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Effect of mercury on corrosion in production

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DOI: 10.1179/147842209X12579401586609

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Effect of mercury on corrosion in production
wells in Gulf of Thailand
T. Pojtanabuntoeng1, C. Saiwan*1, S. Sutthiruangwong2 and D. L. Gallup3
The effect of mercury on the corrosion of materials used for tubing in oil and gas production wells
was studied. Carbon steel (L80) and 13% chromium stainless steel (13Cr) were selected for study
by potentiodynamic polarisation. Simulated produced water, with the composition obtained from
the Gulf of Thailand field, was used as a corrosive solution. Temperature kinetically increased the
corrosion reaction. Chloride ions and carbon dioxide also enhanced the corrosion. Acidity
increased the pitting corrosion of 13Cr and increased the corrosion rate of both 13Cr and L80. A
concentration of 312 ppm of mercury lowered the current density in the passive region and
increased the pitting potential of 13Cr. The corrosion rate of L80 was decreased with small
amount of mercury addition. The 13Cr showed lower uniform corrosion rate than the L80 in all
conditions of the simulated produced water.
Keywords: Corrosion, Mercury, Produced water, Potentiodynamic polarisation

Introduction H2 CO3 ?Hz zHCO{ (1)

In oil and gas production, corrosion is a major cause of
failures. These failures lead to security and environ-
mental problems, a decrease in the production rate and
high repair costs from the leakage of crude oil due to
CO2, fire accidents, water resource contamination and
environmental pollution. All of these incidents cost the
petroleum industry in the USA $1?4bn in 2002.13 This
damage is included in the cost of gas and crude oil. On
the other hand, most of the cost savings for any oil and
gas production facility is in the prevention of failure in
the production equipment. In the Gulf of Thailand, the
amount of CO2 can vary from 18 to 54% mol., whereas
the rest is N2 and hydrocarbons. Fortunately, the
existence of H2S is considered to be trace. The most
common forms of CO2 corrosion are uniform and
pitting. CO2 corrosion products include iron carbonate
(siderite and FeCO3) and iron oxides.
Carbon dioxide reacts with liquid water to form weak
carbonic acid.2,4,5 The corrosion process is controlled by
three cathodic reactions (equations (1)(3)) and one
anodic reaction in equation (4), which is only the
oxidation of iron to ferrous ion in an aerobic condition.
The products of these reactions provide the chemical
environment that promotes the direct formation (equa-
tion (5)) or indirect formation of iron carbonate
(equations (6) and (7)).
1
Petroleum and Petrochemical College, Chulalongkorn University,
Bangkok 10330, Thailand
2
Faculty of Science, King Mongkuts Institute of Technology Ladkrabang,
Bangkok 10520, Thailand
3
Process, Analytical and Catalysis Department, Chevron Energy
Technology Company, Houston, TX, USA
*Corresponding author, email Chintana.Sa@chula.ac.th
3
HCO{ z 2{
3 ?H zCO3 (2)
2Hz z2e{ ?H2 (3)
Fe?Fe2z z2e{ (4)
Fe2z zCO2{
3 ?FeCO3 (5)
Fe2z z2HCO{
3 ?Fe(HCO3 )2 (6)
Fe(HCO3 )2 ?FeCO3 zCO2 zH2 O (7)
An iron scale can form a pseudopassive layer, depend-
ing on its property, the composition and microstructure of
the base alloy, and the properties of the environment.
Pseudopassivity describes a process on a metal that
exhibits a significant decrease in current density over an
extended potential range but which does not occur by
direct oxidation of the metal (such as in passivity).
Processes that develop precipitated films of corrosion
product, for example, iron carbonate films, are considered
to be pseudopassive films (also known as salt films).6,7
The corrosiveness of the environment is a function of
numerous parameters, such as water chemistry, gas/fluid
velocity, CO2 content, temperature4,8 and chloride
content.1,9,10 At low concentration (03%NaCl), the
corrosion rate increases with increasing amount of NaCl
due to enhancement of the conductivity of the solution.
However, with a further increase in the concentration of
NaCl (.3%), the corrosion rate gradually decreases
because the solubility of oxygen is decreased.1,9 Chloride
ion penetrating through the protective film of iron and

2011 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 26 June 2009; accepted 4 November 2009
DOI 10.1179/147842209X12579401586609 Corrosion Engineering, Science and Technology 2011 VOL 46 NO 4 547
Pojtanabuntoeng et al. Effect of mercury on corrosion in production wells in Gulf of Thailand
chromium oxides of stainless steel 304 has also been
reported.10 Divalent cations found in the sea (i.e.
calcium and magnesium) can reduce the corrosion rate
by forming a protective film layer of calcium and/or
magnesium carbonate on the metal surface via calcar-
eous film formation (a form of inhibition) may be
disrupted by dissolution in carbon dioxide. The effect of
CaCl2 in simulated seawater on carbon steel corrosion in
stagnant and flowing conditions of a 46%NaCl solution
saturated with CO2 at 57uC has been reported.11
Mercury exists in reservoirs in many forms, e.g. as
organic mercury and as inorganic mercury. The total
concentration of mercury in the Gulf of Thailand is 3
6 ppm. On a global scale, the implications of the effects
of mercury were not reported until 1973, when a
catastrophic failure of aluminum heat exchangers
occurred at the Skikda liquefied natural gas plant in
Algeria and in the gas gathering system of the Groninger
field in The Nertherlands.12 However, studies about the
effect of dissolved mercury on the corrosion behavior of
metallic materials in a reservoir environment seem to be
very limited in the literature.
A possible mechanism for corrosion caused by the
presence of metallic mercury involves elemental mercury
amalgamating with the surface of a metal (e.g. for al-
uminium). In this case, the protective passive film cannot be
formed and the aluminium corrodes at an exceptionally
high rate. Many metals form amalgams with mercury with
the notable exception of iron. However, where mercury
may be deposited from solution, a local galvanic cell will
operate with the less noble metal (e.g. iron) corroding
preferentially.13
In the presence of CO2 or H2S, the corrosion products
on ferrous alloys are metal carbonates or sulphides,
correspondingly. Although the concentration of mercury
in the natural gas is very low, its effect is cumulative, and
it is likely to gradually increase in concentration on the
metal surface.14 Other mercury species are also present in
natural gas. This mercury(II), is a powerful oxidising
agent [standard potential50?788 V(SHE), compared to
hydrogen], and will act as a cathodic reactant and, as a
consequence, elemental mercury will be deposited with
increased corrosion of the substrate.
The selection of materials used as production tubing
emphasises mechanical properties and corrosion resistance.
Carbon steel is mostly used due to its cost, availability and
strength. However, in some conditions where carbon steel is
not durable enough, stainless steel is more attractive, as it
provides better corrosion resistance.15 Chromium present
in the steel forming a passive chromium oxide layer acts as
a barrier in preventing corrosion when encountering an
aggressive media. Generally, stainless steel is much more
expensive than carbon steel. Instead of the unnecessary use
of stainless steel for the entire design, smart design and
selection of appropriate types of steels for the tubing to
Table 1 Lists of parameters for corrosion study
Experiment Solution
Temperature SPW saturated with CO2
Chloride concentration SPW saturated with CO2
Carbon dioxide partial pressure SPW
Mercury(II) SPW
548 Corrosion Engineering, Science and Technology 2011 VOL
match the environment of production wells could help in
cost minimisation.
In this work, carbon steel (L80) and stainless steel
(13Cr) were used for the study of corrosion in natural
gas production in the Gulf of Thailand. Conditions
corresponding to the gas field were simulated and
factors of temperature, PCO2 , chloride concentration
and mercury concentration were investigated. The
experiments were carried out using the potentiodynamic
polarisation technique.
Experimental
Materials and chemicals
The stainless steel was 13% chromium, AISI 420 type
(13Cr) and the carbon steel type was API 5CT L80
(L80). Produced water was simulated using analytical
grade reagents, sodium chloride (NaCl, 99?0% purity),
sodium bicarbonate (NaHCO3, 99?7% purity), potas-
sium chloride (KCl, 99?8% purity), anhydrous calcium
chloride (CaCl2, 95?0% purity) and magnesium chloride
(MgCl2.6H2O, 99?0% purity). All chemicals were sup-
plied by Labscan Asia. The solution was first deoxyge-
nated by nitrogen purging for 1 h and then saturated
with carbon dioxide. Hydrochloric acid and sodium
hydroxide were used to adjust the pH of the solution.
Ethyl alcohol was used as a cleaning agent for the
electrodes.
Procedure
Simulated produced water (SPW) was prepared based on
the composition provided by Chevron Thailand Explora-
tion and Production Ltd (Table 1). The effect of tempera-
ture was determined in the range of 3060uC in a water
bath, while the simulated produced water was saturated
with CO2. In order to illustrate the effect of carbon dioxide,
nitrogen was used to adjust the carbon dioxide partial
pressure. The effect of chloride was studied by varying the
chloride concentration using sodium chloride in the range
of 0?13?5 wt-%. The initial solution pH of the SPW was
adjusted using hydrochloric acid and sodium hydroxide
solutions before saturation with CO2. The effect of mercury
was studied by adding trace amounts of Hg(II) from 0 to
12 ppm at various temperatures and CO2 pressures, as
summarised in Table 1.
Potentiodynamic polarisation technique
The experiments for this study were carried out using a
conventional three-electrode system connected to an
Autolab PGSTAT20 potentiostat. Platinum was used as
a counter electrode. The reference electrode was a
saturated calomel electrode which was connected to the
system using a Luggin capillary. Therefore, all potentials
reported in this work are based on the potential of a
saturated calomel electrode (SCE). L80 and 13%Cr
coupons or working electrodes were polished with 1200
grit silicon carbide paper and cleaned with ethyl alcohol in
Temperature, uC Remarks
30, 50 and 60
60 [Cl2]50.13.5%
60 PCO2 50, 0.5 and 1.0 atm
30 and 60 [Hg]5012 ppm
PCO2 50, 0.5 and 1.0 atm
46 NO 4
 Pojtanabuntoeng et al. Effect of mercury on corrosion in production wells in Gulf of Thailand

1 Polarisation curves of 13Cr in simulated produced 2 Polarisation curves of L80 in SPW saturated with CO2
water (SPW) saturated with CO2 at 3060uC at 3060uC

an ultrasonic bath, rinsed with deionised water, and dried

with hot air before the experiment. The coupon was held
with a crevice free holder, which provided an exposed area
of 1 cm2 and was prepolarised at 21 V(SCE) before the
start of the potentiodynamic polarisation into the anodic
region. Potentiodynamic polarisation curves were ob-
tained in both cathodic and anodic regions with a scan
rate of 16?7 mV min21. The Tafel extrapolation technique
as a versatile method16 was used to evaluate the corrosion
current density and hence, determine the corrosion rate.

Results and discussion 3 Polarisation curves of 13Cr in SPW containing NaCl

Effect of temperature
The polarisation curves of 13Cr show that the corrosion
potentials were not affected very much by temperature.
The results are summarised in Table 2. Activepassive
behaviour can be observed, as shown in Fig. 1. The
pitting potential decreased from 0?094 to 20?048 V as
the temperature increased from 30 to 60uC. The decrease
in the pitting potential resulted in a smaller passive
region, which indicated that the increase in temperature
led to destabilisation of the passive film on the surface of
the stainless steel and decreased the pitting potential.
For the corrosion current density, on the other hand, the
active corrosion rate of 13Cr was very slightly increased
with temperature.
The polarisation curves of L80 are shown in
Fig. 2, where passive behaviour is not observed. The
corrosion rate increases with increasing temperature.
and saturated with CO2 at 60uC
The corrosion potential, however, remains unchanged
with temperature. Therefore, the increase in the corro-
sion current density due to the temperature was not the
result of the aggressiveness of the solution, but rather
arose from kinetic aspects. The corrosion rate of L80
from the polarisation technique is more affected by
temperature than that of 13Cr.
Effect of chloride
The polarisation curves of 13Cr (Fig. 3) illustrate that
the passive current became noisy as the chloride
concentration increased (due to metastable pitting
events), and subsequently the passive film became more
unstable. An increase in chloride ions in SPW resulted in
a decrease in the pitting potential and reduction in the
size of the passive region (Table 3). At high anodic

Table 2 Corrosion parameters of 13Cr and L80 in SPW saturated with CO2 at different temperatures

Material Temperature, uC Ecorr, V icorr, mA cm22 Epit, V Corrosion rate, g cm22/year

13Cr 30 20.669 1.461023 0.094 1.261022

50 20.683 2.261023 0.020 1.961022
60 20.678 3.361023 20.048 2.861022
L80 30 20.736 9.461023 8.761022
50 20.732 3.961022 3.661021
60 20.735 4.161022 3.861021

Table 3 Corrosion parameters of 13Cr and L80 in SPW saturated with CO2 at 60uC in different chloride concentrations

Material NaCl, % Ecorr, V icorr, mA cm22 Epit, V Corrosion rate, g cm22/year

13Cr 0.1 20.698 2.361023 20.048 2.061022

1.0 20.702 1.961023 20.155 1.661022
3.5 20.697 3.561023 20.414 3.061022
L80 0.1 20.736 8.061022 6.961021
1.0 20.741 5.961022 5.161021
3.5 20.731 4.361022 3.761021

Corrosion Engineering, Science and Technology 2011 VOL 46 NO 4 549

Pojtanabuntoeng et al. Effect of mercury on corrosion in production wells in Gulf of Thailand

4 Polarisation curves of L80 in SPW containing NaCl and

saturated with CO2 at 60uC 5 Polarisation curves of 13Cr in SPW at 60uC with differ-
ent CO2 partial pressures
overvoltage, i.e. above the pitting potential, the metal is
locally attacked by aggressive chloride ions, a behaviour
that is well known.17,18 The corrosion current densities
of all 13Cr samples are y2?561023 mA cm22. The
results suggest that the chloride ions lead to localised
corrosion, whereas uniform corrosion is not greatly
affected by chloride in chromium steel.
It was found that for L80 (Fig. 4), the corrosion
potential and corrosion current density were virtually
unchanged with chloride ion concentration, indicating
that the oxidising power of the solution was not
significantly increased with chloride at the corrosion
potential. However, a higher current density was
observed from a higher concentration of chloride above 6 Polarisation curves of L80 in SPW at 60uC with differ-
the pitting potential. ent CO2 partial pressures

Effect of carbon dioxide partial pressure
Carbon dioxide is the key factor for corrosion in natural
gas production. These experiments were carried out in
SPW at a constant temperature of 60uC with various
partial pressures of CO2: 0, 0?5, and 1 atm. An increase
in corrosion potential was observed in 13Cr from
20?878 to 20?725 to 20?678 V as the partial pressure
of the carbon dioxide was increased from 0 to 0?5 to
1?0 atm, as shown in Fig. 5 and Table 4. Additionally,
the pitting potential in the carbon dioxide saturated
solution was significantly decreased, which confirmed
the effect of carbon dioxide on increasing the possibility
of pitting corrosion on the stainless steel. For L80, the
polarisation curves in Fig. 6 show a large increase in the
cathodic current density. The corrosion potential was
20?873 V in the absence of CO2 and increased to
20?751 and 20?735 V as the carbon dioxide partial
pressure was 0?5 and 1?0 atm respectively. The signifi-
cant increase in corrosion potential may come from the
additional cathodic reaction, i.e. carbonic acid reduction
and hydrogen evolution.
The corrosion rate of 13Cr was slightly affected by the
carbon dioxide partial pressure. The corrosion rate of
13Cr was 1?361022 g cm22/year in the absence of CO2
and increased to 2?061022 and 2?861022 g cm22/year
at PCO2 equal to 0?5 and 1 atm respectively. It can be
clearly seen that the corrosion rate of L80 was much
higher than the corrosion rate of 13Cr. A corrosion rate
of 3?861021 g cm22/year was obtained from the solu-
tion saturated with CO2. Without CO2, the corrosion
rate of L80 is about one order of magnitude lower, as
can be seen in Table 4. The oxide of L80 was able to
react with the dissolved carbon dioxide to produce
ferrous carbonate and a dissolved complex of iron,
FeCO3 2{
2 , which accelerated the dissolution of the iron
element.5
Effect of mercury
Mercury(II) and temperature
The polarisation curves of 13Cr in various concentra-
tions of Hg(II) in SPW are shown in Figs. 7 and 8. There
was no significant difference in the cathodic part. The
anodic polarisation curves show a decrease in the
current density in the passive region with increasing
potential. At extremely low concentrations of Hg(II),
e.g. 3 ppm, the observed passive current density was
lower than that observed from the 6 and 12 ppm curves.
The current densities in the passive region also became
noisy during polarisation. This suggests that mercury, or
Hg(II), influences the passive layer and the pitting

Table 4 Corrosion parameters of 13Cr and L80 in SPW saturated at 60uC with different CO2 partial pressures

Material CO2 partial pressure, atm Ecorr, V icorr, mA cm22 Epit, V Corrosion rate, g cm22/year

13Cr 0 20.878 1.561023 0.118 1.361022

0.5 20.725 2.361023 0.138 2.061022
1 20.678 3.361023 20.049 2.861022
L80 0 20.873 3.461023 3.161022
0.5 20.751 1.161022 9.961022
1 20.735 4.161022 3.861021

550 Corrosion Engineering, Science and Technology 2011 VOL 46 NO 4

 Pojtanabuntoeng et al. Effect of mercury on corrosion in production wells in Gulf of Thailand

7 Polarisation curves of 13Cr in SPW with 012 ppm 9 Polarisation curves of L80 in SPW with 012 ppm Hg(II)
Hg(II) and saturated with of CO2 at 30uC and saturated with CO2 at 30uC

8 Polarisation curves of 13Cr in SPW with 012 ppm 10 Polarisation curves of L80 in SPW with 012 ppm
Hg(II) and saturated with CO2 at 60uC Hg(II) and saturated with CO2 at 60uC

behaviour of 13Cr during anodic polarisation. Since the
standard potentials of Hg(II) is 0?788 V(SHE), it would
be expected to be reduced at all potentials during the
potentiodynamic polarisation experiment. Thus, ele-
mental mercury is expected to be present during both
cathodic and anodic polarisation of the substrate. It was
found that the pitting potentials of 13Cr at the various
Hg(II) concentrations were slightly shifted to a more
noble value and the passive currents were slightly lower.
This may lead to an important role of elemental mercury
during the passivation of 13Cr and suggests that the
passive films with codeposition of mercury are more
resistant. However, for long term corrosion of the metal
substrates in a mercury containing environment, the
corrosion behaviour is expected to be different. In this
case, elemental mercury can be formed and plated on the
surface resulting in a local galvanic effect.13 Hence, since
elemental mercury is more noble than typical carbon
and stainless steels, the site covered by mercury will be
the cathode, while the remainder will be the anode. The
galvanic corrosion promoted in such an environment
will lead to a higher localized corrosion rate.
The corrosion current densities of all curves at 30uC
were nearly the same at 1?361023 mA cm22, as listed in
Table 5; therefore, the uniform corrosion rate of 13Cr is
nearly constant and does not depend on the concentra-
tion of Hg(II) in the range of 012 ppm.
The change of temperature from 30 to 60uC did not
alter much the corrosion behaviour in the anodic part of
13Cr. However, as can be seen in Table 5, the corrosion
rate has doubled as the temperature increased from 30 to
60uC.
For L80, the addition of small amounts of Hg(II) (0
12 ppm) at 30uC (Fig. 9) and 60uC (Fig. 10) resulted in a
slight shift in corrosion potential to a more noble value.
The shift of corrosion potential is probably because of
the stronger oxidising power of the solution, i.e. due to
the presence of Hg(II). The current densities in the
anodic part slightly increased with increasing concentra-
tion of Hg(II). As can be seen in Table 6, the corrosion
current densities from L80 in SPW in the presence of
Hg(II) were lower than that obtained from the SPW.
The corrosion current density or corrosion rate of L80 in
SPW at 60uC was y4?5 times higher than that at 30uC.
Mercury(II) and PCO2
In the presence of 3 ppm Hg(II) at 60uC with varying
partial pressures of CO2, the polarisation curves of 13Cr

Table 5 Corrosion parameters of 13Cr in SPW saturated with CO2 at different Hg(II) concentrations

Temperature, uC [Hg(II)], ppm Ecorr, V icorr, mA cm22 Epit, V Corrosion rate, g cm22/year

30 0 20.669 1.461023 0.094 1.261022

3 20.677 1.361023 0.108 1.161022
6 20.670 1.361023 0.157 1.161022
12 20.672 1.561023 0.133 1.361022
60 0 20.678 3.361023 20.048 2.861022
3 20.715 3.261023 0.079 2.761022
6 20.717 2.561023 0.060 2.161022
12 20.702 3.161023 0.084 2.761022

Corrosion Engineering, Science and Technology 2011 VOL 46 NO 4 551

Pojtanabuntoeng et al. Effect of mercury on corrosion in production wells in Gulf of Thailand

11 Polarisation curves of 13Cr in SPW at 60uC and 12 Polarisation curves of L80 in SPW at 60uC and 3 ppm
3 ppm Hg(II) with varying CO2 partial pressures Hg(II) with varying CO2 partial pressures

(Fig. 11) and the corresponding parameters (Table 7)
indicate that the corrosion current density or corrosion
rate was slightly increased, while the pitting potential of
13Cr was almost constant at between 0?060 and 0?089 V
with partial pressure of CO2 from 0?5 to 1?0 atm. One
point that should be made is that a significant decrease
in current density in the passive region was not
observed, as seen earlier in the absence of CO2.
Figure 12 is the polarisation curves of L80 at 60uC
and 3 ppm Hg(II) with varying CO2 partial pressures.
The corrosion potential of the L80 in the presence of
3 ppm Hg(II) was shifted from 20?810 to 20?740 V as
the CO2 partial pressure was increased from 0 to 1 atm
(Table 7). A higher oxidising power of solution for L80
was obtained in the presence of CO2. The corrosion
current density was also increased in the presence of
CO2.
For the polarisation curve of L80 without CO2,
pseudopassivity was briefly observed from about 20?630
to 20?470 V with a rather high current density of
y2?061022 mA cm22. This effect seems to exist with
the higher partial pressure of CO2, but the occurrence
took place at much higher potential and yield to a much
higher current density. Because of this high current
density, it is, therefore, not a true passivation.
Conclusions
The potentiodynamic polarisation technique was
employed to investigate the corrosion behavior of 13Cr
Table 6 Corrosion parameters of L80 in SPW saturated with CO2 at different Hg(II) concentrations
and L80 in various conditions of SPW, including the
effect of dissolved mercury. The following can be
concluded from this work:
1. The corrosion rate of 13Cr is slightly increased by
the carbon dioxide partial pressure. The pitting potential
is lower in the presence of carbon dioxide.
2. A small amount of Hg(II) lowers the current
density in the passive region and increases the pitting
potential of 13Cr.
3. The corrosion rate of L80 is decreased with the
addition of a small amount of Hg(II).
4. Dissolved CO2 could be an important chemical
species for helping Hg(II) to interact with the passive
layer of the 13Cr.
5. The 13Cr shows a lower uniform corrosion rate
than the L80 in all conditions of simulated produced
water.
Acknowledgements
The authors would like to thank Chevron Thailand
Exploration and Production for the research funds.
Many thanks are extended to the Chevron staff
members who were involved in the research project,
especially at the Process, Analytical and Catalysis
Department, Chevron Energy Technology Company,
Houston, TX, USA, and Mr T. Sasichay and his
colleagues from Chevron Thailand Exploration and
Production for their kind coordination. Also, thank is
extended to Mr R. White for revision of English.

Temperature, uC [Hg(II)], ppm Ecorr, V icorr, mA cm22 Epit, V Corrosion rate, g cm22/year

30 0 20.736 9.461023 8.761022

3 20.712 3.761023 3.461022
6 20.703 4.361023 4.061022
12 20.726 4.961023 4.561022
60 0 20.735 4.161022 3.861021
3 20.740 1.861022 1.761021
6 20.722 1.861022 1.761021
12 20.737 2.261022 2.061021

Table 7 Corrosion parameters of 13Cr and L80 in SPW with varying CO2 partial pressures at 3 ppm Hg(II) and 60uC

Material CO2 partial pressure, atm Ecorr, V icorr, mA cm22 Epit, V Corrosion rate, g cm22/year

13Cr 0 20.766 2.061023 0.060 1.761022

0.5 20.712 2.761023 0.089 2.361022
1 20.715 3.261023 0.079 2.761022
L80 0 20.810 2.361023 2.161022
0.5 20.740 1.861022 1.761021
1 20.740 1.861022 1.761021

552 Corrosion Engineering, Science and Technology 2011 VOL 46 NO 4

 Pojtanabuntoeng et al.
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