Caspian Journal of Applied Sciences Research, 1(5), pp.

41-47, 2012
Available online at http://www.cjasr.com
ISSN: 2251-9114, 2012 CJASR

The Effect of H2S Concentration and Temperature on Corrosion Behavior of

Pipeline Steel A516-Gr70
Hossein Taheri1, Saeid Kakooei2*, Mokhtar Che Ismail2, Abolghasem Dolati3
1

Corrosion Engineering Group, Engineering Faculty, Kish University, Kish Island, Iran
Center For Corrosion Research, Mechanical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri
Iskandar, 31750 Tronoh, Perak, Malaysia.
3
Department of Materials Engineering, Sharif University of Technology, Tehran, Iran
*Corresponding Author: Saeid Kakooei; Email: skakooei59@hotmail.com

Present study the effect of H2S concentration and temperature on corrosion behavior was studied for ASTMA516-Gr70 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 H 2S where corrosion behavior was evaluated by
potentiodynamic polarization, weight loss, and scanning electron microscopy (SEM). The result show that the
hydrogen induced cracking can take place in H2S containing solution for A516-Gr70 steels.
Key words: Hydrogen sulfide; Corrosion; Hydrogen induced cracking; pipeline steel A516-Gr70

temperature (200-900C) due to the presence of

hydrogen gas at high pressures that usually happen
in the various units of oil refineries (Groysman et
al. 2011). The mechanism of the effect of hydrogen
sulfide in formation of hydrogen atoms that cause
by the formation of a molecular surface complex
(Fe H-S-H) which on cathodic polarization. Then
some of the hydrogen atoms will diffuse, whereas
other may recombine (Elboujdaini et al., 2003).

1. INTRODUCTION
Many scientific articles have been discussed about
hydrogen induced cracking (HIC) of carbon steel
pipe. The diffused hydrogen could be a reason of
blistering or hydrogen induced cracking
(HIC)(Venegas et al., 2005; Nasirpouri et al.,
2011). Hydrogen damage divided to two
categories: 1) at low temperature (20-100C)
because of electrochemical process and 2) at high

Fe + H2S + H2O FeSHads +H3O+

FeSH

ads

FeSH

ads

FeS + H

FeSH

ads

+2e

(1)
(2)

(3)

FeSH+ads + H3O+ Fe2+ +H2S +H2O

When the concentration of hydrogen reaches a
critical value due to welding and cooling, the crack
initiation happens(Rogante et al. 2006). Exposure
of iron in saturated media with H2S cause
formation of different layer of hydrogen sulfide
such as Pyrite (FeS2), Marcasite (FeS2), Pyrrhotite
(monoclinic and hexagonal (Fe1-xS)), Triolite
(FeS), and Makinawite (FeS1-x). Also solubility of
these different layers in the presence of hydrogen
sulfide at room temperature and 1.18 MPa are
1:10:40:80:6000
for
Makinawite,
Triolite,
monoclinic Pyrrhotite, hexagonal Pyrrhotite, and
Pyrite, respectively (Dehkordi et al., 2007).
Development of the FeS formation as a corrosion
product is a function of pH, temperature and the
exposure time (Smith et al. 2011). According to

(4)

literature, corrosion rates of steel A516-Gr70 at

temperatures above 100C enhanced when
concentration of hydroxide or sulfide increases
(Hazlewood et al., 2006). Wilken and Martin
(2003) investigated Hydrogen Induced Cracking
(HIC) of Steel A516-Gr70 in different pH
environment. They found that in media with pH
below 7.1, hydrogen permeation was considerable
and HIC can increase at non-metallic inclusions
(Wilken and Martin, 2003).
The influence of different H2S concentration on
corrosion behavior of pipeline steel A516-Gr70
under various temperatures were investigated in
this work.

41

Taheri et al.
The effect of H2S concentration and temperature on corrosion behavior of pipeline steel A516-Gr70

steel is shown in Table 1. Steel specimens were

connected to copper wire and covered with epoxy
resin with an exposed area of 1cm2. The specimens
were polished, rinsed and degreased. Different
concentrations of Na2S.9H2O were consumed to
produce different concentrations of H2S containing
solution (Table 2). The base solution was 3% NaCl
solution.

2. MATERIALS AND METHODS

Experiments were performed at 25C and 50C in
a typical three-electrode glass cell (Fig. 1). A
saturated calomel electrode (SCE) as the reference
electrode, a platinum counter electrode, and A516Gr70 steel specimens as the working electrodes
were used. Elemental composition of A516-Gr70

Table 1: Elemental composition of A516-G70 steels (in wt %).

Elements

Chemical
Composition (wt %)

Fe
C
Si
Mn
P
S
Ni
Cr

98.02
0.24
0.33
1.05
0.035
0.04
0.0387
0.0331

Weight loss experiment was done for corrosion rates estimation by using following equation:
C.R

534W
DAT

(1)

Where C.R. is corrosion rate (mpy), W is the

weight loss (mgr), D is specimen density (gr/cm3),

A is specimen exposure surface (in2), and T is

exposure time (hr).

Fig. 1: Schematic of the experimental test cell: 1-platinum counter electrode 2- temperature probe 3-reference
electrode, 4-Chemical in, 5- sample holder (working electrode) 6-gas out, 4-Luggin capillary.
Table 2: Different concentration of chemicals for test matrix
Material

Concentration of Solution (mol/Lit)

C1
C2
C3
C4

Na2S.9H2O
CH3COOH

0.015
0.035

0.035
0.082

The morphology of corrosion products on

sample surface and hydrogen induce cracking was
characterized by SEM. Corrosion products on the

0.055
0.128

0.075
0.175

corroded samples were analyzed using Energy

dispersive X-ray spectroscopy (EDAX).

42

Caspian Journal of Applied Sciences Research, 1(5), pp. 41-47, 2012

H2S concentration at 25C and 50C are shown in

Fig.2 and 3. As it can be seen cathodic curve
(hydrogen evolution reaction) was accelerated by
increasing H2S concentration while anodic curves
showed similar current densities. This anodic curve
is related to dissolution of iron. The change in
corrosion values can be explained by growth
mechanism of iron sulfide film. Iron sulfide layer
has a thickness limitation. When film grows to
critical values, it will be break up. So when the
corrosion rates are minimum, the iron sulfide
thickness is the best values and electrons and
ferrous ions will transfer through the iron sulfide
film.

3. RESULTS AND DISCUSSION

Table 1 shows chemical composition of test
samples. The existence of high sulfur content in
A516-Gr70 steel is one reason of high corrosion
rate of this steel in sour environment. Decreasing
of sulfur and manganese content can decrease
corrosion rate in A516-Gr70 steel since MnS
content decreases. Furthermore susceptible place
for initiating crack in A516 are more than other
pipeline steel such as API- X70 due to high MnS
content in A516-Gr70 steel.
The potentiodynamic polarization curves for
A516-Gr70 steel in solutions containing different

Fig. 2:
Potentiodynamic polarization curves of A516-Gr70 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 25C .

Fatah et al. (2011) indicated that change in the

nature of cathode reaction in the presence of S2
ions is the main responsible of changes in cathodic

reaction in both Tafel slop and redox potential as

shown in the following reactions:

Na2S + H2O 2Na+ +HS +OH

2HS +2e 2S2 (ads) + 2H (ads)
Table.3 shows the permeable hydrogen
concentration. It can be consider as amount of
hydrogen that penetrate into steel and cause HIC.
In first step hydrogen attaches the steel by

(5)
(6)

adsorption onto the water to steel interface and

then by being absorbed into the steel as hydrogen.
The amount of hydrogen penetration depends on
the corrosion rate of the steel surface and the

43

Taheri et al.
The effect of H2S concentration and temperature on corrosion behavior of pipeline steel A516-Gr70

concentration of anions such as HS- that reduce the

tendency to produce hydrogen gas and promotes
the hydrogen (Ho) to enter the steel (Tung et al.,

2001). By increasing the temperature, hydrogen

concentration increases.

Fig. 3: Potentiodynamic polarization curves of A516-Gr70 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 .
Table 3: Permeable hydrogen concentration

A516-Gr70

25OC

52OC

Hydrogen concentration (ml)

H2S concentration

C1

0.5

C2

0.4

C3

0.2

C4

0.6

C1

0.9

C2

1.2

C3

0.7

C4

Fig.4 and 5 show result of corrosion rate in

weight loss experiment. Changes in corrosion rate
are due to iron sulfide film role in surface
passivation. Corrosion rate will increase when this
protective layer detaches from surface. The most
corrosion rate is measured in H2S concentration C2

at 25C, which has a good correlation with

potentiodynamic polarization results. A cover of
black corrosion film was detected on all
specimens surfaces after exposure in test solution.
Fig.6 illustrates a SEM image specimen after
exposure 96 hr at 25C in sour environment.

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Caspian Journal of Applied Sciences Research, 1(5), pp. 41-47, 2012

Cracks in FeS film show that this layer is not a

stable layer for surface passivation and it cannot

protect steel surface form further corrosion.

Fig. 4: 3D column chart of corrosion rate of A516-Gr70 steel vs. different H2S concentration C1, C2, C3, and C4 with
different exposure time at 25 C.

Fig. 5: 3D column chart of corrosion rate of A516-Gr70 steel vs. different H2S concentration C1, C2, C3, and C4 with
different exposure time at 50 C.

Fig. 6: SEM image of corrosion product on A516-Gr70 steel surface

45

Taheri et al.
The effect of H2S concentration and temperature on corrosion behavior of pipeline steel A516-Gr70

Fig. 7: EDAX analysis of corrosion product

Fig. 8: Metallographic cross section of A516-Gr70 steel at 25 C after 96 hr

Fig. 9: Color mapping of corrosion product on A516-Gr70 steel surface

46

Caspian Journal of Applied Sciences Research, 1(5), pp. 41-47, 2012

According to Fig.7, EDAX analysis of

corrosion product shows high sulfur content due to
FeS film in sample surface. Fig.8 depicts
metallographic cross sections of HIC on sample
surface after 96 hr exposure at 25C in sour
environment. HIC is clear in this image.
Color mapping of corrosion product on A516Gr70 steel surface is shown in Fig.9 that
emphasize on presence of FeS on specimen
surface.

Induced Cracking. CORROSION 2003. San

Diego Ca, NACE International.
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: 347352.
Groysman A, Feldman B, Kaufman A, Balali R
(2011). HYDROGEN DAMAGE AND
PREVENTION IN THE OIL REFINERY.
CORROSION 2011. Houston, Texas, NACE
International.
Hazlewood PE, Singh PM, Hsieh JS (2006).
Corrosion behavior of carbon steels in
sulfide-containing caustic solutions. Ind.
Eng. Chem. Res., 45: 7789-7794.
Nasirpouri F, Alizadeh H, Hosseingholizadeh M
(2011). Failure analysis of a carbon steel
screw under the service in the presence of
hydrogen sulphide. Eng. Fail. Anal., 18:
2316.
Rogante M, Battistella P, Cesari F (2006).
Hydrogen interaction and stress-corrosion in
hydrocarbon storage vessel and pipeline
weldings. Int. J. Hydrogen Energy, 31: 597601.
Smith SN, Brown BN, Sun WN (2011). Corrosion
At Higher H2S Concentrations And
Moderate Temperatures. CORROSION
2011. Houston, Texas, NACE International.
Tung N, Hung P, Tien H, Loi C (2001). Study of
Corrosion Control Effect of H2S Scavengers
in Multiphase Systems.
Venegas V, Caleyo F, Gonzalez J, Baudin T,
Hallen J, Penelle R (2005). EBSD study of
hydrogen-induced cracking in API-5L-X46
pipeline steel. Scripta materialia, 52: 147152.
Wilken G, Martin TG (2003). Hydrogen Induced
Cracking Failure of ASTM A 516 Grade 70
Steel in Near Neutral to High pH Solution:
Part 2 Laboratory Studies. CORROSION
2003. San Diego Ca, NACE International.

4. CONCLUSION
Very thin iron sulfide film was created on the all
sample surface exposure in different concentration
of H2S. By increasing the temperature, hydrogen
concentration increased. It seems that a stable FeS
layer protect surface against more corrosion. The
result show that the hydrogen induced cracking can
take place in H2S containing solution for A516Gr70 steels. Corrosion rates enhance about two
times in H2S concentration (C2), which means FeS
film was very unstable in this concentration.

Acknowledgments
Authors acknowledge the contributions from
Universiti Teknologi Malaysia and Kish University
of Iran that have resulted in this article.
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Dehkordi E, Tavakoli A (2007). The Effect of
Time on the Formation & Growth of Passive
Layer on Carbon Steel A516 Gr. 70 in Sour
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IRON AND STEEL SOCIETY OF IRAN,
4: 28-33.
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

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