Accepted Manuscript

Evaluation of the corrosion resistance of SA-543 and X65 steels in emulsions

containing H2S and CO2 using a novel emulsion flow loop

Muhammad Nauman Zafar, Rihan Rihan, Luai Al-Hadhrami

PII: S0010-938X(15)00087-6
DOI: http://dx.doi.org/10.1016/j.corsci.2015.02.013
Reference: CS 6218

To appear in: Corrosion Science

Received Date: 17 November 2014

Accepted Date: 4 February 2015

Please cite this article as: M.N. Zafar, R. Rihan, L. Al-Hadhrami, Evaluation of the corrosion resistance of SA-
543 and X65 steels in emulsions containing H2S and CO2 using a novel emulsion flow loop, Corrosion Science
(2015), doi: http://dx.doi.org/10.1016/j.corsci.2015.02.013

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pertain.
 Evaluation of the corrosion resistance of SA-543 and X65 steels in
emulsions containing H2S and CO2 using a novel emulsion flow loop
Muhammad Nauman Zafar1, Rihan Rihan2,*, and Luai Al-Hadhrami2
1
Center of Research Excellence in Corrosion
2
Center for Engineering Research - Research Institute
King Fahd University of Petroleum & Minerals,
Dhahran 31261, Saudi Arabia
*
Corresponding Author, e-mail: rihanr@gmail.com
Phone: +966 3 860 2888
Fax: +966 3 860 3996

ABSTRACT
A novel emulsion flow loop was constructed to investigate the corrosion resistance (R P) of
SA-543 and X65 steels in oil-in-water emulsions containing H 2S and CO2. Results show that
RP of SA-543 steel is significantly better than that of X65 steel. The R P, which increases with
increasing oil concentration, velocity, and temperature, is lower in the developing flow region
when compared to that in the fully developed region.

Keywords:
A. Steel
B. Electrochemical calculation
B. Polarization
B. Weight loss
C. Acid corrosion

1. Introduction
An emulsion is a mixture of two or more liquids which are immiscible, with one or more
of the liquids remaining suspended as a dispersion of small droplets in another liquid.
Emulsions are categorized into oil-in-water emulsions and water-in-oil emulsions depending
on the nature of the dispersion phase and the continuous phase. Emulsions, which are
encountered at many stages in the petrochemical and process industries [1], facilitate crude
oil extraction. Emulsions are formed when water is injected into oil wells to reduce the drag
and pressure loss, thus easing the extraction of viscous crude oil [ 2]. However, as the
properties of emulsions are totally different from their constituent fluids, and the corrosion
rate in emulsions is higher than that in individual oil and water phases [3], the formation of
emulsions can be detrimental to equipment and pipelines. An emulsion is normally more
viscous than either oil or water, and they are often formed in the risers, during transportation
of oil or in pumps and valves.
The effect of the presence of oil was studied by Zhang and Cheng [46]. They found that
the presence of 10 % oil in the solution decreased the anodic current density and increased
the cathodic current density in comparison with oil free solution due to the formation of an
oily layer on the steel surface.
Corrosion of pipelines also depends on the type of well (sour or sweet well), temperature,
CO2 and H2S content, flow rate, oil or water wetting nature, and the composition and surface
condition of the steel [4]. Sour and sweet wells contain H2S and CO2 gases, respectively,

1
which form acidic media in aqueous solutions and provide a favourable environment for iron
dissolution. Although the removal of sulphide from crude oil makes the cost of extraction
higher, the higher demand for oil and thus the higher prices, have made the process viable.
Corrosion in sour environments is normally initiated by the formation of iron sulphide films
[5]. Iron sulphide scales are formed in the pipelines associated with sour wells and their
formation is mostly temperature dependant, with protective and adherent films being formed
at higher temperatures (>80 oC) [6,7]. Hydrogen sulphide, which forms iron sulphide with the
generation of hydrogen gas, is the main cause of hydrogen embrittlement [ 5,8,9]. The
corrosion behavior of carbon steel in the presence of CO 2 [10-12] and H2S [12,13] has been
studied in detail.
Carbon dioxide present in sweet wells forms a weak carbonic acid (H2CO3) solution in
aqueous media. CO2 is also used to lower the viscosity of oil to ease the extraction process
and increase the efficiency of a well [4,14,15,16], which is one of the techniques used in
“enhanced oil recovery”. Carbon dioxide corrosion typically forms iron carbonate (FeCO3)
with the evolution of H2 [17]. Corrosion is substantially reduced when FeCO3 is precipitated
on the steel surface due to the formation of a dense and protective film, which acts as a
diffusion barrier against corrosive species reaching the metal surface [ 4,18]. Many studies
have been conducted on CO2 corrosion, but none of them has specifically studied the effect of
emulsions on corrosion.
As H2S is a toxic flammable gas, handling of which requires special safety measures, non-
toxic sodium thiosulphate (Na2S2O3) was used as a substitute in this study. This novel
approach was first proposed by Tsujikawa et al. [19], in which they used Na2S2O3 for a study
on the stress corrosion cracking of low alloy steels and found that the results are in good
agreement with those for solutions containing H2S. Thiosulphate (S2O3-2) being a meta stable
anion, reduces to form H2S gas at the metal surface (Eqs. 1 and 2), and the reaction is
spontaneous at the open circuit potential of steel [5,20].

S2O3-2 + 6H+ + 4e- = 2S + 3H2O (1)

2S + 4H + 4e = 2H2S
+ -
(2)
The exact disproportion reaction of thiosulphate is still not fully understood, but it is
believed that the reduction of thiosulphate anion produces elemental sulphur, this elemental
sulphur can be in physical contact with the steel through a direct deposition at the steel
surface, then reacts with protons to form H2S as shown in Eqs. 1 and 2 [4,5,20,21]. The
generation of H2S is not solely dependent upon kinetics of thiosulphate to H 2S, but also on
other variables like N2 flow rate and hydrodynamics conditions [20]. Thus, the formation of
FeS on the surface is due to elemental sulphur and H 2S. Mackinawite (FeS) is initially formed
on the surface because its formation is faster than any other FeS species [ 4,22-24]. This layer
is loose, less adherent, and rich in defects, and contributes to good electron conduction. This
surface sulphide film, which sometimes inhibits anodic dissolution [ 4,5,25], is pH dependent.
An increase in pH reduces the solubility of sulphide and the maximum sulphide precipitation
occurs at pH 4 [5]. However, the amount of Mackinawite generally increases with time due to
its high stability [5].
In recent studies [20,26], it was found that the rate of generation of H2S is a maximum for
0.01 M Na2S2O3. Increasing the concentration of S2O3 reduced the rate of generation of H2S
due to the formation of a thick sulphide film. It was also found that the sulphide film can act
as a catalyst for the cathodic reactions [ 5]. The film growth rate is also higher in thiosulphate
solutions when compared with H2S containing solutions. Although corrosion due to CO 2 and
Na2S2O3 has been studied individually, their combined effects have not been investigated yet.

2
 In recent years, the low chromium (Cr) containing steels have been used as candidate
pipelines in CO2/H2S environment. The presence of Cr in steels reduces the corrosion rate in
CO2/H2S environment. The corrosion behavior of this kind of low Cr alloyed steels has also
been widely studied in aqueous solutions. It is well established that the presence of a small
quantities of Cr (0.5 - 3 wt %) can improve the corrosion resistance of low alloy steels by
encouraging the formation of a stable protective Cr oxide film [29-34].
With the ever increasing demand for oil and gas, the industry requires new high strength
materials for equipment. SA-543 steel, which is a high strength quenched and tempered steel,
is increasingly used for the fabrication of reactors in major industrial petrochemical plants
now. Introduction of SA-543 steel has allowed the fabrication of thin walled pressure vessels,
which are of a higher strength than those constructed with ordinary carbon steel. With its
increasing use, it is necessary to investigate the corrosion behaviour of reactors made of SA-
543 steel in H2S/CO2 environments to ensure their safety and reliability.
In this study, H2S was generated using Na2S2O3 to investigate the corrosion resistance of
X65 and SA-543 steels in emulsions formed in the presence of H2S and CO2. The SA-543
steel which showed better corrosion resistance after the initial studies was subjected to further
tests at a range of oil concentrations, flow rates, and temperatures. To the best of our
knowledge, the corrosion behavior of X65 and SA-543 steels has not been investigated in
emulsions formed in the presence of H2S and CO2, and a novel emulsion flow loop was used
for the first time to study this aspect. Also, the corrosion behavior of X65 and SA-543 steels
in H2S generated from Na2S2O3 has not been studied previously. Therefore, this is a
pioneering study to gain a better understanding of the performance of SA-543 steel to
determine whether it is suitable for the fabrication of pipes for transporting oil and gas.

2. Experimental procedure

2.1. Experimental setup

A schematic diagram of the novel emulsion flow loop that was designed and fabricated for
this study are shown in Fig. 1. The emulsion flow loop is made of Hastelloy C-276, and its
main components are the mixing tank, an autoclave, test sections, a transparent pipe, and
Hastelloy C-276 pumps. Two pumps were installed on the flow loop in order to achieve
higher flow rates, which were monitored using magnetic flow meters. The flow loop can be
operated up to 20 bar and 180 oC, and the heaters are placed on the outlet wall of the
autoclave and the mixing tank. Special spiral mixers were inserted before the entrance to each
test section to facilitate the formation of a uniform oil-in-water emulsion.
The middle test section of the three test sections of the flow loop is made of both 25.4 and
12.7 mm diameter pipes. The two outer test sections are made of 38.1 and 50.8 mm diameter
pipes as shown in Fig. 1, and the remaining piping in the flow loop is of 25.4 mm diameter.
The 38.1 and 50.8 mm test sections are 1.2 m long with an option to position electrodes at the
inlet, midway, and at the exit as shown in Fig. 1. Electrodes can be similarly positioned in the
25.4 and 12.7 mm test sections, which are 0.8 m and 0.4 m long, respectively. The middle test
section can be used to study the convergence effect on the corrosion behaviour of an
emulsion and the corrosion kinetics at high flow velocities (> 6 m/s). The strategic placement
of electrodes along the test section allows the study of the corrosion behaviour in the
developing and developed flow environments. A transparent pipe was installed to follow the
flow pattern, and to determine that a uniform emulsion is formed. However, transparent
piping cannot be used at high pressures. The electrodes are of a cylindrical shape with a
curved front face.

3
 The emulsion was produced by adding 3 L of oil and 7 L of 0.01 M Na2S2O3 solution to
the mixing tank, and using a mixer to form the emulsion, which was transferred to the
autoclave using pump 1 (Fig. 1). After all of the emulsion is pumped and the mixing tank is
empty, the mixing tank valve was closed and the emulsion was allowed to flow through a
small primary loop comprising of spiral mixers. The pumps suck the emulsion from the
autoclave through the spiral mixers, and deliver it back into the autoclave. The purpose of
passing the emulsion through the primary loop is to achieve the desired temperature before
introducing the emulsion into the test sections. Meanwhile, the emulsion in the autoclave was
de-aerated by purging with high purity N2, which is important to mimic the rig conditions and
to avoid the oxidation of sulphide to sulphur [5,26]. After purging with N2, CO2 was
introduced to adjust the pH to 5±0.2, which increases during the experiment, typically after
24 hours, with the pressure also increasing upto 0.05 bar. This slight overpressure prevents
the oxygen ingress. Increase of the pressure is due to the generation of H2S and H2 inside the
closed system, which was also reported by Kappes [5].
When the desired temperature was achieved, the middle test section valve was opened and
the emulsion was allowed to flow into the main loop (Fig. 1), at which time the
electrochemical measurements were commenced, with the pump speed adjusted to maintain a
flow rate of 1±0.01 m/s. The emulsion, which has a milky appearance, was continuously
monitored through the transparent pipe. Duration of each experiment is 26 hours, and once
the experiment was complete the pumps were switched off and the solution was allowed to
move back to the autoclave. Before the drainage valve was opened to empty the autoclave the
H2S exhaust system was switched on to remove gases present inside the system. Prior to the
commencement of each experiment a 316 stainless steel rod as the counter electrode and a
Ag/AgCl reference electrode, were positioned.

2.2. Test Material

Cylindrical specimens of the two steel grades (X65 and SA-543) with a diameter of 10 mm
and length of 100 mm were tested. The end of each specimen exposed to the test solution and
acting as the working electrode, was curved to match the curvature of pipe to ensure that
there were no perturbations in the flow due to protruding electrodes, as shown in Fig. 2. For
each working electrode there was a counter electrode of the same size and geometry, placed
diametrically opposite to the working electrodes in order to ensure a symmetrical current
distribution during electrochemical polarization measurements. The working and counter
electrodes were enclosed in Teflon sleeves to avoid contact with the body of the test section
as illustrated in Fig. 2.
The exposed area of the working electrode of the 25.4 mm diameter test section is 1.028
cm2. Surface of the electrodes was ground using 600 grit silicon carbide paper, and the
chemical composition of the as-received alloys is given in Table 1.
The microstructure of the two metals, etched with 2% Nital (2 mL nitric acid + 98 mL
ethyl alcohol) then washed with ethanol and dried, is shown in Fig. 3. The images of the
microstructure were taken using MEIJI Metallurgical Microscope, Model MX7100, Japan.
The microstructure of SA-543 steel is tempered martensite with probably some bainite. The
microstructure of X65 steel is pearlite (dark) in a ferritic matrix (bright).

2.3. Corrosion measurements

All electrochemical measurements were performed using an AUTOLAB potentiostat

128N, and an AUTOLAB multiplexer was used to scan the two electrodes in each
experiment. Two multiplexer channels were used, with one connected to Electrode (A) (inlet

4
of 25.4 mm diameter pipe) and the other connected to Electrode (B) (outlet of 25.4 mm
diameter pipe), and the remaining openings for positioning electrodes were closed. Each
experiment lasted about 26 hours, and linear polarisation resistance (LPR) was determined
every 30 minutes during the initial 24 hours. The measurement program first measures the
open circuit potential of Electrode (A) for 120 seconds, and then measures its LPR. This
procedure was repeated after 5 seconds, for Electrode (B) and the entire program was
repeated every 30 minutes. The potential was swept from -15 mV to +15 mV against the open
circuit potential (OCP) at a scan rate of 0.167 mV/s.
After conducting the above experiment for 24 hours, potentiodynamic polarisation was
performed from -250 mV to +250 mV with reference to the OCP at a scan rate of 0.167
mV/s. The potentiodynamic polarisation experiments lasted almost one hour for each
electrode. The corrosion rate was calculated using Stern and Geary equation [35-38].

2.4. Solutions

Afresh solution of 0.01 M Na2S2O3 was prepared by dissolving 17.36 g of Na2S2O3 in 7L

of distilled water at the beginning of each experiment. The chemical and physical properties
of Exxsol D80 oil, which was used along with Na 2S2O3 to form the oil-in-water emulsions,
are shown in Table 2. The oxygen level was measured using the modified Winkler Method to
be less than 0.1 ppm. The initial experiments were performed to test X65 and SA-543 steel
grades in an emulsion formed by 30% oil and 70% 0.01 M Na 2S2O3 solution, with and
without CO2. A solution of 0.01 M Na2S2O3 was used due to the higher rate of H 2S generation
at this concentration. The experiments were conducted at a flow velocity of 1 m/s, 25 oC, and
a pH 5 (for tests conducted in the presence of CO2).

3. Results and discussions

3.1. Effect of carbon dioxide

Initially, the SA-543 and X65 steels were tested in an emulsion containing 30% oil and
70% 0.01 M Na2S2O3 solution at a pH of about 7 to 7.2. As shown in Fig. 4, the more
positive corrosion potential (Ecorr) of SA-543 steel indicates that it is more corrosion resistant
than X65 steel. The high corrosion resistance can be attributed to the higher Cr, Ni, and Mo
content of SA-543 steel (Table 1), which reduces the corrosion rate. Higher chromium steels
provide good corrosion resistance in CO2 environments [27,28]. Low Cr steels are believed to
form protective corrosion products which improves CO2 corrosion resistance [28]. Also, the
distinct microstructural phases in X65 steel lead to the separation of anodic and cathodic sites
that directly affects the rate of metal dissolution [39]. The anodic (βa) and cathodic (βc) Tafel
slopes of the SA-543 and X65 steels are shown in Table 4. The corrosion rate at the inlet
electrode (Electrode (A)) is higher than that at the exit electrode (Electrode (B)), and this
trend is observed in all experiments. As indicated by the potentiodynamic polarisation curves,
the corrosion potential at Electrode (B) is slightly more negative than that at Electrode (A),
except for the X65 steel in Na2S2O3 (Fig. 4b). At the inlet, the flow is developing and some
perturbations and turbulence are present as the flow passes the inlet flange. These
perturbations affect the formation of a protective surface film. Secondly, just before the
entrance to the 25.4 mm test section there are spiral mixers for emulsion formation, which
render the flow spiral and turbulent at the entrance to the test section. This is the reason for
the higher corrosion rate at the inlet electrode when compared to that at the exit electrode,
where the flow is fully developed.

5
 In the experiments conducted at pH 5±0.1 with the introduction of CO2, the polarisation
curves shift in the noble direction and the Ecorr becomes more positive. While the SA-543
steel shows a better corrosion resistance than X65 steel in the presence of CO2, the corrosion
rate is higher at the inlet electrode when compared to that at the outlet electrode, similar to
the experiments conducted without CO2. Under aerated conditions, the only reduction
reactions taking place involve thiosulphate and carbonate/bicarbonate anion reduction, while
carbonate reduction dominates at pH 5 [40].
As depicted in Fig. 5, the polarisation resistance (RP) value for both steels increases with
time in presence of CO2. However, SA-543 steel has a higher RP than X65 steel, and in
Na2S2O3 the RP is constant. The reduction of thiosulphate anion produces elemental sulphur
and H2S, and the reaction of H 2S with steel forms a layer of iron sulphide (FeS) [ 9,41]. The
sulphide film formed initially is Mackinawite, which is a less adherent, defect rich thin film
and it has been identified in all the H2S and thiosulphate solutions [23,25,42,43]. The film
grows with time, which inhibits the movement of ions and suppresses the anodic dissolution.
The sulphide films provide a good base for the reduction reaction [5,44], and the reduction of
CO2 forms an iron carbonate (FeCO3) precipitate on the steel surface. FeS precipitates much
easier than FeCO3, and both iron carbonate and Mackinawite are formed at low H 2S
concentration and high Fe+2 concentrations [4]. Iron scales formed at later stages of
experiment are more compact at the base layer, thus behaving as a barrier for the iron
dissolution [45]. Iron carbonate along with iron sulphide reduces the iron dissolution to a
large extent. The RP at the outlet electrode is higher than that at the inlet electrode, and the
fluctuations of RP at the start of the experiment can be attributed to the formation and
removal of a sulphide film.
Corrosion potential (Ecorr) plotted as a function of time for both steels with and without
CO2, as shown in Fig. 6, indicates that Ecorr shifts in the noble direction with time. While E corr
of SA-543 steel is more noble than that of X65 steel, the presence of CO 2 also shifts the Ecorr
to more noble values. The reason for the active E corr of Electrode (B) when compared to
Electrode (A) was explained earlier.
Fig. 7 depicts the corrosion rates of both steels, which shows that the SA-543 steel is a
more corrosion resistant material when compared to the X65 steel. The corrosion rate of SA-
543 is lower both in the presence and absence of CO 2, and the corrosion rate at the inlet
electrode is higher when compared to that at the outlet electrode. The results show that SA-
543 steel has better corrosion resistance than X65 steel. Thus, SA-543 steel was further
investigated under varying oil percentage, flow rate, and temperature, at conditions listed in
Table 3, to determine its reliability for the potential use in industrial applications.

3.2. Effect of the amount of oil

The corrosion behaviour of SA-543 steel in emulsions formed by 10, 20, and 30% of oil
and the 0.01 M Na2S2O3 solution was investigated at 25±1 oC, a flow velocity of 1 m/s, and a
pH of 5. Polarisation curves show that the E corr becomes more positive as the oil percentage is
increased (Fig. 8), thereby decreasing the conductivity of the emulsion. As observed in the
previous section, corrosion at the inlet electrode is higher than that at the exit electrode.
As shown in Fig. 9 depicting the variation of RP of SA-543 steel with time at the three oil
percentages, RP increases with increasing oil percentage. The RP at the inlet electrode (A) is
lower than that at the outlet electrode (B), and the observed fluctuations of R P with time may
be attributed to the formation of an oily layer on the steel surface which inhibits steel
dissolution [20,22]. The presence of the oily layer adsorbed on the surface increases the
activation energy of the reaction, thus reducing corrosion [46].

6
 The variation of Ecorr of SA-543 steel with time at the three oil percentages plotted in Fig.
10 shows that Ecorr becomes more noble with time, which suggests that the corrosion rate
decreases with time.
The measured corrosion rates, depicted in Fig. 11, support this conclusion. The difference
between the corrosion rates in emulsions containing 10% and 20% oil is not significant
because the properties of the two emulsions are similar [47].

3.3. Effect of flow velocity

The polarisation curves at different flow velocities (Fig. 12) show that the Ecorr shifts in the
noble direction with increasing velocity. As Mackinawite is a loose film, it will be easily
detached at higher velocities, resulting in the formation of higher sulphide phases which are
compact, adherent, and stable. These higher sulphide phases are responsible for the increase
of Ecorr and their compactness hinders the dissolution of iron into the emulsion, which results
in a decrease of the corrosion current [25].
The Ecorr at the inlet electrode (A) is slightly more positive than that at the exit electrode
(B). The increase of the flow rate results in an increase in the reduction reaction at the steel
surface, which results in the formation of a sulphide film at higher flow rates [ 46,48]. The
thick sulphide film is compact, adherent, and stable, which hinder the dissolution of iron into
the emulsion [25]. Pipes that are subjected to higher fluid flow rates normally have
significantly more scale [49]. The protective iron carbonate layer cannot be removed by
mechanical forces exerted by the flow alone [18].
Fig. 13 shows that RP increases with time, with values being higher at higher flow rates
and at the exit electrode for all flow rates. The RP for 1.5 m/s and 1 m/s is almost the same for
the first 10 hours, beyond which the formation of a thick sulphide film increases RP at higher
flow rates.
The variation of Ecorr with time, shown in Fig. 14, indicates that Ecorr at 1.5 m/s is more
noble than that at 1 m/s and 0.5 m/s and there is a significant difference between them, with
Ecorr becoming more active as the flow rate is decreased. The Ecorr becomes more noble with
time for all flow rates, stressing that corrosion is being inhibited by the formation of a
protective surface film. The corrosion rate at 1.5 m/s is almost double that at 0.5 m/s (Fig.
15).

3.4. Effect of temperature

SA-543 steel was tested at 25 and 50 oC at pH 5 and a flow velocity of 1 m/s in an

emulsion containing 30% of oil. In general, the corrosion rate increases with increasing
temperature, as the temperature affects the kinetic parameters of the reaction [ 50]. At higher
temperatures, the Ecorr moves in the noble direction and there is a significant difference
between Ecorr at 25 and 50 oC (Fig. 16). It is noteworthy that increasing temperature results in
moving Ecorr in the noble direction as shown in Fig. 16. The increase of temperature generally
enhances various interfacial reactions, which results in increasing the corrosion of steel, while
scale formation due to corrosion inhibiting it [46]. Also, the decrease in the corrosion of the
steel can be related to the formation of sulphide films, which are known to transform to very
strong pyrite films at high temperatures [48] and significantly slow down the corrosion rate
and augment the Ecorr.
Fig. 17 shows that RP at 50 oC is initially less than that at 25 oC, suggesting that the
corrosion increases with temperature, but an increase in RP at latter stages suggests that a firm
film has been formed on the surface. The protective film formed takes some time to become

7
firm and inhibits corrosion at the latter stages of the experiment. The increase in temperature
enhances the kinetics of the reaction and various other interfacial reactions. The reduction
reaction will occur at a higher rate, thus forming a stable sulphide film. At higher
temperatures pyrite (a firm iron sulphide film) is normally formed [23,48]. It is adherent and
strong and inhibits iron dissolution significantly, with the precipitation of iron carbonate also
increasing significantly with temperature [4]. A study by Munoz et al. [51] indicates that the
corrosion rate increased at lower temperatures as a result of the continued formation of Fe2+
ions. But on the other hand, the increase in temperature also leads to an increase in the anodic
and cathodic reactions, which is the reason for the absence of a significant difference in RP
between these two temperatures.
The variation of Ecorr with time shown in Fig. 18 indicates that Ecorr at higher temperature
(50 oC) is more active than that at the lower temperature (25 oC) at the beginning,
corroborating the fast kinetics at higher temperature. But there is a variation up to 7 hours,
after which Ecorr becomes almost constant, gradually moving towards the positive side. This
trend emphasizes that the formation of a stable, adherent protective film takes time to
stabilize, but once the film is stable it enhances the corrosion inhibition significantly. The
previously determined trend was observed for the values at the inlet and outlet electrodes,
with Ecorr more active for the outlet electrode which has a higher RP.
Fig. 19 shows that the corrosion rate is higher at lower temperatures, which is expected
from the results described above.

4. Conclusions

1. SA-543 steel has a lower corrosion rate than X65 steel, which can be attributed to the
higher Cr, Ni, and Mo content of SA-543 steel.
2. The addition of CO2 to the Na2S2O3 solution decreases the corrosion rate of SA-543
and X65 steels due to the formation of a more stable and firm iron carbonate film.
3. The corrosion rate at the inlet electrode (A) is higher than that at the exit electrode (B)
as the flow at the inlet electrode was developing and had some perturbations and
turbulence as the flow passed the inlet flange. These perturbations affect the
formation of a protective surface film.
4. The corrosion rate decreases with increasing oil concentration due to the inertness of
oil and the formation of an oily layer on the steel surface, which inhibits steel
dissolution.
5. The corrosion rate decreases with the increasing flow rate due to the removal of the
loose Mackinawite film leading to the formation of higher sulphide phases which are
compact, adherent, and stable.
6. The corrosion rate decreases with increasing temperature, which is due to the
formation of sulphide films.

Acknowledgement

The authors would like to acknowledge the support provided by the King Abdulaziz City
for Science and Technology (KACST) through the King Fahd University of Petroleum and
Minerals (KFUPM) for funding this work through project no: DRP-3-14. The authors would
like to acknowledge Dr. Chandana Senaratne at the Research Institute-KFUPM for editing
the manuscript.

8
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11
Figures

Fig. 1. A schematic diagram of the emulsion flow loop.

12
Fig. 2. A detailed drawing showing the holder of the working and counter electrodes.

13
Fig. 3. The microstructure of SA-543 steel (top) and X65 steel (bottom).

14
Fig. 4. Potentiodynamic polarization curves of SA-543 (a) and X65 (b) steels in an emulsion
formed by 0.01 M Na2S2O3 solution and 30% oil, with and without CO2, at 1 m/s and 25 oC.

15
Fig. 5. Variation of RP of SA-543 (a) and X65 (b) steels with time in an emulsion formed by
0.01 M Na2S2O3 solution and 30% oil, with and without CO2, at 1 m/s and 25 oC.

16
Fig. 6. Variation of Ecorr of SA-543 (a) and X65 (b) steels with time in an emulsion formed
by 0.01 M Na2S2O3 solution and 30% oil, with and without CO2, at 1 m/s and 25 oC.

17
Fig. 7. Corrosion rate of SA-543 and X65 steels in an emulsion formed by 0.01 M Na2S2O3
solution and 30% oil, with and without CO2, at 25 oC and 1 m/s.

18
Fig. 8. Potentiodynamic polarization curves of SA-543 steel in emulsions formed by 0.01 M
Na2S2O3 and varying oil percentages with CO2 at 25 oC and 1 m/s.

19
Fig. 9. Variation of RP of SA-543 steel with time in emulsions formed by 0.01 M Na2S2O3
and varying oil percentages with CO2, at 25 oC and 1 m/s.

20
Fig. 10. Variation of Ecorr of SA-543 steel with time in emulsions formed by 0.01 M Na2S2O3
and varying oil percentages with CO2, at 25 oC and 1 m/s.

21
Fig. 11. Corrosion rate of SA-543 steel in emulsions formed by 0.01 M Na2S2O3 and varying
oil percentages with CO2, at 25 oC and 1 m/s.

22
Fig. 12. Potentiodynamic polarization curves of SA-543 steel in an emulsion formed by 0.01
M Na2S2O3 and 30% oil with CO2, at 25 oC and varying flow rates.

23
Fig. 13. Variation of RP of SA-543 steel with time in an emulsion formed by 0.01 M Na2S2O3
and 30% oil with CO2, at 25 oC and varying flow rates.

24
Fig. 14. Variation of Ecorr of SA-543 steel with time in an emulsion formed by 0.01 M
Na2S2O3 and 30% oil with CO2, at 25 oC and varying flow rates.

25
Fig. 15. Corrosion rate of SA-543 steel in an emulsion formed by 0.01 M Na2S2O3 and 30%
oil with CO2 at varying flow rates.

26
Fig. 16. The potentiodynamic polarization curves of SA-543 steel in an emulsion formed by
0.01 M Na2S2O3 and 30% oil with CO2, at 1 m/s and the two temperatures.

27
Fig. 17. Variation of RP of SA-543 steel with time in an emulsion formed by 0.01 M Na2S2O3
and 30% oil with CO2, at 1 m/s and the two temperatures.

28
Fig. 18. Variation of Ecorr of SA-543 steel with time in an emulsion formed by 0.01 M
Na2S2O3 and 30% oil with CO2, at 1 m/s and the two temperatures.

29
Fig. 19. Corrosion rate of SA-543 steel in an emulsion formed by 0.01 M Na2S2O3 and 30%
oil with CO2 at 1 m/s and at the two temperatures.

30
Tables

Table 1
Chemical composition of SA-543 and X65 steels.
Steel C P Mn Si S Cu Ni Cr Mo Fe
SA-543 0.11 0.003 0.35 0.25 0.001 0.01 3.27 1.66 0.58 Balance
X65 0.091 0.0075 1.31 0.249 0.0044 0.0274 0.0177 0.0117 Trace Balance

31
Table 2
Chemical and physical properties of Exxsol D80
oil. Appearance Transparent
Initial Boiling Point 237 oC
Flash Point 82 oC
Density (15.6 oC) 0.795 g/ml
Kinematic Viscosity (25 oC) 2.18 mm2/s
Aromatic Content 0.2 wt %

32
Table 3
Experimental conditions used for testing SA-543 steel.
Variable Parameter Value of Parameter Fixed Parameters
10
Oil concentration 1 m/s
20
(vol %) 25 oC
30
0.5
Velocity 30 % Oil
(m/s) 1.0
25 oC
1.5
Temperature 25 30 % Oil
( C)
o
50 1 m/s

33
Table 4
The anodic (βa) and cathodic (βc) Tafel slopes of the SA-543 and X65 steels
(the values of Tafel slopes are in mV/Decade).
Variable Value of
Parameter Electrode (A) Electrode (B)
Parameter Material βa βc βa βc
SA-543 89 -114 90 -161
Na2S2O3 X65 117 -158 129 -182
Solution
Na2S2O3 + SA-543 123 -144 94 -145
CO2 X65 108 -237 109 -182

Oil 30 % SA-543 123 -144 94 -145

concentration 20 % SA-543 110 -163 87 -147
10 % SA-543 113 -129 111 -126
Velocity 0.5 m/s SA-543 124 -214 103 -159
1 m/s SA-543 123 -144 94 -145
1.5 m/s SA-543 96 -146 97 -96
Temperature 25 oC SA-543 123 -144 94 -145
50 oC SA-543 119 -109 110 -124

34
Highlights.

 The corrosion resistance (RP) of SA-543 and X65 steels was investigated.

 A novel emulsion flow loop was designed and constructed to perform the
experiments.

 The RP of SA-543 steel is better than X65 steel in emulsion containing H2S and CO2.

 The RP at the developing flow region was less than at the fully developed region.

 The RP increased with increasing oil concentration, velocity, and temperature.

35