 2012

Fig. 3: Potentiodynamic polarization curves of A516 steel in the 3% NaCl solution with different concentration of H2S(C1, C2, C3, and C4) for different exposure times a) 24, b) 48,
c) 72, d) 96 hr at 50C .

Kakooei et al.
Corrosion Investigation of A516-Gr70 and API 5LX70 Steels in H2S Containing Solution

Fig. 4: 3D column chart of corrosion rate of X70 steel vs. different H2S concentration C1, C2, C3, and C4 with different exposure time at 50C.

Fig. 5: 3D column chart of corrosion rate of A516 steel vs. different H2S concentration C1, C2, C3, and C4 with different exposure time at 50C.

Caspian Journal of Applied Sciences Research, 1(11), pp. 1-10, 2012

Fig. 6: EDAX analysis of corrosion product after removing form steel surfaces

Kakooei et al.
Corrosion Investigation of A516-Gr70 and API 5LX70 Steels in H2S Containing Solution

Figures 7 and 8 respectively illustrate the SEM

images of the X70 and A516 steel samples after
exposure to H2S for 96 h at 50 C. The cracks in
the FeS film demonstrate that this layer is unstable
for surface passivation in X70 steel and cannot
protect the steel surface from further corrosion
(Figure 8). By contrast, the FeS film on the A516
steel surface is stable and uniform; hence, it can
protect this steel from further corrosion.

Metallographic cross sections of the hydrogeninduced cracking in both steel types are shown in
Figures 9 and 10. The color mapping of the
corrosion product on the A516 steel surface
emphasizes the presence of FeS on the specimen
surface (Figure 11).

Fig. 7: SEM image of corrosion product on A516 steel surface

Fig. 8: SEM image of corrosion product on X70 steel surface

Caspian Journal of Applied Sciences Research, 1(11), pp. 1-10, 2012

Fig. 9: Metallographic cross section of A516 steel at 50C

Fig.10: Metallographic cross section of X70 steel at 50C

Fig. 11: Color mapping of corrosion product on steel surface

for the X70 and A516 steel types. The width of
the crack in the A516 steel was greater than that in
the X70 steel, indicating that A516 steel is more
susceptible to HIC . However, the presence of
alloying components, such as Cu and Nb, can
reduce the occurrence of HIC in X70 steel. The
average corrosion rates of the X70 specimens

4. CONCLUSION
The FeS film was detected on the surfaces of both
steel types, although with different morphologies
and stabilities. The result shows that hydrogeninduced cracking can occur in solutions with H2S

Kakooei et al.
Corrosion Investigation of A516-Gr70 and API 5LX70 Steels in H2S Containing Solution

Fatah M, Ismail M, Ari-Wahjoedi B, Kurnia K

(2011). Effects of sulphide ion on the
corrosion behaviour of X52 steel in a
carbon
dioxide
environment
at
temperature 40 C. Materials Chemistry
and Physics, 127(1-2): 347352.
Kittel J, Martin J, Cassagne T, Bosch C (2008).
Hydrogen Induced Cracking (HIC)laboratory testing assessment of low alloy
steel linepipe. CORROSION. New
Orleans LA, NACE International.
Nasirpouri F, Alizadeh H, Gholizadeh MH
(2011). Failure analysis of a carbon steel
screw under the service in the presence of
hydrogen sulphide. Engineering Failure
Analysis, 18(8): 23162323.
Rogante M, Battistella P, Cesari F (2006).
Hydrogen interaction and stress-corrosion
in hydrocarbon storage vessel and
pipeline weldings. International Journal of
Hydrogen Energy, 31(5): 597-601.
Tang J, Shao Y, Guo J, Zhang T, Meng G, Wang
F (2010). The effect of H2S concentration
on the corrosion behavior of carbon steel
at 90 C. Corrosion Science, 52(6): 20502058.
Taheri H, Kakooei S, Ismail MC, Dolati A (2012).
The effect of H2S concentration and
temperature on corrosion behavior of
pipeline steel A516-Gr70. Caspian
Journal of Applied Sciences Research,
1(5): 41-47.

were higher than those of the A516 specimens.

The corrosion rates of X70 steel did not show
considerable changes under the different H2S
concentrations, whereas A516 exhibited a C2
value that enhanced the corrosion rate by twice
the initial rate. This condition indicates the
unstability of the FeS film under C2
concentration.
Acknowledgments
Facilities and funding for this study were provided
by Kish University, Iran. Also authors would like
to thank Universiti Teknologi PETRONAS for
supporting the research work.
REFERENCES
Brown B, Lee KL, Nesic S (2003). Corrosion in
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of H2S. CORROSION. San Diego Ca,
NACE International.
Carneiro RA, Ratnapuli RC, de Freitas Cunha
Lins V (2003). The influence of chemical
composition and microstructure of API
linepipe steels on hydrogen induced
cracking and sulfide stress corrosion
cracking.
Materials
Science
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Engineering: A, 357(1): 104-110.
Elboujdaini M, Derushie C, Revie RW (2003).
Effects of Metallurgical Parameters and
Non-Metallic Inclusions on Behavior for
Oil and Gas Industry Steels on Hydrogen
Induced Cracking. CORROSION 2003.

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