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Effects of NaCl Concentration on Wear-corrosion Behavior of SAF

2507 Super Duplex Stainless Steel

RSC Advances Accepted Manuscript

Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
a, b a a,* a,*
Gaofeng Han , Pengfei Jiang , Jianzhang Wang , Fengyuan Yan
Wear-corrosion behavior of SAF 2507 super duplex stainless steel (SDSS) in different concentration of NaCl (0.5% to 8%,
w/v) was investigated by using a pin-on-disk tester. Friction coefficient and mass loss rate were determined and
meanwhile the synergistic effect of wear and corrosion was analyzed by tribocorrosion-related parameters. It was
indicated that wear-corrosion regimes were significantly influenced by NaCl concentration and the related mechanism
was attributed to the two different phases inside SAF 2507. Self-protection behavior between the two phases inside SAF
2507 led to significantly different wear-corrosion mechanism, as comparing to the single-phase metal. To the best of our
knowledge, this is the first study about wear-corrosion behavior of SAF 5207 inside solution with different corrosivity.
This research provided a new sight for researchers to look into the tribocorrosion behavior of alloys with different
phases, and helped us to better understand the principle that we should follow when alloys employed in corrosive
environment was developed.

particular conditions. Generally, wear could reduce the pitting

1. Introduction
Wear-corrosion process of metal in electro conductive media
1
is influenced by properties of immersed media , such as salt
2 3 4 5, 6
concentration , dissolved oxygen , pH and temperature ,
etc. Sodium chloride (NaCl) solution is one kind of typical
electro conductive media which could destroy the dense oxide
layer formed by chromium (Cr) and nickel (Ni) in stainless
7-9
steels (SS) containing these elements . Particularly, NaCl can
10
make austenitic stainless steels stress corrosion cracking .
Meanwhile, NaCl solution could also cause pitting corrosion
when the concentration reached the minimum limit, which
11, 12
was determined by intrinsic properties of metal . For
example, Co1.5CrFeNi1.5Ti0.5Mo0.1 alloy is susceptible to >1M
13
NaCl solution at 25 °C . Under normal circumstances, ferritic
stainless steels (such as 430 SS) were less corrosion resistant
than austenitic stainless steels (such as 304 SS). It was found
that pitting corrosion of 430 SS occurred at a critical chloride
11 −
concentration of 4 M . However, concentration of Cl for the
initiation of pitting corrosion for 304 SS is around 6 M at room
11, 14
temperature . This was normally due to the different
15
phases and elements content in the two metals .
Furthermore, wear-corrosion behavior of different metals
under different concentration of NaCl was more complicated.
Wear-corrosion behavior was determined by the combined
effect of wear and corrosion behavior of metal under
16
potential of metals and accelerated the corrosion rate . On
the contrary, sometimes corrosion could inhibit the wear loss
of metal, which was due to lubricity of corrosion product. For
example, Corrosion of Co-Cr could protect the matrix from
17
erosion . The wear loss rate of 304 SS reduced after corrosion
18, 19
due to the lubricity of solution and corrosion product .
Super duplex stainless steel (SDSS) has two-phase
(α-ferrite phase and γ-austenite phase) organization and it
combines high tensile and impact strength with a low
coefficient of thermal expansion and high thermal conductivity
7, 20
. In general, SDSS is defined as duplex stainless steel (DSS)
with a pitting resistance equivalent of 40-45 and it has a higher
20-22
pitting corrosion resistance . And due to the high pitting
resistance, SDSS was widely used in harsh corrosion condition
23
such as ocean engineering, oil and gas industry, etc. .
Because of the complicated structure, corrosion resistance of
SDSS depends on the actual chemical composition strongly.
22
Lee et al. studied the open circuit potential (OCP) of SDSS
and found it was more active compared with the separate
α-ferrite phase and γ-austenite phase, which was due to a
number of phase boundaries with variations in alloying
elements to affect the corrosion behaviors. In SDSS, the main
alloying elements (Cr, Mo, Ni and N) are not equally
distributed in ferrite and austenite. The austenite mainly
consists of Ni and N, while the ferrite mainly consists of Cr and
Mo. The different distribution of these elements affected
21, 24-26
corrosion resistance of the entire alloy . In aggressive
−
solution contained Cl , pitting corrosion usually took place
15
preferentially in ferrite phase rather than austenite phase .
27
Moser et al. found that S32304 exhibited low corrosion
−
susceptibility when the concentration of Cl was 0.5 M, but
−
S32205 was resistant to corrosion at 1.0 M Cl . Von der Ohe et

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al. found that wear-corrosion synergistic effect of SDSS was Figure 1 Schematic diagram of wear-corrosion tester
higher than that of austenite stainless steel. In a word, 2.2. Tribocorrosion tests
wear-corrosion behavior of SDSS under different concentration
The schematic diagram of tribo-electrochemical tester used in
of NaCl solution was significantly different from ferritic
this study is shown in Figure 1. It was reformed by combining a
stainless steel and austenitic stainless steel, the more careful
tribometer (MMW-1, Jinan, P.R. China) with an
and detailed research need to be conducted for better
electrochemical workstation (CHI 760C, Shanghai CH
understanding the correlation between material properties
Instruments, P.R. China). The wear-corrosion behavior of SAF
and wear-corrosion behavior.
2507 was studied in different NaCl solution with mass fraction
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In this context, the wear-corrosion behavior of SAF 2507

ranging from 0.5% to 8% (correspondence between salinity
SDSS was studied by changing the concentration of NaCl
and conductivity of different concentration of NaCl was shown
solution. The synergism of wear-corrosion was investigated in
in Table 1). The applied load was 54N and the sliding velocity
the solutions employing various electrochemical

RSC Advances Accepted Manuscript

was 0.25 m/s. The OCP variation curves of SAF 2507 were
measurements and scanning electron microscopy (SEM). The
tested before, during and after sliding. The potentiodynamic
wear-corrosion regimes were obtained by calculation
polarization measurements were performed by changing the
according to ASTM G119-09 29. In addition, Raman spectra,
potential automatically from – 1000 to 0 mV versus OCP with a
contact angles and hardness of worn surfaces in different NaCl -1
scan rate of 10 mV·s . And that the potential rang under
solution were also obtained to analyze the wear-corrosion
friction was – 600 to + 400 mV with the same scan rate. All
behavior. To the best of our knowledge, this is the first study
tests were conducted at room temperature. The variations of
about wear-corrosion behavior of SAF 5207 immersed in 2
current density (icorr, mA/cm ) were monitored before, during
different NaCl solution, which indicated that self-protection
and after sliding at different applied potentials. In addition,
behavior inside SDSS showed significant influence on
cathodic protection technology with a protect potential which
wear-corrosion regimes. This research provided a new sight for
was 0.5 V negative to the open circuit potential (OCP) to
researchers to look into the tribocorrosion behavior of alloys 30
eliminate electrochemical corrosion . The friction coefficient
with different phases, and helped us to better design the
and mass loss rate were obtained by weighing method.
metallic materials employed in the corrosive environment.

Table 1 Correspondence between salinity and conductivity of different concentration of

NaCl
2. Experimental
2.1. Materials NaCl
0.5 2.0 3.5 5.0 6.5 8.0
The material used in this work is SAF 2507 (UNS S32750) (wt %)
1
supplied by Sandmeyer Steel Company and its chemical Salinity
5.1 20.8 36.9 53.3 65.72 78.62
(‰)
composition is 0.02 C, 25.00 Cr, 7.00 Ni, 4.00 Mo, 0.27 N and
balance Fe in mass fraction. The ring samples of SAF 2507 with Conductivity1
9.1 33.3 55.7 76.8 97.1 116.2
(mS/cm)
outer diameter 54 mm and inner diameter 38 mm was shown
in Figure 1. A protected layer of polyurethane was sprayed to 1 They were tested by Cond 1970i portable conductivity meter by WTW,
the area which was not employed for the tribocorrosion Germany.
experiment. The surface for wear corrosion was ground with
2 The marked values were calculated by linear fitting of salinity-conductivity.
SiC grinding papers from grade 180 to 1500, then degreased
and cleaned ultrasonically by acetone and dried. The rotating All tests were performed three times under the identical
pin was made of alumina (99% in purity) with a diameter of 4.7 conditions and the result was reported as mean ± standard
mm. deviation. The mass loss rates during wear-corrosion were
29 31
calculated according to ASTM G119-09 and G102 . The
parameters which were employed for determine the
wear-corrosion regimes were calculated according to the
equation shown in supplementary information (Eq.1 to Eq.13).
2.3. Characterization of worn surface
Contact angles of worn surfaces were measured by optical
contact angle measuring device (DSA 100, Kruss, USA) and
Raman spectra were characterized by Labram HR Evolution
Raman Spectrometer (Horiba scientific, France). Hardness of
the worn surfaces was tested by a Vickers micro-hardness
tester (MH-5-VM, PR China). Moreover, the morphologies of
the worn surfaces and etched cross-section were examined by
scanning electron microscope (SEM, JEOL 5600, Japan). And
the roughness of the worn surfaces was measured by 2206
surface roughness tester (Links, China). The metallographic

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TM
morphologies were etched by ElectroMet 4 polisher etcher
(Buehler, USA) after mechanical polishing. The electroetching
was applied 5 V for 5 s in 400 g/L NaOH solution.

3. Results
3.1. Electrochemical response
Figure 2a showed open circuit potential (OCP) evolution with
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time of SAF 2507 immersed in different NaCl solution. The OCP

was measured before, during and after sliding motion. It was
found that sliding motion caused a sudden decrease in OCP,
which was attributed to damage of passive film and following

RSC Advances Accepted Manuscript

exposure of naked metal surface to NaCl solution. This
32-38
phenomenon has been described in many other metals .
Once the sliding motion stopped, the passive film was able to
recover in time, therefore a significant increase of OCP was
16
observed . Meanwhile, it was found that OCP of SAF 2507
dispersed in higher concentration of NaCl solution showed a
lower value, which means corrosion was accelerated with NaCl
1
concentration increasing .
In order to characterize pure mechanical wear loss rate, a
negative potential was applied to all samples, which would
efficiently inhibit the corrosion process (cathodic protection)
thus the whole mass loss was only attributed to sliding motion.
Figure 2b showed that sliding motion led to a sudden decrease
in current density and it was negative in whole process, which
represented that sliding motion induced mechanical loss. After
the sliding motion stopped, current density increased to about
– 0.5mA. Since this was similar as the original value before the
sling motion started, it meant that mass loss stopped as the
sliding motion stopped under the cathodic protection.
As shown in Figure 2c, sliding motion made the corrosion
potential decrease significantly, which made the Tafel slopes
move to the left side of graph. Besides, it was found that
increasing NaCl concentration also led to drop of corrosion
potential. Therefore, it was indicated that mechanical sliding
and higher NaCl concentration both promoted corrosion
process. The corrosion potential quantified from Figure 2c was
shown in Figure 2d. When SAF 2507 was under cathodic
protection, it was indicated that corrosion potentials in static
state and with wear decreased linearly in the range of 0.5% ~ 8%
and the protected potential was determined by the corrosion
potential with wear minus 0.5 V. Moreover, corrosion rate
increased linearly with increasing of concentration of NaCl by
functions of C0 =0.00101ωNaCl +8.19E-5 without wear and
Cw =0.02914ωNaCl +0.19055 with wear. It was clearly that the corrosion
rate changed faster under wear than that without wear. It was
because of the increasing of corrosiveness of solutions and
friction accelerated corrosion rate. And friction had an
accelerated effect obviously compared to the solutions of
increasing NaCl.

Figure 2 Electrochemical characterization of tribocorossion behavior of SAF 2507

dispersed in 0.5%, 2%, 3.5%, 5%, 6.5% and 8% (w/v) NaCl solution. (a) Variations of OCP

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during the tribocorrosion study. (b) Time-current curve during tribocorrosion study (c)
Potentiodynamic polarization curves (dotted line was obtained before sliding and solid
line was obtained after 30 min steady sliding) and (d) corrosion potentials under
tribocorrosion or cathodic protection.
3.2. Friction and wear
Furthermore, friction coefficient and mass loss rate of SAF
2507 under wear-corrosion (tribocorrosion) or cathodic
protection (pure mechanical wear) in different NaCl solution
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were characterized. As shown in Figure 3a, friction coefficient
of tribocorrosion and pure mechanical wear decreased with
increasing NaCl concentration. It has been reported that NaCl
solution accelerated formation of surface oxide layer and thus
reduced friction coefficient 39. So friction coefficients reduced
with the increasing NaCl concentration. Furthermore, when
NaCl concentration was ranging from 0.5% to 5%, friction
coefficients of SAF 2507 under tribocorrosion were obvious
lower than that under cathodic protection, which was due to
lubricity of corrosion products 9, 39, 40. When the concentration
was 6% and 8%, the friction coefficients were quite similar,
which was due to the lubricity of NaCl solution because of the
corrosion had little effect on the friction 9.
Figure 3 Coefficient of friction (a) and mass loss rate (b) of SAF 2507 in different NaCl
solution.
Analysis of Laser Raman Spectrum of worn surfaces of SAF
2507 showed that there were three kinds of iron oxide
(α-Fe2O3, α-FeOOH and γ-FeOOH as shown in Figure 4a)
formed during the tribocorrosion process. And it clearly
showed that the oxides increased with the increase of NaCl
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due to the increasing peak intensity. It was the increasing
corrosion strength of NaCl solutions and the main factor of
reducing. In addition, contact angle (shown in Figure 4b) of
worn surfaces showed that higher NaCl concentration
significantly increase the hydrophobicity of the surface.
Contact angles were related to many factors, such as
roughness, contamination, surface heterogeneity, surface
41-43
deformation, solution concentration and other factors .
The relationship between contact angle and friction
coefficients was studied before and it was indicated that
fricition coefficient decreased with increase of contact angles
44, 45
due to weaker intermolecular interactions . Moreover,
RSC Advances Accepted Manuscript
Figure 3b shows wear loss rate of tribocorrosion was
decreased firstly (0.5% ~ 2%) and then increased suddenly
(3.5%) followed with the decreasing (3.5% ~ 8%) but higher
than that of 0.5% and 2%. However, pure mechanical wear
rate decreased with the increasing of NaCl concentration.
There was an inflection point at 3.5% which indicated that
wear-corrosion regime changed.
Figure 4 The laser Raman spectra (a) and contact angles (b) of worn surfaces of SAF
2507 in different NaCl solution.
In addition, Figure 5 showed the hardness of the worn
surfaces, which decreased along with increasing NaCl
concentration. This was due to the denser oxide layer under
higher NaCl concentration.
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Figure 5 Micro-hardness of worn surfaces of SAF 2507 in different NaCl solution.

3.3. Synergy analysis

Figure 6 Synergetic contributions of mechanical wear and corrosion to each other and
total mass loss of SAF 2507 in different NaCl solution.

In order to further determine the wear-corrosion regimes of

SAF 2507 under different conditions, parameters such as W0,
ΔWc, C0, ΔCw and S were calculated according to the equation
in SI. Figure 6a,c showed that pure mechanical wear rate (W0)
decreased with increasing NaCl concentration, which was due
9
to the increasing lubrication effect . And the increased wear
rate due to corrosion (ΔWc) was negative when NaCl
concentration was ranging from 0.5% to 2%. The negative ΔWc
meant that wear loss was inhibited. This was due to lubricity of
corrosion products and protection of oxides film on the worn
17, 18
surface . ΔWc was positive when the concentration
increased to 3.5%, which meant that corrosion accelerated the
wear loss. And ΔWc decreased from 3.5% to 8%, which was
9, 39,
due to lubricity of NaCl solutions and its corrosion products
40
. Meanwhile, C0 (corrosion rate without wear) and ΔCw
(increasing corrosion rate due to wear) both increased with
increasing NaCl concentration. The C0 increase meant that
higher NaCl concentration induced more serious corrosion,
which has been proved in many metals 46, 47. However, C0 was
almost negligible compared to wear, which was due to high
corrosion resistance of SAF 2507 because of formation of the
oxide layer 39. ΔCw was also significantly larger than C0, which
was a special property of passive materials compared to
non-passive materials because of corrosion after removing of
passive films increased was much larger than corrosion of

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39, 47, 48
passive film . W0+C0 (sum of W0 and C0) and S (sum of mechanical behavior. However, lubricity of NaCl and corrosion
the interactions between corrosion and wear) of SAF 2507 products interaction reduced wear-corrosion rate at 8%. It had
shown in Figure 6d had a similar trend of W0 and ΔWc shown in the lowest friction coefficient and wear loss rate at the range
Figure 6a, respectively. This phenomenon was due to the high of 5% ~ 8%. Hence the wear-corrosion rate would reduce due
proportion of W0 and ΔWc (Figure 6c), which meant that this to the increase of corrosion within certain limits.
wear-corrosion process was wear loss dominate. Moreover, the corrosion had a critical value that between
3.4. Microstructure analysis synergistic effect and antagonistic effect based on the analysis
of synergism in Figure 6c and the Figure 7c and 7d were also
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shown the revulsion on the worn surfaces.

RSC Advances Accepted Manuscript

Figure 8 The roughness of worn surfaces of 2507 SDSS in different NaCl solution

4. Discussion
Corrosion augmentation factor (1+ΔCw/C0), wear
augmentation factor (1+ΔWC/W0) and total synergism factor
(T/(T-S)) were further determined to better understand the
wear-corrosion regimes. As was shown in Figure 9a, corrosion
augmentation factor decreased with increasing NaCl
concentration. As NaCl concentration increased, the lubricity
9, 18
of NaCl solution was improved , therefore area of
mechanically re-passivated surface was small and the
increment of corrosion rate due to wear was low. It was
indicated that increasing NaCl solution led to the result that
Figure 7 SEM morphologies of worn surface of SAF 2507 in different NaCl solution.
corrosion without wear (C0) increased more than 10 times but
the increment of corrosion due to wear (ΔCw) increased only 2
times. This result was completely different from 304 SS in
Surface microstructure was further characterized to 18
artificial seawater with different halide concentration . Zhang
analyze the wear-corrosion mechanism under different
et al. reported that as NaCl concentration increased, corrosion
condition. As shown in Figure 7a, 7b and Figure 8, there was 18
of 304 SS increased slowly but the ΔCw increased rapidly .
no significant difference on the worn surface in 0.5% and 2%
The difference of corrosion between 304 SS and SAF 2507 was
NaCl. Grooves were observed on the surfaces in solutions
mainly due to the better corrosion resistance of SAF 2507 than
more than 2% NaCl. Pits and cracks were obviously shown on 48
304 SS . Besides, wear augmentation factor and total
the worn surface of SAF 2507 in 3.5% NaCl solution. According
synergism factor were much smaller than corrosion
to the wear-corrosion results (Figure 3b), it had been indicated
augmentation factor, which meant that wear due to corrosion
that 3.5% NaCl with wear showed the most significant mass
increased in percentage was lower than that of corrosion
loss, thus the surface was rougher than that under all the
changed due to wear.
other conditions (Figure 7c, 8). With the increase of NaCl
concentration at a range of 5% ~ 8%, the surfaces had the
same cracks and grooves. It was due to the close corrosion and
lubricity effect on the wear-corrosion 47. Compared with
hardness of the worn surface showed in Figure 5, they were
similar to each other, indicated that the surface had same

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Figure 9 Synergistic effect and wear-corrosion regimes of SAF 2507 in different NaCl
solutions.
When the NaCl concentration was 0.5% and 2%, the total
synergism factor in was larger than 1, which meant that
29, 49
synergistic effect was negative . Negative synergism
occurred when the corrosion product during wear provides
better protection than the initial surface. The values of ΔCw
/ΔWc under 0.5% and 2% were less than zero (as shown in
Figure 9b). It meant that corrosion product dissolved and thus
29
inhibited wear loss . This phenomenon also led to decrease
of wear augmentation factor. Once the concentration
increased to 3.5%, the higher corrosivity of NaCl led to pitting
27, 47
corrosion . Therefore, wear augmentation factor increased
immediately, and the total synergism factor decreased
suddenly from 2% to 3.5%. The values of ΔCw /ΔWc was in the
range of 0 ~ 0.1 at 3.5% to 6.5%, it was synergistic dominate
which meant that corrosion was affecting wear to a great
29
extent than wear was affecting corrosion . Therefore, from
3.5%, the total synergism factor increased and approached to
1 until 8%, which meant that there was nearly no interaction
50
between corrosion and wear . The value of ΔCw /ΔWc was
more than 0.1 in the 8% NaCl solution and this process was
additive-synergistic dominate which meant that the “additive”
and “synergistic” interactions were equal and corrosion
29
affecting wear was close to wear affecting corrosion .
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Figure 10 Schematic diagram of self-protect mechanism (the cross-section of unworn
RSC Advances Accepted Manuscript
surface of SAF 2507).
As was known, one of the most important driving force
for corrosion is the potential difference between two or more
metals or alloys in the conductive medium, which generates
51-53
current flow between the anodic and cathodic members .
When it occurred between the phases with different potentials
in one metal, corrosion would be also affected. It has been
proved that the different phases in Mg–Al–Zn–Mn alloy under
cell culture media condition had a “self-protection”
phenomenon owing to redistribution of the cathodic β phases
54
compared to anodic α-Mg phases . SAF 2507 SDSS has two
phases which have different corrosion potentials. When
immersed in corrosive solutions, γ phase was protected by α
7, 22
phase due to the higher corrosion potential of γ phase
(Figure 10). As shown in Figure 10, it is very clearly shown the
possibility and process of self-protected effect attributed to
the two phases have different elements and non-uniform
21
distribution . When the concentration was low (0.5% ~ 2%),
the wear rate was inhibited because of the protection
behavior of γ phase. That is why corrosion inhibited wear loss.
Compared to 0.5%, 2% NaCl solution has better lubricity, which
led to significant decrease of the total mass loss rate. As the
concentration increased to 3.5%, corrosion broke through the
critical limit to destroy the surface and enhance the wear rate.
Thus there was sudden change in the mass loss rate at 3.5%.
When the concentration was higher than 3.5%, the
self-protection effect of different phases was so weak that
wear and corrosion accelerated each other and synergistic
effect occurred. And when the concentration of NaCl was 8%,
corrosion rate was maximized and the regimes of
wear-corrosion changed to additive-synergistic.
5. Conclusions
In this paper, the effect of NaCl concentration on
tribocorrosion behavior for SAF 2507 SDSS was studied on a
pin–on–disc tribometer and the obtained results of
investigation could lead to the following conclusions:
1. Within the entire studied range of NaCl concentration (0.5%
~ 8%), corrosion was claimed to be accelerated by wear. Wear
was claimed to be inhibited first (0.5%~ 2%), which was due to
the self-protection behavior of SAF 2507. Then wear-corrosion
rate was accelerated (3.5%~ 8%) by corrosion but reduced as
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the NaCl concentration increased. The wear-corrosion rate 11.
reached maximum at 3.5%.
2. In all conditions, wear-corrosion behavior of SAF 2507 was 12.
modulated by self-protection behavior, the lubricity and
13.
corrosivity of NaCl solution and the surface properties. The
self-protection behavior was influenced by NaCl concentration,
14.
which was divided into two parts: protective effect (0.5%~2%)
and no protection (3.5%~8%).The wear-corrosion regimes of 15.
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S. Hastuty, A. Nishikata and T. Tsuru, Corrosion Science,
2010, 52, 2035-2043.
T. Wan, N. Xiao, H. Shen and X. Yong, Ultrasonics
Sonochemistry, 2016, 33, 1-9.
Y. L. Chou, J. W. Yeh and H. C. Shih, Corrosion, 2011, 67,
065003-1-065003-7.
T. Suter, E. G. Webb, H. Böhni and R. C. Alkire, Journal
of The Electrochemical Society, 2001, 148, B174.
L. F. Garfias-Mesias, J. M. Sykes and C. D. S. Tuck,

SAF 2507 can be divided into three parts depending on NaCl Corrosion Science, 1996, 38, 1319-1330.
concentration: antagonistic (0.5%~2%), synergistic 16. Y. Zhang, X. Yin, J. Wang and F. Yan, Corrosion Science,
(3.5%~6.5%) and additive-synergistic (8%). 2014, 88, 423-433.
3. Self-protection behavior of two phases in SAF 2507 was 17. M. M. Stack and T. M. A. E. Badia, Wear, 2006, 261,

RSC Advances Accepted Manuscript

found to be the most important factor for modulating 1181-1190.
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