Journal of Natural Gas Science and Engineering 86 (2021) 103718

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Journal of Natural Gas Science and Engineering

journal homepage: http://www.elsevier.com/locate/jngse

Effect of temperature on the electrochemical pitting corrosion behavior of

316L stainless steel in chloride-containing MDEA solution
Xianglong Hou a, Quanyou Ren a, Youkun Yang a, Xianlong Cao a, *, Jie Hu a, Cheng Zhang b, **,
Hongda Deng a, Daliang Yu a, Kejian Li a, Wei Lan a
a
School of Metallurgy and Materials Engineering, Chongqing University of Science and Technology, Chongqing, 401331, China
b
Research Institute of Production Engineering, Sinopec Zhongyuan Oil Field, Puyang, 457001, China

A R T I C L E I N F O A B S T R A C T

Keywords: Here, the effect of temperature on the electrochemical corrosion of 316L stainless steel (SS) in methyl dieth­
Stainless steel anolamine (MDEA) solution with/without 1.0 wt% NaCl in the presence/absence of CO2 was investigated using
MDEA solution potentiostatic polarization, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS).
Chloride ion
The electrochemical measurements showed that although the MDEA solution was highly basic, both chloride and
Pitting corrosion
temperature played greater roles in the pitting corrosion of 316L SS, similar to plain NaCl solution. The critical
Electrochemical technique
Critical pitting temperature pitting temperature (CPT) of 316L SS in MDEA solution with 1.0 wt% NaCl decreased from 67.2 ◦ C to 59.6 ◦ C,
and the breakdown potential underwent a negative shift of approximately 400 mV, and the EIS Bode impedance
decreased. Furthermore, the breakdown potential shifted negatively with increasing temperature when the
temperature was lower than CPT in the MDEA solution containing Cl− ; however, the breakdown potential
decreased slowly, and its temperature dependence was unclear when the temperature was higher than the CPT.
In addition, the passive film resistance of 316L SS in all MDEA solutions decreased as the temperature increased.
Particularly for the MDEA solution containing Cl− , the passive film resistance decreased by one order of
magnitude when the temperature increased from 50 ◦ C to 60 ◦ C. Although the presence of CO2 in the MDEA
solution decreased the passive film resistance, it seemed to reduce the individual corrosion contribution of Cl− .
The pitting corrosion process of 316L SS in MDEA solution containing chloride ions was discussed by combining
these results with classical pitting mechanisms of stainless steel.

Credit author statement
Xianglong Hou: Investigation, Data curation, Writing – original draft,
Formal analysis. Quanyou Ren: Investigation, Formal analysis. Youkun
Yang: Investigation, Funding acquisition. Xianlong Cao: Conceptuali­
zation, Methodology, Supervision, Investigation, Project administration,
Funding acquisition, Writing – review & editing. Jie Hu: Investigation,
Validation. Cheng Zhang: Supervision, Writing – review & editing.
Hongda Deng: Investigation, Visualization.Daliang Yu: Investigation,
Resources. Kejian Li: Investigation, Formal analysis. Wei Lan: Funding
acquisition, Project administration.
1. Introduction
With the development of petroleum and natural gas industries, many
oil and gas fields with high H2S and CO2 pressures have been discovered
(Hao et al., 2008; Ma et al., 2017; Zeng et al., 2014). These highly acidic
natural gas components can be extremely corrosive and are toxic when
inhaled; therefore, they are eliminated through a process called natural
gas purification. A purification process using alkanolamine-based solu­
tions is widely used because it is the most economical and effective
strategy to remove CO2, H2S, and other acidic components in a cyclic
adsorption/regeneration process. The alkanolamine system plays a
critical role in the purification process because it circulates to various
natural gas purification units (Kittel et al., 2012; Verma N., Verma A.,
2009). Among alkanolamine solutions, methyl diethanolamine (MDEA),
a tertiary amine, is the most promising because of its lower alkalinity
than primary or secondary amines, as well as its ability to react with
acidic compounds (Jaafari et al., 2018; Pal et al., 2014; Sadeek et al.,
2018). MDEA can increase the capacity of existing units, decrease the

* Corresponding author.
** Corresponding author.
E-mail addresses: xianlong@cqust.edu.cn (X. Cao), flyupwind@163.com (C. Zhang).

https://doi.org/10.1016/j.jngse.2020.103718
Received 4 June 2020; Received in revised form 1 October 2020; Accepted 12 November 2020
Available online 21 November 2020
1875-5100/© 2020 Elsevier B.V. All rights reserved.
X. Hou et al.
capital cost of new units, and lower the energy consumption required for
purification. Therefore, gas purification using MDEA seems to be far
more stable and does not require frequent plant shutdowns and main­
tenance over longer periods (Banat et al., 2014; Pal et al., 2014; Pal
et al., 2015). In addition, to prevent the corrosion of pipelines and
equipment of MDEA desulfurizing amine systems, a regeneration tower,
absorption tower, and other key components are made of stainless steel;
however, many mineral salt impurities, such as chloride ions, come from
the feed gas, makeup water, and process chemicals, and they accumulate
in the MDEA solution over time. The chloride ion content in amine so­
lutions can reach 8000 μg/g. Chloride ions can increase the risk of local
corrosion in equipment made from austenitic stainless steels (SS), such
as 316L SS and 304 SS, which may cause catastrophic perforation and
rupture of equipment (Marcus et al., 2008; Meng et al., 2014).
The destructive action of Cl− on stainless steel under different service
conditions is widely recognized (Liu et al., 2008; Marcus et al., 2008;
Meng et al., 2014; Webb and Alkire, 2002). Many studies have also
focused on the effects of Cl− on the pitting corrosion of stainless steel in
oil and gas fields. For example, He et al. (2009) studied the synergistic
effect of chloride and H2S on passive oxide film formation and metal
substrate dissolution of 316L SS in CO2–H2S–Cl− environments. They
observed that the chloride concentration had a critical effect on the
semiconductor properties of the passive film, but the acid gas had little
influence. Moreover, chloride can locally weaken the passive film and
further promote sulfur penetration. Adding H2S to the solution con­
taining Cl− significantly increased the corrosion current density of the
stainless steel and also promoted its corrosion sensitivity (Ding et al.,
2014). They also noticed that the anodic dissolution rate of 316L SS in
H2S–CO2–Cl− was accelerated during service, the passive film was
destroyed, and the pitting corrosion rate was accelerated (Ding et al.,
2013). Zhang et al. (2016) investigated the effect of Cl− concentration
on corrosion behavior of 316L SS in MDEA desulfuring solution con­
taining H2S/CO2 and found that the corrosion process was primarily
affected by H2S. Furthermore, CO2 corrosion weakened as the chloride
concentration increased due to its complex effect. Schmitt and Han (Han
et al., 2011; Schmitt, 1984) also demonstrated that the increased Cl−
concentration inhibited CO2 corrosion by reducing the CO2 solubility in
corrosive solution at room temperature. Li et al. (2019) found that the
presence of CO2 lowered the pitting potential of stainless steel in a so­
lution with low Cl− concentrations and increased the pitting tendency.
But when Cl− increased to a certain extent, the Cl− adsorption decreased
the solubility of CO2 and slowed further pitting. Liu et al. (2014) showed
that increasing the Cl− content reduced CO2 solubility; moreover, Cl−
destroyed the corrosion product films and changed the film morphol­
ogies. Besides, Hausler found that Cl− did not significantly affect CO2
corrosion (Hausler, 1984; Dunlop et al., 1984). Qi et al. (2016) found
that 316L SS in CO2–H2S–Cl− environments displayed a high SCC (Stress
Corrosion Cracking) susceptibility, likely due to hydrogen penetration
and corrosion pits, and when MDEA was in presence in CO2–H2S–Cl−
environments, 316L SS possessed dramatically higher SCC resistance
associated with the MDEA-induced removal of H2S/CO2 and absorption
on the metal surface.
Besides chloride ions, temperature and pH also play key roles in
pitting corrosion of stainless steel. The lowest temperature of pitting in a
specific environment is called critical pitting temperature (CPT). Brig­
ham et al. (Brigham and Tozer, 1973, 1974) first proposed the concept of
CPT and used it to evaluate the corrosion resistance of stainless steel in
the 1970s. The CPT of stainless steel was determined by the Cl− con­
centration, and ion diffusion is difficult at high Cl− concentrations,
which makes it easier to maintain pitting growth, resulting in a lower
CPT (Ernst and Newman, 2007). Furthermore, Cl− had no significant
effect on the local corrosion rate in 1–20 wt% Cl− at 80 ◦ C. For the in­
fluence of pH on CPT, Quarfort (Quarfort (1989) found that for
high-alloy austenitic stainless steels, the critical pitting temperature
does not change with pH between 1 and 7. The pitting corrosion was
more sensitive to the chloride concentration than the pH (Naganuma
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Journal of Natural Gas Science and Engineering 86 (2021) 103718
et al., 2015), and increasing Cl− concentration promoted pit growth and
propagation (Webb and Alkire, 2002). Freire (Freire et al., 2010)
considered that under alkaline conditions (pH = 9–13), a thin protective
film was formed on the surface of 316L SS, which prevented pitting. The
corrosion rate decreased with increasing pH and reached the highest at
pH 4 and the lowest at pH 9 (Malik et al., 1992). Unfortunately, the
effect of temperature on the pitting behavior of SS in highly alkaline (pH
~ 10.5) MDEA solution with or without chloride ions has not been re­
ported in detail. Only Tan et al. investigated the electrochemical pitting
corrosion behavior of 316L SS in 45 wt% MDEA solution saturated with
H2S and CO2 in oilfields and found that increasing the temperature
caused the corrosion potential of 316L SS to undergo a negative shift.
The charge transfer resistance decreased, and the anodic dissolution rate
significantly accelerated.
These previous studies have shown that Cl− usually plays a key role
in the pitting corrosion of SS, and high levels of Cl− can accumulate
during natural gas purification. When SS is placed in an alkaline MDEA
environment, Cl− may cause severe pitting corrosion. The synergistic
effect of Cl− and acid gas can cause pitting corrosion of SS used in oil and
gas fields, but most scholars have only investigated the effect of acid gas
but not Cl− . No research has evaluated the individual effect of Cl− from
the synergistic effect of Cl− and acid gas. If the individual contribution of
Cl− to the pitting corrosion is not fully considered, the effect of Cl− in
MDEA may be underestimated or even ignored. Temperature is one of
the most important factors affecting the pitting corrosion either in pure
aqueous solutions containing Cl− or in MDEA solutions containing both
acid gas and Cl− ; however, it is still unclear how temperature affects
pitting corrosion in MDEA solutions containing only Cl− .
The individual effect of Cl− on the pitting corrosion of SS in the
MDEA solution is still unclear, as is the effect of temperature on the
corrosion of SS in MDEA solution containing Cl− . Once the contribution
of Cl− to the corrosion of SS in the MDEA solution is determined, we can
assess whether Cl− should be controlled during the service of SS in
MDEA solutions. Therefore, this work was dedicated to understanding
the individual role of Cl− and the effect of temperature on the electro­
chemical corrosion behavior of 316L SS in MDEA aqueous solutions
containing Cl− using electrochemical techniques. For comparison, the
experiments under identical conditions in the presence of CO2 were also
conducted.
2. Experimental
2.1. Materials and solutions
The chemical composition of the 316L SS alloy used in the work is
listed in Table 1. All 316L SS samples were cut into cylinders with di­
mensions of ϕ10 mm × 8 mm and then connected with copper wire with
an insulating layer. The 360L SS samples were embedded in cured epoxy
resin, and only one surface with an area of 0.785 cm2 uncovered for use.
The left surface was sequentially polished with abrasive carbide papers
with grits of 800, 1000, 1200, 1500, and 2000, and then polished with
diamond paste using 0.05 μm grit. Samples were then rinsed with
anhydrous ethanol and deionized water for 10 min, and finally dried
with cold compressed air and stored in a desiccator.
The experimental solution included 50 wt% plain MDEA solution
(solution A), and 50 wt% MDEA solution containing 1.0 wt% NaCl
(solution B) prepared by adding analytical reagent grade NaCl. For the
experiments in presence of acid gas, CO2 was continuously introduced
into the solutions A and B for 1 h to prepare a CO2-saturated MDEA
solution (solution C) and CO2-saturated MDEA solution containing 1.0
wt% Cl− (solution D).
2.2. Electrochemical measurements
Electrochemical measurements were conducted using a three-
electrode system connected to a PARSTAT 4000 electrochemical
X. Hou et al.
Table 1
Chemical composition of 316L SS (wt.%).
C Si Mn P S
0.023 0.47 1.97 0.011 0.004
workstation produced by Princeton Applied Research Company. The
316L SS sample sealed with epoxy was used as the working electrode
(WE), a high-purity graphite electrode as the counter electrode (CE), and
an Ag/AgCl/0.1 mol/L− 1 KCl electrode as the reference electrode (RE).
The open-circuit potential (OCP), potentiodynamic polarization,
potentiostatic polarization, and electrochemical impedance spectros­
copy (EIS) were performed.
The temperature was controlled by a water bath with a digital
thermostat. All electrochemical measurements were performed in both
plain MDEA solution and MDEA solution containing 1.0 wt% chloride in
the presence/absence of CO2 at different temperatures controlled by a
constant temperature bath. The solution temperature was set to increase
stepwise in a 10 ◦ C increment from 20 ◦ C to 80 ◦ C (±1 ◦ C). Each test was
repeated three times to ensure reproducibility. The potential scanning
range for the potentiodynamic polarization curves was − 0.3 ~ +1.5 V
(vs. OCP) and the scanning rate was 1 mV/s. EIS was performed in the
frequency range from 0.01 Hz to 100 kHz, and the test amplitude po­
tential was 10 mV. To determine the critical pitting temperature, the
sample was first stabilized at the OCP for 30 min at 20 ◦ C, and then an
anodic potential of 300 mV versus Ag/AgCl/0.1mol/L− 1 KCl was
applied, and the temperature of the test solution was increased at a rate
of 1–2 ◦ C/min. The current density was recorded simultaneously during
the experiment. Before all experiments, nitrogen was slowly introduced
into the MDEA solution to eliminate the influence of oxygen. During
electrochemical experiments in solutions C and D, CO2 was continuously
Fig. 1. Potentiodynamic polarization curves of 316L SS in four different MDEA solutions at different temperatures: (a) plain MDEA solution, (b) MDEA solution
containing 1.0 wt% Cl− , (c) CO2-saturated MDEA solution, (d) CO2-saturated MDEA solution containing 1.0 wt% Cl− .
3
Journal of Natural Gas Science and Engineering 86 (2021) 103718
Cr Ni Mo Cu Fe
17.46 14.55 2.3 0.01 Bal
introduced at a fixed flow rate. When the current density suddenly
increased and reached 100 μA/cm2, the temperature was taken as the
critical pitting temperature.
3. Results and discussion
3.1. Potentiodynamic polarization measurements
Fig. 1 shows the potentiodynamic polarization curves of 316L SS in
four solutions (A, B, C, and D) at different temperatures. For 316L SS in
these four solutions at different temperatures, none of the anodic
branches of the potentiodynamic polarization showed the expected
Tafel behavior. Instead, their passivation plateau zones were observed.
All of the cathodic branches in the polarization curves showed nearly the
same shape but did not follow perfect Tafel behavior. Nevertheless, we
tried to solely use the cathodic branches to determine the corrosion
current density (Icorr) by Tafel extrapolation, even though the fitting
results obtained through both anodic and cathodic branches are gener­
ally preferred over the cathodic branches. Table 2 summarizes the fitting
results of the potentiodynamic polarization curves, where Icorr is the
corrosion current density (μA/cm2), Ecorr the corrosion potential (V), ba
the anodic Tafel slope (mV/dec), and bc the cathodic Tafel slope (mV/
dec). Unfortunately, although the same experiments were conducted
several times, Icorr for each sample did not exhibit a regular change with
temperature but fluctuated (Table 1), which may be related to the errors
X. Hou et al. Journal of Natural Gas Science and Engineering 86 (2021) 103718

Table 2 its metal substrate will be exposed to the corrosive service environment.
Electrochemical parameters for the potentiodynamic polarization curves of 316L Therefore, a more positive Eb for 316L SS in the plain MDEA solution
SS in four different MDEA solutions at different temperatures. (solution A) than the MDEA solution containing Cl− (solution B) and the
Solution T E (V) ba (mV/ -bc Icorr potential difference of approximately 400 mV, implies that the local
(◦ C) dec) (mV/ (μA/ corrosion performance of the passive film was more stable in solution A.
dec) cm2) A clear breakdown potential for 316L SS was observed in the MDEA
Plain MDEA solution 20 − 0.520 459 170 0.667 solution containing 1.0 wt% Cl− (solution B) compared with solution A.
30 − 0.525 304 190 1.187 Eb shifted negatively with increasing temperature, indicating that the
40 0.504 309 171 1.596
−
temperature promoted local attack and subsequent pitting propagation
50 − 0.500 315 166 2.737
60 − 0.498 314 143 2.771 under anodic polarization. At lower temperatures, a more positive Eb
70 − 0.467 217 135 0.985 was observed, which corresponded to transpassive dissolution but not
80 − 0.488 185 187 0.595 local corrosion. At higher temperatures, Eb decreased upon increasing
MDEA solution containing 20 − 0.536 339 151 0.713 temperature and chloride addition. In addition, the presence of CO2 did
1.0 wt% Cl− 30 0.508 213 198 0.699
not significantly affect the breakdown potential of 316L SS in the MDEA
−
40 − 0.487 223 159 0.526
50 − 0.461 195 461 0.503 solutions with/without Cl− , particularly at lower temperatures.
60 − 0.501 201 101 0.559 To measure the critical pitting temperature, the potentiodynamic
70 − 0.540 112 226 0.317 polarization curves of samples at different temperatures should be ob­
80 0.659 105 81 0.271
−
tained to map the breakdown potential with temperature (Abd El
CO2 saturated MDEA 20 − 0.678 359 71 0.341
solution 30 − 0.827 349 68 0.719 Meguid and Abd El Latif, 2007; Laycock et al., 1998; Moayed and
40 − 0.835 – 71 2.159 Newman, 2006). The temperature corresponding to the sudden inflec­
50 − 0.612 192 178 0.436 tion point of the breakdown potential is called the CPT. Fig. 2 illustrates
60 − 0.629 223 240 0.550 how Eb changes with temperature for 316L SS in the four different MDEA
70 0.566 153 137 0.381
solutions. Eb shifts negatively with increasing temperature, when the
−
80 − 0.568 125 175 0.670
CO2 saturated MDEA 20 − 0.810 – 88 0.844 temperature is lower than 60 ◦ C in the MDEA solution containing Cl−
solution containing 1.0 30 − 0.799 13 79 1.181 (solution B), indicating that metastable pitting becomes severe with
wt% Cl− 40 − 0.775 75 84 1.465 increasing temperature. This behavior was due to rapid chemical and/or
50 0.826 102 4.699
− –
electrochemical reactions at higher temperatures. Therefore, the
60 − 0.627 115 258 0.850
70 − 0.610 126 86 0.133 breakdown potential Eb was ascribed to the activity induced by chloride
80 − 0.600 107 200 1.185 at the passive oxide film/MDEA solution interface, but also to the
induced modification by temperature on the passive film, as reported by
Janik Czachor et al. (Janik Czachor et al., 1975). A similar effect of
from the high ohmic resistance of the solution caused by the presence temperature on the protective performance of the passive oxide film was
MDEA or from the Tafel fitting. Therefore, Icorr is not an effective found by Wang et al. (1988), who found that increasing the temperature
parameter for evaluating the corrosion behavior of 316L SS in these four decreased the breakdown resistance of the passive oxide film. According
MDEA solutions. to these observations, the protective performance of the passive oxide
Carefully observing the anodic branches during anodic polarization films deteriorated as the MDEA solution temperature increased. When
for 316L SS in these four different MDEA solutions shows that all curves the temperature was higher than 60 ◦ C, Eb decreased slowly with
have different features at different temperatures. There were some small increasing temperature, and its temperature dependence was not very
current fluctuations in the potential range more positive than Ecorr, in clear, due to changes in the pitting corrosion kinetics. This implies that
particular for the 316L SS in the MDEA solution containing Cl− (solution metastable pitting transformed into stable pitting; therefore, it can be
B and D). A current plateau also appeared in the anodic potential range, inferred that the CPT of 316L SS in the MDEA solution containing 1.0 wt
which corresponds to a passivation zone where a steady state is estab­ % Cl− in the absence of CO2 was between 50 ◦ C and 60 ◦ C.
lished between substrate dissolution and passive oxide film formation, Moreover, the current fluctuation of the anodic branches of the 316L
but steady pitting did not occur. Additionally, the width of the current
plateau strongly depends on the solution composition and temperature.
First, at the same temperature, the passivation zones of 316L SS were
broader in the plain MDEA solution than that in the MDEA solution
containing Cl− (solution B), indicating that there is a worse passivation
ability for 316L SS in solution B due to Cl− pitting. In the presence of
CO2, the passivation zones of 316L SS became broader than those in the
absence of CO2, which means that CO2 may have improved passivation
under our experimental conditions. In particular, the presence of CO2
seemed to reduce the corrosivity of Cl− in the MDEA solution. Tem­
perature also plays a key role in the width of the passivation potential
zones, which became narrower upon increasing the temperature in these
four solutions, indicating that the passivation state was easily destroyed.
There are three distinct regions in the potentiodynamic polarization
curves, including active, passive, and transpassive regions. Those re­
gions at 20 ◦ C are presented in Fig. 1. A breakdown potential (Eb) or
pitting potential (Epit), usually corresponding to a current density of
about 100 μA/cm2, is indicated by a continuous increase in the current
density in the passive region. The anodic passivation potential domain
extends to the breakdown potential (Eb), as reported by the previous
literature of 316L SS pitting. Generally, Eb of a given metal in corrosive
environments may indicate the ability for its protective film to suppress
Fig. 2. Breakdown potential plot for 316L SS in four different MDEA solutions
local corrosion. Once a passive film breaks down through its defect sites, with temperature.

4
X. Hou et al.
SS in the MDEA solutions containing Cl− (solutions B and D) seemed
more obvious than in the MDEA solutions without Cl− (solutions A and
C) during the passive and transpassive stages, as illustrated in Fig. 1. The
current density fluctuation during pitting may be caused by the random
rupture of the passive film. Upon entering the transpassive region, the
anodic branches of 316L SS in the MDEA solutions containing Cl− are
nearly parallel with the current density axis, indicating that the current
density increased more quickly than in the MDEA solutions without Cl− .
This further verifies that Cl-in the MDEA solution significantly contrib­
uted to the corrosion of 316L SS.
3.2. Potentiostatic polarization measurements
Potentiostatic polarization (Deng et al., 2007; Eghbali et al., 2011;
Ebrahimi et al., 2011a, 2011b, 2012) also can be used to investigate the
critical pitting temperature (CPT) of 316L SS. This technique is based on
changes in the current density with temperature and elapsed time in the
considered system at an applied potential, which can be used to accu­
rately evaluate the CPT of 316L SS in different solutions.
Fig. 3 shows the potentiostatic polarization curves of 316L SS at an
anodic potential of 300 mV vs. Ag/AgCl/0.1 mol/L− 1 KCl in four
different MDEA solutions at different temperatures. The potentiostatic
polarization curves showed that the corrosion current density of 316L SS
increased with the temperature and measurement time, and the current
density related to the applied anodic potential decreased in the early test
stage. This lower current density was attributed to the thicker passiv­
ating film on the 316L SS surface due to strong anodic polarization. This
reduction of current density remained until 28 ◦ C for solution A, 25 ◦ C
for solution B, 40 ◦ C for solution C, and 35 ◦ C for solution D. According
to the changes in the corrosion current density, each potentiostatic po­
larization curve can be divided into three different stages: pitting
Fig. 3. Potentiostatic polarization curves of 316L SS at an anodic potential of 300 mV vs. Ag/AgCl (0.1 mol/L− 1 KCl) in two solutions at different temperatures over
time: (a) plain MDEA solution, (b) MDEA solution containing 1.0 wt% Cl− , (c) CO2-saturated MDEA solution, (d) CO2-saturated MDEA solution containing 1.0 wt
% Cl− .
5
Journal of Natural Gas Science and Engineering 86 (2021) 103718
nucleation, metastable pitting, and stable pitting.
At the initial stage of pitting nucleation, the polarization current
density did not significantly change as the temperature increased. This
implies that the passive film of 316L SS can stably exist; however, at the
metastable pitting stage, the polarization current density began to
slowly increase upon further increasing the temperature. In particular,
some intermittent and vertical fluctuation peaks can be observed that
coincided with the experimental results obtained by Ilevbare (Ilevbare
and Burstein, 2003). These vertical fluctuation spikes during the
meta-stable pitting may be induced by the dissolution of the 316L SS
substrate in solutions A and B, as well as the repassivation of the fresh
316L SS substrate. This indicates the initiation of metastable pitting, but
no stable pits were obtained. Furthermore, the polarization current
density increased with temperature and time during the metastable
pitting, which implies that some stable pitting occurred on the 316L SS
surface. During the stable pitting stage, the polarization current density
quickly increased with time and temperature. When the temperature
reached 67.2 ◦ C for solution A, 59.6 ◦ C for solution B, 74.6 ◦ C for so­
lution C, and 66.7 ◦ C for solution D, their corrosion current density
reached 100 μA/cm2, where the corresponding temperature is the
so-called CPT. These values are in agreement with the reported CPT for
many stainless steels, which range from 10 to 100 ◦ C (Arnvig and Bis­
gard, 1996). When the temperature was higher than the CPT, the passive
film on the surface was broken, and metastable pitting began to trans­
form into stable pitting. In general, pit initiation should be mainly
considered in this region above the CPT. Further increasing the tem­
perature over the CPT increased the corrosion current density and the
pitting process tended to become stable.
Similar to breakdown or pitting potential, CPT can be used to indi­
cate the susceptibility to pitting corrosion, or to evaluate the resistance
to stable pitting propagation because it is independent of applied
X. Hou et al.
constant potential over a wide range of environmental factors (Arnvig
and Bisgard, 1996). Here, the CPT of 316L SS was higher in the plain
MDEA solution than the MDEA solution containing 1.0 wt% Cl− , which
means that the pitting corrosion occurred at a lower temperature in the
latter solution, in agreement with the potentiodynamic polarization
curves. Usually, the CPT is correlated with the dual effect of a salt film on
either stabilizing pit growth by supplying a reservoir of acid-generating
salt at higher temperatures or the promotion of repassivation by
consuming acids at the interface at lower temperatures (Beck, 1982;
Grimm and Landolt, 1994). In addition, the current fluctuations in the
potentiostatic polarization curves seem to be smaller, and the CPTs are
higher in the presence of CO2, compared to that in the absence of CO2,
which means that CO2 does not promote the pitting corrosion of 316L SS
in the MDEA solutions under our experimental conditions. CO2 may play
a role at higher temperatures.
3.3. EIS measurements
Electrochemical impedance spectroscopy (EIS) can be used to mea­
sure the critical pitting temperature of materials, and usually the CPT
measured by EIS was more conducive for revealing the reaction mech­
anism (Hoseinpoor et al., 2014). The EIS plots of the corrosion of 316L
SS in four different MDEA solutions at different temperatures are illus­
trated in Figs. 4 – 7. Both the diameter of the capacitive arc in the EIS
Nyquist plots and the low-frequency impedance amplitude in the Bode
plots decreased as the temperature increased, which indicates that 316L
SS in these four solutions become more susceptible to pitting corrosion
at higher temperatures. According to the phase angle in the Bode plots,
only one time constant was distinguished, and the peak phase angle
moved towards higher frequencies as the temperature increased, which
shows that the passive film became less stable, and the risk of corrosion
began to increase.
Fig. 4. EIS plots of the corrosion of 316L SS in plain MDEA solution at different temperatures: (a) Nyquist plot, (b) impedance amplitude, and (c) phase angle.
6
Journal of Natural Gas Science and Engineering 86 (2021) 103718
At the same temperature, the low-frequency impedance amplitude of
316L SS was significantly higher in the plain MDEA solution (solution A)
than in the MDEA solution containing Cl− (solution B), which indicates
that the corrosion risk in the latter solution was higher. Fig. 5 shows that
in the MDEA solution containing Cl− , the capacitive loop diameter of
316L SS decreased slowly when the temperature increased from 20 ◦ C to
50 ◦ C, but when the temperature rose from 50 ◦ C to 60 ◦ C, the capacitive
loop diameter greatly decreased, and the corresponding Bode imped­
ance amplitude at 0.01 Hz also decreased from 50 kΩ cm2 to 30 kΩ cm2.
This sudden change implies that the passive film was completely broken,
and the steady-state pitting occurred in this temperature range. This is in
accordance with the potentiodynamic and potentiostatic polarization
results.
Two equivalent circuits related to critical pitting temperature were
proposed to fit the EIS results, as illustrated in Fig. 8. At temperatures
lower than the CPT, the simplest equivalent circuit composed of one
time-constant can be used to describe the 316L SS behavior, which is
different from that at temperatures higher than the CPT. This time-
constant was ascribed to the response of the passive oxide film. At
temperatures higher than the CPT, an equivalent circuit with two time-
constants was used. The time-constant at high and medium frequencies
was correlated with the barrier properties of the passive surface film,
and the time-constant at low and medium frequencies was associated
with interfacial reactions, i.e., pitting. In these two equivalent circuit
models, Rs is the MDEA solution resistance, CPEf is the passive film
capacitance, Rf is the passive film resistance, CPEpit is the double layer
capacitance at the interface between the 316L SS surface and MDEA
solution in pits, and Rpit is the charge transfer resistance associated with
pits. A constant phase element (CPE) is used here to more accurately
analyze the corrosion impedance behavior of the electric double layer,
and n is the dispersion parameter related to the surface morphology.
Fig. 9 displays the proposed equivalent circuit of the 316L SS surface in
X. Hou et al.
Fig. 5. EIS plots of the corrosion of 316L SS in MDEA solution containing 1.0 wt% Cl− at different temperatures: (a) Nyquist plot, (b) impedance amplitude, and (c)
phase angle.
the MDEA solution containing 1.0 wt% chloride ions before (Fig. 9a) and
after stable pitting formation (Fig. 9b). Once stable pits were formed, the
surface of 316L SS was divided into two different parts: a passive surface
and a pitting zone. For the passive surface, the proposed equivalent
circuit was similar to the one at temperatures lower than the CPT.
However, in the presence of stable pits on the surface, two new physical
elements involving stable pits were added in the circuit: CPEpit and Rpit.
The fitted electrochemical impedance parameters of 316L SS in these
four solutions at different temperatures are listed in Table 3. The solu­
tion resistance Rs reached 1095 Ω cm2 in the plain MDEA solution at
20 ◦ C, while Rs significantly decreased by about 53 Ω cm2 after adding
1.0 wt% Cl− , indicating that the conductivity of the plain MDEA solution
was much lower than the MDEA solution containing Cl− . In addition,
when the temperature reached 80 ◦ C, Rs decreased by 178.2 Ω cm2 and
6.832 Ω cm2, respectively. The passive film resistance Rf of 316L SS in
the MDEA solution containing Cl− was much smaller than that in the
plain MDEA solution at the same temperature. A similar change was
observed when CO2 was introduced into solutions A and B. In all four
solutions, Rf decreased with an increase in temperature. In particular,
for the MDEA solution containing Cl− , Rf significantly decreased; when
the temperature increased from 50 ◦ C to 60 ◦ C, Rf decreased by one
order of magnitude, which further indicates that both temperature and
chloride impurities are critical factors that affect the pitting corrosion of
316L SS in the MDEA solution. The charge transfer resistance Rpit of
316L SS did not show obvious variation upon increasing the tempera­
ture, which implies that Rpit remained constant once stable pits were
formed, and Rf was decisive during corrosion inhibition. Furthermore,
the introduction of CO2 in solutions A and B reduced the film resistance
of 316L SS, but the effect is not critical.
7
Journal of Natural Gas Science and Engineering 86 (2021) 103718
3.4. Pitting corrosion of 316L SS in MDEA solution containing chloride
ions
The breakdown potential Eb from the potentiodynamic polarization
curves, the polarization resistance Rp = Rf + Rct from EIS, and polari­
zation current density from potentiostatic polarization, show that both
Cl− and temperature play critical roles in the pitting corrosion of 316L
SS in slightly alkaline MDEA solution. In the following section, the
pitting corrosion of 316L SS in MDEA solution containing chloride ion is
addressed from three aspects by combining our findings with classical
pitting mechanisms of stainless steel, including penetration, break­
through, and adsorption (Burstein et al., 2004; Ernst and Newman,
2007; Frankel, 1998; Laycock and Newman, 1997; Laycock et al., 1998;
Newman, 2001; Quarfort, 1989; Zamaletdinov, 2007).
First, compared with the plain MDEA solution, the presence of Cl−
made 316L SS easily subjected to pitting corrosion attack in the MDEA
solution due to the breakdown of the passive film at random sites. The
pitting corrosion process was attributed to the significant pitting effect
of Cl− due to three of its characteristics: (a) it is an anion of a strong acid
that causes Fe2+ to dissolve in chloride solutions; (b) it easily adsorbs on
the surface of 316L SS, particularly at defects and inclusions on the
surface; (c) it is a relatively small anion with high diffusivity in solution
(Ernst and Newman, 2007; Frankel, 1998). Therefore, Cl− tends to
interfere with the passivation of 316L SS in MDEA solution and cause
pitting nucleation, which is promoted as the MDEA environment be­
comes increasingly aggressive with respect to chloride ions. Cl− can
result in strong induced ion conductivity, allowing the passive film to
maintain a high current density at a certain point, which makes the
cations move randomly and become active.
X. Hou et al.
Fig. 6. EIS plots of the corrosion of 316L SS in CO2 saturated MDEA solution at different temperatures: (a) Nyquist plot, (b) impedance amplitude, (c) phase angle.
When the electric field at the passive film/MDEA solution interface
reaches a critical value, the passive film ruptures. After pitting nucle­
ation, the puts will continue to grow and form microscale pits, before
becoming passivated again. The continual breakdown and reparation of
the thin passive film is called meta-stable pitting, which may be the most
important stage since only the pits surviving from this stage may become
stable growing pits (Quarfort, 1989). Finally, the dynamic equilibrium
between rupture and repair of the passive film at local defects is broken,
and they become stable pits. Then, the surface inside a pit in a local
activation state (low potential) serves as the anode, and most of the
surface outside the pit is still passivated (high potential) and serves as
the cathode; therefore, an activated-passive electrochemical corrosion
cell with a “big cathode and small anode” is formed inside and outside
the pit (Frankel, 1998; Newman, 2001). As the anodic reaction proceeds,
the concentration of metal cations (such as Fe2+) in the pit increases. To
maintain charge neutrality in the pit by balancing the charge related to
the cation, chloride anions electromigrate into the pit. Cation hydrolysis
and the absence of a local cathodic reaction reduces the pH in the pits.
Once an acidic chloride environment forms in the pits, the pit growth
can be promoted due to an autocatalytic pitting mechanism.
The temperature dependence of breakdown potential, the back­
ground current density, and EIS impedance show that the pitting
corrosion of 316L SS in MDEA, i.e. nucleation and growth of a stable pit,
increased with the increase of MDEA solution temperature. This was
attributed to two aspects (Wang et al., 1988). The porosity of the passive
oxide film on stainless steel increased with temperature. The passive
oxide film on stainless steel may undergo an intrinsic modification of its
physical structure and/or chemical composition at higher temperatures,
which may change the density of voids or vacancies in the passive film.
For example, Manning et al. (Manning and Duquette, 1980) pointed out
that the passive oxide film on stainless steel showed p-type behavior at
8
Journal of Natural Gas Science and Engineering 86 (2021) 103718
room temperature, but it changed to n-type behavior at higher tem­
peratures. However, there is not enough information to clarify the exact
effect of temperature on the structure or/and composition of the passive
oxide films. Szklarska-Smialowska (Szklarska-Smialowska and
Janik-Czachor, 1971) found that a higher temperature can increase the
chemisorption strength of chloride ions on metal surfaces. Temperature
is still an important factor that influences the protective performance of
the passive oxide films on 316L SS in an MDEA solution.
MDEA may inhibit pitting corrosion due to its own high basicity.
Generally speaking, the pH in the corrosion pit becomes lower due to
cation hydrolysis and the absence of a local cathodic reaction. The lower
pH may supply favorable conditions for pit growth (Malik et al., 1992).
Thus, the acidic chloride-containing environment generated in the
corrosion pits aggressively propagates pit growth and can accelerate the
dissolution of the 316L SS substrate (Malik et al., 1992; Yang, 2007).
However, MDEA can act as a chelating agent for H+, which then changes
the pH in the pit. MDEA is an alkanolamine, whose molecular formula is
CH3–N(CH2CH2OH)2, which contains one hydroxyl group and two
amino groups; therefore, MDEA can be hydrolyzed to produce OH− in
water and shows kind of alkalescence. The reaction between MDEA and
water is reversible. At low temperatures (20–40 ◦ C), the forward reac­
tion is favored, and a large amount of OH− is produced, which inhibits
the redox reaction rate and reacts with metal ions to form a new passive
film, which increases the stability of the passive film.
The metal constantly dissolves in the pits, so to keep the solution
electrically neutral, the anions (Cl− and OH− ) outside the pits migrate
into the hole. However, the limiting conductivity of OH− is higher than
that of Cl− , so OH− competes with Cl− for adsorption sites on the oxide
surface, even though Cl− has a dominant effect (Marcus et al., 2008;
Szklarska-Smialowska and Janik-Czachor, 1971; Szklarska-Smialowska,
1971). OH− flows into the metal surface pits and reacts with the metal
X. Hou et al. Journal of Natural Gas Science and Engineering 86 (2021) 103718

Fig. 7. EIS plots of the corrosion of 316L SS in CO2 saturated MDEA solution containing 1.0 wt% Cl− at different temperatures: (a) Nyquist plot, (b) impedance
amplitude, and (c) phase angle.

Fig. 8. Equivalent circuit of the pitting corrosion of 316L SS in MDEA solution with and without 1.0 wt% chloride ions at a temperature lower than the CPT (a) and at
a temperature higher than the CPT (b).

Fig. 9. Proposed model for the equivalent circuit of the pitting corrosion of 316L SS in MDEA solution containing 1.0 wt% chloride ions at a temperature lower than
the CPT (a) and a temperature higher than the CPT (b).

ions diffusing from the pits to generate a dense solid covering that can passive oxide film. Due to its physicochemical characteristics, MDEA can
inhibit Cl− diffusion to the pits, increase the diffusion resistance of metal easily absorb on the steel surface, resulting in the separation between
from the bottom of the pits to the outside, and slow the dissolution of the steel and corrosion ions. However, upon increasing the temperature, the

9
X. Hou et al. Journal of Natural Gas Science and Engineering 86 (2021) 103718

Table 3
The fitted impedance parameters of 316L SS in two solutions at different temperatures.
Solution T Rs CPEf nf Rf (104 Ω CPEpit npit Rpit
(◦ C) (Ω•cm2) (10− 5Ω− 1•Sn•cm− 2) cm2) (10− 5Ω− 1•Sn•cm− 2) (Ω•cm2)

Plain MDEA solution 20 1095 64.29 0.91 15.06 / / /

30 683.0 50.31 0.89 14.42 / / /
40 406.8 6.262 0.89 9.424 / / /
50 302.3 6.241 0.87 8.442 / / /
60 248.1 5.776 0.89 7.819 / / /
70 203.6 6.712 0.88 6.281 6.665 0.88 204.3
80 178.2 7.244 0.87 3.309 7.163 0.87 179.2
MDEA solution containing 1.0 wt% Cl− 20 53.15 131.3 0.84 8.116 / / /
30 22.43 15.91 0.81 4.744 / / /
40 15.88 15.15 0.82 3.549 / / /
50 14.43 124.7 0.83 2.701 / / /
60 6.023 131.2 0.77 0.792 6.37 0.81 180.2
70 11.98 114.9 0.83 0.547 5.25 0.82 173.6
80 6.832 126.1 0.81 0.378 9.51 0.86 196.1
CO2-saturated MDEA solution 20 157.9 6.976 0.88 10.27
30 55.86 8.527 0.88 4.012
40 25.74 8.999 0.87 3.698
50 7.411 9.453 0.86 3.371
60 8.899 10.44 0.86 4.207
70 28.59 10.15 0.87 3.410
80 19.67 11.19 0.84 3.520
CO2-saturated MDEA solution containing 1.0 wt 20 31.91 8.019 0.85 3.982
% Cl− 30 22.79 8.018 0.86 3.000
40 17.18 8.720 0.85 2.697
50 14.74 8.294 0.86 2.046
60 13.98 9.337 0.85 2.413
70 36.95 8.97 0.86 2.930
80 18.80 10.52 0.84 1.763

reverse reaction of MDEA begins to strengthen, the OH− concentration Declaration of competing interest
gradually decreases, and then the protective effect of MDEA on the
passive film is weakened. At the same time, upon increasing the tem­ The authors declare that they have no known competing financial
perature, the porosity of the passive oxide film on stainless steel in the interests or personal relationships that could have appeared to influence
MDEA solution increases, and more active sites were exposed on the the work reported in this paper.
metal surface, making it easier for Cl− to penetrate the passive film; thus,
the 316L SS substrate may be prone to destruction. Acknowledgments

4. Conclusions Authors would like to appreciate the Chongqing Natural Science

316L SS displayed a narrower passivation zone in the MDEA solution
containing Cl− than in the plain MDEA solution, and the passivation
zone became narrower upon increasing the temperature. 316L SS
showed a more negative Eb in the MDEA solution containing Cl− , and Eb
shifted negatively with increasing temperature. Above the CPT, Eb
decreased slowly, and its temperature dependence was not unclear.
Potentiostatic polarization results showed that the CPT of 316L SS in
the MDEA solutions decreased due to the presence of Cl− , and the pitting
corrosion of 316L SS occurred at a lower temperature in MDEA solution
containing Cl− , which is in agreement with the potentiodynamic po­
larization results.
The passive oxide film resistance Rf of 316L SS in the MDEA solutions
became smaller when Cl− was added. Rf decreased upon increasing the
temperature in all four test solutions, and Rf significantly decreased in
the MDEA solution containing Cl− . In particular, when the temperature
reached the CPT (around 60 ◦ C), Rf sharply decreased. The charge
transfer resistance Rct of 316L SS did not greatly change upon increasing
the temperature.
The pitting corrosion process of 316L SS in the MDEA solution con­
taining chloride ion was closely related to the temperature and the
characteristics of both the chloride ion and MDEA, which was illustrated
based on the classical pitting mechanisms of stainless steel.
In the presence of CO2, a similar corrosion change pattern with
temperature in the MDEA solutions in the absence of CO2 was observed,
but the role of Cl− during the pitting corrosion of 316L SS seems to be
weakened by CO2.
Foundation Project (cstc2019jcyj-msxmX0188) and Postgraduate Sci­
ence and Technology Innovation Project of CQUST (YKJCX1820209 &
YKJCX1920218).
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