Corrosion Behavior of 2205 Duplex Stainless Steels in HCL Solution Containing Sulfide
Corrosion Behavior of 2205 Duplex Stainless Steels in HCL Solution Containing Sulfide
3 Research Institute of Petroleum Exploration and Development, China National Petroleum Corporation,
[email protected]
* Correspondence: [email protected]; Tel.: + 86-028-8303-7360
Abstract: The corrosion behavior of 2205 DSS in HCl solutions containing sulfide were investigated
using mass loss test, electrochemical measurements, scanning Kelvin probe, scanning electron
microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The results showed that Na2S had
significant effect on corrosion behavior of 2205 DSS in dilute HCl solutions. Slight Na2S can prevent
the passive film from localized attacking of Cl- in HCl solution with a concentration lower than 0.1
mol/L. However, when the concentration of HCl solution higher than 0.137 mol/L, Na2S addition
will tremendously promote corrosion. The intergranular corrosion combined surficial active
dissolution of 2205 DSS could happen in HCl + Na2S solution.
1. Introduction
In oil and gas production and refining industries, the 2205 duplex stainless steels (DSS) as a
promising material is widely used due to its excellent mechanical behavior and high corrosion
resistance [1–3]. However, some severe corrosion cases of 2205 DSS occurred in such industries
recently. Firstly, the corrosion situation was worsened with the increasing of quantity of sulfide,
chloride and carbon dioxide in crude oil [4,5]. Secondly, in the atmospheric distillation columns and
overhead condensation systems of refinery, the primary equipment directly undergo the corrosion
risk from the concentrated detrimental contains (i.e., chloride and sulfide) in crude oils even after the
desalting and dehydration processes [6,7]. In such systems, acidic corrosion occurred due to the
combined action of hydrochloric acid and hydrogen sulfide contained [8–11]. The hydrochloric acid
was formed by the hydrolysis of chlorine salt or organic chloride at high temperature, and finally
became aqueous solution under dew point temperature.
The effect of single chloride or sulfide on corrosion of DSS has attracted many attentions [12–17]
because both of them can affect the stability of passive metal significantly. For instance, Jeonet al.
[12] focused their study on pitting corrosion of DSS in NaCl and NaCl + HCl solutions. They
demonstrated that super DSS in NaCl solution of pH 7 showing pitting corrosion and in NaCl + HCl
solution of pH 1 showed both uniform and pitting corrosion. It was also revealed that the ferrite
phase was corroded more than the austenite phase due to different corrosion resistances in chloride
solutions. Wan et al. [13] proved that Cl- had a strong effect on cavitation corrosion of DSS by
promoting preferential dissolution of ferrous oxides and reducing the ability of passive film. In other
study, Dong and Luo et al. [14] reported the pitting corrosion behavior of 2205 DSS in chloride
solutions. They showed that the temperature and the concentration of chloride played important
roles in changing the thickness of passive film and the shape of pits. Lo et al. [15] studied the
selective dissolution of 2205 DSS between two phases, the result is that with increasing concentration
of HCl, austenite phase dissolution was more faster than ferrite phase dissolution. Besides, the stress
corrosion cracking in sulfur-contained condition has been investigated, for instance by Liu et al. [16]
who studied the stress corrosion cracking of 2205 DSS in CO2-H2S contained environment. It has
been suggested that H2S could primarily promote the reduction of H+ and the oxidation of steel to
form FeS in the solution of pH lower than 3. Liu et al. [17] reported that the cathodic reaction can be
accelerated in H2S-contained solution, which led the fast break of passive film.
Researchers also probed the passive film property [18] and the passivation mechanism [19] of
DSS in different acidic environments. However, the corrosion behavior of 2205 DSS in various
concentrations of HCl solution with sulfide at high temperature had obtained less attention.
Although some studies presented the results on the combination effect of chloride and sulfide in
corrosive mediums with different pH values [20–23], such studies are mainly focused on carbon
steel and austenite steels.
For the corrosive condition of hydrochloric acid plus sulfide solution with different
concentration, how the combination effect of hydrochloric acid and sulfide affect the corrosion
mechanism of 2205 DSS is still unknown. It is very important for probing the passivation destruction
mechanism of 2205 DSS and defining the limitation of 2205 DSS in application. In the industrial
aspect, the understanding of corrosion mechanism of 2205 DSS in HCl + H2S solution which often
occurs in atmospheric distillation columns and overhead condensation systems is mandatory to be
further explored. Besides, there are other similar conditions that 2205 DSS may be applied in, for
instance, the well casing under fracturing operation in H2S contained reservoir in oil and gas
production.
This work aims to provide an improved understanding of the corrosion micro-morphology,
corrosion process, electrochemical mechanism and passivation destruction of 2205 DSS in the
hydrochloric acid plus Na2S at high temperature. The corrosion behaviors of 2205 DSS in HCl plus
Na2S solutions were comparably studied by mass loss, polarization curve, electrochemical
impedance spectra (EIS), scanning Kelvin probe (SKP), scanning electron microscope (SEM) and
X-ray photoelectron spectroscopy (XPS).
2. Experimental Part
( − ) × 87600
= (1)
× ×
Where S (cm2), M1 (g), M2 (g), T (h) and ρ (g/cm3) represent the samples surface area, the weight
of specimens before and after test, the time of test and the density of specimens respectively.
3. Results
−
Growth Ratio (%) = × 100 (2)
CR and CR0 represent corrosion rates of the samples between presence and absence of 0.385
mmol/L Na2S. The corrosion rate is slightly reduced in HCl concentration below 0.137 mol/L by Na2S
addition, indicating that Na2S has an inhibition effect in HCl solutions of lower concentration. In
0.137 mol/L and 0.274 mol/L HCl concentrations without Na2S, the corrosion rates are 0.0114 mm/a
and 0.0130 mm/a, respectively. However, the presence of 0.385 mmol/L Na2S makes the corrosion
rates of 2205 DSS grow up to 12.364 mm/a and 24.506 mm/a respectively in 0.137 mol/L and 0.274
mol/L HCl solutions. Moreover, the corrosion rate growth ratios increase to 108549% and 188551%
accordingly. As 2205 DSS presents an active dissolution, the corrosion rates in 0.548 mol/L HCl with
and without Na2S, rise to 52.734 mm/a and 81.252 mm/a respectively, while growth ratio declines to
54%.
The results presented in Table 1 shows that by adding Na2S, the critical HCl concentration for
active dissolution corrosion of 2205 DSS reduces from 0.548 mol/L to 0.137 mol/L.
Table 1. Corrosion rates of 2205 DSS in different concentrations of HCl solution with or without
Na2S at 90 °C.
sulfide ion can inhibit OH- or O2 and adsorb on the metal surface, hence obstructing the regeneration
of passive film [29].
Figure 1c shows the polarization curves of 2205 DSS in 0.137 mol/L HCl solutions with Na2S
concentration up to 0.385 mmol/L. When adding 0.128 mmol/L and 0.256 mmol/L Na2S in solution,
the corrosion potential shifts to more positive direction and a wider passivation region is attained.
The passivation current density remains at similar values, suggesting localized corrosion is inhibited
by sulfide [30]. However, it may be seen that corrosion potential decreases rapidly and anodic
current densities increased respectively when the concentration of Na2S increases to 0.385 mmol/L.
Such behavior agrees with the mass loss test, implying that the corrosion process is promoted by
sulfide and 2205 DSS cannot passivate anymore.
1.5
1.0
0.5
0.0
-0.5
1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3
Metals 2019, 9, 294 6 of 27
E/V(SCE)
0.0
-0.5
1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0.01
-2
i/Acm
Figure 1. Polarization curves of 2205 DSS in (a) HCl solutions, (b) 0.1 mol/L HCl + Na2S solutions and
(c) 0.137 mol/L HCl + Na2S solutions at 90 °C.
-Z"/(cm )
5 0.0
2
1.0x10 Fitted 0.0 1.5x10
4
4
5.0x10
0.0
4 5 5
0.0 5.0x10 1.0x10 1.5x10
2
Z'/(cm )
4
4.0x10
0.0
4 4
0.0 4.0x10 8.0x10
2
Z'/(cm )
0
2
0 4 8 12
4
4.0x10
4
2.0x10
0.0
4 4 4
0.0 2.0x10 4.0x10 6.0x10
2
Z'/(cm )
Figure 2. Nyquist plots and the fitting curves for 2205 DSS in (a) HCl solutions, (b) 0.1 mol/L HCl+
Na2S solutions and (c) 0.137 mol/L HCl+ Na2S solutions at 90 °C.
On the other hand, the kinetic parameters affected by sulfide addition have been explored by
using the equivalent circuit shown in Figure 3 [19] for the passive film growth stage. The circuit has
Metals 2019, 9, 294 8 of 27
two time constants. The physical interpretation of this equivalent electric circuit diagram could be
interpreted as a defects-contained passive film growing on the surface of 2205 DSS in the beginning
hours of immersion. The parameter constant phase element CPE1 represents the capacitive behavior
of passive film. The R1 parameter defines the film resistance of growing oxide film. The constant
phase element CPE2 represents the capacitive behavior, R2 for the corresponding charge-transfer
resistance [34,35] of electrochemical reaction at solution/metal interface and Rs is the solution
resistance. The EIS fitting results of 2205 DSS in 0.1 mol/L and 0.137 mol/L HCl solutions with
different addition of Na2S are listed in Table 2.
Table 2. EIS fitting data of 2205 DSS in HCl solution with different Na2S at 90 °C.
Based on the results from Table 2, the film resistance R1 seems to be improved due to the
addition of Na2S in 0.1 mol/L HCl solution, revealing an enhancement of passive film. It worth
noting that in 0.1 mol/L HCl solution with 0.385 mmol/L Na2S addition, the CPE2 decreases and R2
increases comparing with the results found for samples without Na2S, respectively. The results
demonstrate that the corrosion of 2205 DSS can be successfully inhibited by adding minor amount of
Na2S. Moreover, after adding Na2S, the CPE2 increased and R2 decreased by increasing the Na2S
concentration, indicating the promotion of charge-discharge process of double layer related to
anodic dissolution and cathodic reduction. If consider the total resistance (R1 + R2) representing the
overall corrosion reaction resistance. It becomes higher by adding 0.385 mmol/L Na2S. But the total
resistance decreases with increasing Na2S concentration in 0.1 mol/L HCl solution.
For 2205 DSS in 0.137 mol/L HCl solution without Na2S, R1 and R2 are both slightly reduced
compared with the values obtained for 0.1 mol/L HCl. By adding Na2S with a concentration from 0
to 0.256 mmol/L, the film resistance R1 rises with the increase of Na2S concentration in 0.137 mol/L
HCl and the value of R2 has no significant change. Consequently, the total resistance (R1 + R2) is
increased by small addition of Na2S, which indicates the corrosion inhibition effect of Na2S also
presents in 0.137 mol/L HCl solution. It is in agreement with the result of polarization curve
Metals 2019, 9, 294 9 of 27
measurement (Figure 1c). However, in 0.137 mol/L HCl + 0.385 mmol/L Na2S solution, CPE1 and
CPE2 obviously increased, while R1 and R2 remarkably decreased, corresponding to the active
dissolution of 2205 DSS.
Figure 4. Surface potential 3D mappings of 2205 (a) before and (b) after immersion for 20 s in 0.137
mol/L HCl + 0.385 mmol/L Na2S solution.
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Figure 5. Metallographic images of 2205 DSS (a) before and (b) after 4 h of corrosion in 0.137 mol/L
HCl + 0.385 mmol/L Na2S solution, corrosion product was removed.
The SEM images of 2205 DSS after mass loss tests in HCl and HCl + Na2S solutions are shown in
Figure 6. Figure 6a reveals that 0.1 mol/L HCl solution causes pitting corrosion in local site. At
higher HCl concentration (0.137 mol/L) more defects can be observed on the surface as presented in
Figure 6b. These results indicate that 2205 DSS is more sensitive to localized corrosion in 0.137 mol/L
HCl solution. In 0.1 mol/L HCl solution, the corrosion of 2205 DSS is retarded when added 0.385
mmol/L Na2S (Figure 6c). Although several corrosion pits are observed in 0.1 mol/L HCl + 3.846
mmol/L Na2S, no dramatic corrosion occurs (Figure 6d). Figure 6b,e show that 0.128 mmol/L Na2S
addition prevented the effect on the pitting corrosion of 2205 DSS in 0.137 mol/L HCl solution.
However, 0.385 mmol/L Na2S addition can cause dramatic active corrosion in 0.137 mol/L HCl
solution (Figure 6f). It can be seen from the cross-section images that many corrosion defects of
about 20 μm depth are formed under the corroded layer.
Metals 2019, 9, 294 11 of 27
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Figure 6. Corrosion micro-morphology SEM images of 2205 DSS after 8 h of immersion in (a) 0.1
mol/L HCl, (b) 0.137 mol/L HCl, (c) 0.1 mol/L HCl + 0.385 mmol/L Na2S, (d) 0.1 mol/L HCl + 3.846
mmol/L Na2S, (e) 0.137 mol/L HCl + 0.128 mmol/L Na2S, (f) 0.137 mol/L HCl + 0.385 mmol/L Na2S, (g)
0.548 mol/L HCl, and (h) without corrosion product film 0.137 mol/L HCl + 0.385 mmol/L Na2S, (i)
without corrosion product film 0.548 mol/L HCl.
The active corrosion is observed also for 0.548 mol/L HCl solution as noted from surface
morphology shown in Figure 6g. In Figure 6f,g, the corrosion products covered the entire surface.
Several factors may produce such fractures in the corroded layer, as for instance, the dehydration of
hydroxide corrosion products and modification of H2 pathway formed by hydrogen evolution in
electrolyte/metal interface. The corresponding SEM images after removing the corrosion products
from Figure 6f,g are revealed in Figure 6h,i respectively.
After the immersion of 2205 DSS in 0.137 mol/L HCl + 0.385 mmol/L Na2S solution, several
micro-crack-like defects were shown in the SEM image (Figure 6h). These defects propagated deeply
inside and most likely are formed at grain boundaries scale of austenite and ferrite phases. The
conjunction of these defects may occur during their propagation which created the ravine-like and
cave-like morphologies under the surface (Figure 6f shows their sectional view).
On the contrast, no such defects are observed on the surface of 2205 DSS after immersion in
0.548 mol/L HCl solution without Na2S (Figure 6i). Hydrogen induced cracking (HIC) of low alloy
steel or stainless steel is often found in the corrosion of H2S contained solutions [37]. Thus, a similar
mechanism can be inferred for the behavior found also here for the 2205 DSS. However, these
micro-cracks do not look like a typical hydrogen induced crack morphology [38] and no selective
corrosion of austenite or ferrite phases has been observed according to the cross section image in
Figure 6f,h. The SEM images show the remarkable feature of 2205 DSS corrosion in HCl + Na2S
solution is that active dissolution happens along the grain boundaries compared to the selective
dissolution of ferrite phase in H2SO4/HCl solution [39,40].
The passive film formed on 2205 DSS surface in 137 mol/L HCl solution with 0.385 mmol/L Na2S at
90 °C for 8 h is also presented. For both two passive films, Cr, Fe, Mo, Ni and O are detected on the
surface. For the corrosion product film, Cr, Mo, Ni, S, O, and some Cl traces were detected. The C 1s
peaks (284.6 eV) in has been used as the reference to calibration.
(a) Ni2p
O1s Fe2p
C1s Cr2p
Counts /s
Mo3d
5
3x10 C1s Cr2p
Mo3d Ni2p
Mo3p
5
2x10 Cl2p
1x10
5 S2p
0
0 200 400 600 800
Binding Energy/eV
Figure 7. Large scale scanning XPS spectra of (a) passive films on 2205 DSS surface in 0.137 mol/L
HCl solution and 0.137 mol/L HCl solution with 0.128 mmol/L Na2S, (b) corrosion product film on
2205 DSS surface in 137 mol/L HCl solution with 0.385 mmol/L Na2S at 90 °C for 8 h.
Figure 8 illustrates the high-resolution scanning XPS spectra for each element detected for the
two passive films. It can be seen from Figure 8 that the Cr 2p spectra can be separated into several
constituent peaks of metallic Cr, Cr2O3, Cr(OH)3. The intensities and quantities of Cr2O3 peaks are
higher comparing to Cr(OH)3 and metallic Cr, hence Cr2O3 is the major oxide that constitutes the
passive film. The Fe 2p spectra is in accordance with Fe, Fe2O3 and Fe3O4 metallic species. The Mo
intensities are lower than others, however the overlapping peaks reveal that metallic Mo, Mo4+ and
Mo6+ are present in the passive film. The Ni 2p spectrum reveals the presence of three constituent
peaks representing metallic Ni and NiO. The O1s peak can be split into three components of O2−,
OH− and bound H2O. Based on XPS analysis, it may be concluded that both passive films contain
mainly oxides and hydroxides based on Cr, Mo, Ni and Fe as previously already reported [41].
Metals 2019, 9, 294 14 of 27
Cr2O3
25000
Counts /s
Cr(OH)3
20000
Cr
15000
10000
572 576 580 584 588 592
Binding Energy/eV
(a2) 0.137 mol/L HCl + 0.128 mmol/L Na2S
25000 Cr2O3
Cr2O3
Cr(OH)3
Counts /s
20000
Cr
15000
10000
572 576 580 584 588 592
Binding Energy/eV
Fe 2O 3
28000 Fe
Counts /s
24000
20000
Fe2O3
24000
Counts /s
Fe
20000
16000
6+
8500 Mo 3d3/2
8000
7500
4+
Mo3d3/2 Mo 3d3/2
7000
224 228 232 236 240 244
Binding Energy/eV
(c2) 0.137 mol/L HCl + 0.128 mmol/L Na2S
8000 6+
4+
Mo 3d5/2
Mo 3d5/2
7500 Mo3d 6+
Mo 3d3/2
Counts /s
5/2
7000
6500
4+
6000 Mo3d3/2 Mo 3d3/2
42000
40000
848 852 856 860 864 868 872 876 880
Binding Energy/eV
NiO
38000
36000
Counts /s
2-
O
30000
H2O
20000
10000
30000 2-
O
20000 H2O
10000
Figure 8. High-resolution scanning XPS spectra of passive films on 2205 DSS surface in 0.137 mol/L
HCl solutions at 90 °C for 8 h: (a1) Cr 2p, (a2) Cr 2p, added 0.128 mmol/L Na2S, (b1) Fe 2p, (b2) Fe 2p,
added 0.128 mmol/L Na2S, (c1) Mo 3d, (c2) Mo 3d, added 0.128 mmol/L Na2S, (d1) Ni 2p, (d2) Ni 2p,
added 0.128 mmol/L Na2S, (e1) O1s and (e2) O1s, added 0.128 mmol/L Na2S.
Figure 9 shows the high-resolution scanning XPS spectra for each element found in corrosion
products. The XPS peaks are separated into different combined states referring to XPS analysis of
similar corrosion product [42]. The Fe 2p has been not detected and one possible explanation is that
the iron can be easily dissolved into acidic solution. The peak of chromium can be deconvoluted into
three peaks corresponding to Cr2O3 and CrCl3, as shown in Figure 9a. According to Figure 9b, high
quantity of molybdenum is present in the corrosion product in form of Mo4+ and Mo6+. Some traces
of nickel have been detected as shown in Figure 9c, most likely in oxide, hydroxide and chloride
form. The spectrum of S 2p shown in Figure 9d presents two constituents of S2- in the corrosion
products, indicating sulfide ions from Na2S addition had taken part in corrosion reactions and
different metallic sulfides were formed. The mechanism relating to sulfide ion role during the
corrosion kinetics will be discussed in following section.
Metals 2019, 9, 294 18 of 27
(a) 19000
18500 Cr2O3
Cr2O3
CrCl3
18000
Counts /s
17500
17000
16500
572 576 580 584 588 592
Binding Energy/eV
(b) 25000 6+
Mo 3d5/2
20000 4+
Mo 3d5/2 6+
Mo 3d3/2
Counts /s
15000
4+
Mo 3d5/2
10000
5000 4+
Mo 3d3/2
(c) 19000
NiCl2
18000 NiO Ni
Ni(OH)2
Counts /s
17000
16000
(d)
8000
MoS3
MoS2
Counts /s
6000
MoS2 sulphates
MoS3
4000
40000
(e)
2-
O
30000
Counts /s
-
OH
2-
O
20000
10000
524 528 532 536 540
Binding Energy/eV
(f)
4400
NiCl2
CrCl3
4200
Counts /s
4000
3800
3600
194 196 198 200 202 204
Binding Energy/eV
Figure 9. High-resolution scanning XPS spectra of (a) Cr 2p, (b) Mo 3d, (c) Ni 2p, (d) S 2p, (e) O 1s
and (f) Cl 2p in corrosion product film on 2205 DSS surface after immersion in 137 mol/L HCl
solution with 0.385 mmol/L Na2S at 90 °C for 8 h.
Metals 2019, 9, 294 20 of 27
Figure 9e illustrates of O1s peaks corresponding to O2- and OH- that is in accordance with the
presence of Cr2O3, NiO, Ni(OH)2. The peaks of Cl 2p shown in Figure 9f correspond to NiCl2 and
CrCl3. Figure 10 shows the atom fraction for each element of 2205 DSS in superficial films under
different states. No significant differences have been found for atom fractions in passive film
whatever the solution composition (i.e., 0.137 mol/L HCl + 0.128 mmol/L Na2S).
0.8
(a)
(b)
(c)
0.6
Atom fraction
0.4
0.2
0.0
Cr Mo Ni Fe O S Cl
Element
Figure 10. Atom fraction of elements in surficial films of 2205 DSS: (a) passive film in 0.137 mol/L
HCl solution, (b) passive film in 0.137 mol/L HCl + 0.128 Na2S solution, (c) corrosion product film in
0.137 mol/L HCl + 0.385 Na2S solution.
Nevertheless, the composition characterization of corrosion product film in 0.137 mol/L HCl +
0.385 mmol/L Na2S solution shows that the molybdenum content increase while the chromium
content decrease significantly compared with those in passive film. The molybdenum has low
reactivity in hydrochloric acid (dissolution reaction) compared to other metallic elements. However,
it reacts with H2S or dissolved oxygen in acidic solution to form molybdenum sulfide, oxides and/or
hydroxides, which are also stable in dilute HCl solution.
In summary, the passive film on 2205 DSS is mainly constituted of Cr(III) oxide-hydroxides
with high chemical stability, which offers excellent protection of 2205 DSS matrix. In contrast, once
active dissolution of 2205 DSS occurs in the solution of strong acidic and reductive properties at high
temperature (the critical concentration is 0.137 mol/L HCl + 0.385 mmol/L Na2S), the intermediate
products of ferrous oxide or sulfide would form at the interface competing with the formation of
dense oxide-hydroxides. The passivation would not exist and the surficial chromium oxides would
not be enough for hindering the corrosion.
4. Discussion
Several micro-cracks and deep micro-holes can be seen on corroded surface of 2205 DSS in 0.137
mol/L HCl + 0.385 mmol/L based on morphology characterization by SEM (Figure 6f, Figure 6h)
showing intergranular corrosion which indicates that corrosion of 2205 DSS is significantly
influenced by Na2S addition.
Moreover, it is clear that the corrosion mechanism is closely associated with the role of Na2S,
which hydrolyzes easily and form H2S, HS- and S2- ions, then being preferentially absorbs on metal
surface competing with Cl- in hydrochloric acid solution. According to the following reaction, Na2S
is dissociated to H2S in acidic solution [43,44]. In agreement with the pH-sulfide equilibrium
diagram, at pH > 5.5, the main species is HS-, otherwise it is mainly H2Saq [45,46]. The content of
sodium sulfide is very low, which has little effect on the pH value in 0.1 mol/L HCl and 0.137 mol/L
HCl, so the main species is H2Saq.
Metals 2019, 9, 294 21 of 27
In what concerns the 2205 DSS, the Na2S concentration up to 3.846 mmol/L could not promote
its corrosion distinctly in 0.1 mol/L HCl solution at 90 °C. However, in 0.137 mol/L HCl solution, the
corrosion of 2205 DSS was extremely accelerated when Na2S concentration reaches only 0.385
mmol/L. On the other hand, 2205 DSS has preserved a stable passivation in hydrochloric acid
solution without Na2S until the HCl concentration increases to 0.584 mol/L. Therefore, it seems that
the combination effect of hydrochloric acid and sodium sulfide has two critical conditions: the first
one is the HCl concentration and the second one is the sodium sulfide addition concentration. The
possible corrosion mechanism of 2205 DSS investigated here is presented in Figure 12. As shown in
Figure 12a, 2205 DSS keeps stable passivation in 0.1 mol/L HCl even if the passive film could be
dissolved in localized area by Cl- attacking. However, in such case the passive film of attacked area
would be repaired fast owing to excellent passivation ability of 2205 DSS. When the concentration of
HCl solution increases, the attacking of Cl- becomes more severe, while the hydrogen reduction is
enhanced. Thus, more defects would appear in the passive film and its stability is apparently
reduced in 0.137 mol/L HCl solution (Figure 12b). This is supported by the suddenly drop of pitting
potential from 0.75 V to 0.4 V in polarization curve measurement (Figure 1a). Figure13c shows the
corrosion mechanism of 2205 DSS in 0.1 mol/L HCl + Na2S solution. The adsorption of S2- and HS-
ions could accelerate the corrosion in some localized areas without passive film protection by
promoting the cathodic reaction of hydrogen reduction as indicated by the decrease of charge
transfer resistance of electrolyte/metal interface with increasing Na2S concentration (R2 of Table 2).
On the other hand, most of the surface is under a stable passive film protection which become more
stable by adding Na2S from as evidenced from the increase of film resistance (R1) (Table 2). This
phenomenon might be attributed to the competitive adsorption of S2- and/or HS- ions to prevent Cl-
attacking passive film. However, as more defects exist in the passive film and surface in 0.137 mol/L
HCl solution, 2205 DSS is not able to keep stable passivation when N2S reaches 0.385 mmol/L. A
Metals 2019, 9, 294 22 of 27
significant degradation process is taking places as described in Figure 12d to Figure 12e. The
hydrogen reduction and anodic dissolution are significant accelerated in early stages at localized
superficial defects. With more and more hydrogen generation and active dissolution sites
expanding, the sample cannot maintain the passivation longer, hence an active dissolution occurred.
As shown in Figure 12e,f, the destruction of passivation can be ascribed to the interaction of
H2S, HS- ion, S2- ion, H+ ion and Cl- ion in defects when of hydrochloric acid and Na2S concentrations
are high enough in the same time. Besides the effect of sulphur species on the adsorption and
reduction of hydrogen on metal surface (Figure 11), H2S, HS- and S2- ions absorbed into surface
defect sites of 2205DSS could form FeS intermediate products [51]. Next, the dissolution of FeS in
hydrochloric acid produces H2S and regeneration of H2S facilitates the corrosion of 2205 DSS. When
H2S and HCl concentrations reach critical values, this process of autocatalysis could accelerate
corrosion remarkably - acidic dissolution happens. At the same time of acidic dissolution, the
promoted diffusion of H into inside trap at grain boundaries causes a dramatic deterioration in
hydrogen induced corrosion resistance. Consequently, grain boundaries are the preferential
corrosion site, severely intergranular corrosion between austenite and ferrite phases combined with
surficial active dissolution are presented.
Metals 2019, 9, 294 23 of 27
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Figure 12. Corrosion mechanism models of 2205 DSS: (a) 0.1 mol/L HCl, (b) 0.137 mol/L HCl, (c) 0.1
mol/L HCl + Na2S, (d) corrosion initiation in 0.137 mol/L HCl + Na2S, (e) initiation and propagation of
localized defect in 0.137 mol/L HCl + 0.385 mmol/L Na2S, (f) corrosion propagation in the entire
surface of 2205 DSS in 0.137 mol/L HCl + 0.385 mmol/L Na2S
5. Conclusions
The corrosion behavior of 2205 DSS in HCl solutions of different concentration with Na2S
additions at 90 °C were investigated using mass loss, potentiodynamic polarization tests, EIS, SKP,
SEM and XPS in this paper and some important points are emphasized as below:
(1) 2205 DSS exhibited high corrosion resistance when HCl concentration was lower than 0.274
mol/L. When 0.385 mmol/L Na2S is added in HCl solution of 0.137 mol/L or higher concentration, the
corrosion resistance of 2205 DSS would be tremendously reduced and active dissolution happens.
(2) The SKP result showed that the surface potential distribution of 2205 DSS obviously
changed after corrosion and the anodic area enlarged. The micromorphology characterization
demonstrated that the intergranular corrosion of 2205 DSS could occur in HCl + Na2S solution, while
it only occurred general corrosion in HCl solution.
(3) The passive film of 2205 DSS in dilute HCl solution with Na2S addition is mainly constituted
of Cr(III) oxide-hydroxides, which have high chemical stability. Thus, the passive film offers
excellent protection for 2205 DSS matrix. In contrast, the corrosion product film formed in active
dissolution is mainly composed of metals (except Fe) oxides and/or hydroxides, sulfides, elemental
sulphur and chlorides.
(4) HS-, S2-ions performed high activities of absorption in HCl solutions on 2205 DSS. In 0.1
mol/L HCl solution, competitive absorption between HS-, S2- and Cl- ions would prevent the
dissolution of passive film. However, in 0.137 mol/L HCl + 0.385 mmol/L Na2S solution, HS- and S2-
ions mainly promoted the process of hydrogen evolution and surface depassivation. The
combination effect of H+, Cl-, HS- and S2- ions would accelerate the active corrosion remarkably when
hydrochloric acid and Na2S concentrations are high enough in the same time.
Author Contributions: Conceptualization, J.T., H.W. and X.Y; methodology, J.T., X.Y.; software, Y.X.;
validation, J.T., Y.W. and H.W.; formal analysis, X.Y. and Y.W.; investigation, X.Y. and Y.X.; resources, Z.N.;
data curation, H.W.; writing—original draft preparation, J.T. and X.Y.; writing—review and editing, H.W.,
M.A. and B.N.; supervision, B.N.; project administration, H.W.; funding acquisition, H.W.
Funding: This research was funded by Scientific Research Innovation Team of Universities Affiliated to Sichuan
Province, grant number 18TD0012, Applied Basic Research Programs of Science and Technology Department of
Sichuan Province, grant number 2017JY0044 and National Science and Technology Major Project, grant number
2017ZX05030-001.
Acknowledgments: The authors thank Dr. Zhanfeng He for the scanning Kelvin probe characterization using
VersaSCAN system in the State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, SWPU.
Metals 2019, 9, 294 25 of 27
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design of the
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to
publish the results.
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