Materials Today Communications 25 (2020) 101649

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Materials Today Communications

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Influence of Ce on the corrosion properties of Fe-Mn-Si-based shape

memory stainless steel
L.F.S. Baroni a, b, *, R. Silva a, b, G.S. Vacchi a, b, V.L. Sordi b, C.A.D. Rovere a, b, *
a
Munir Rachid Corrosion Laboratory, Department of Materials Engineering, Federal University of São Carlos, Rodovia Washington Luis Km 235, 13.565-905 São Carlos,
SP, Brazil
b
Federal University of São Carlos, Graduate Program in Materials Science and Engineering, Brazil

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

Keywords: Among shape memory materials, iron based shape memory alloys are of special interest. Its relative low cost
Fe-Mn-Si encourages mass scale production, such as concrete reinforcement. Metallurgical design of new compositions is
Pitting corrosion abundant, and corrosion resistance must always be a concern. In the present work, the influence of cerium in the
Simulated pore solution
corrosion properties of a Fe-14Mn-4Si-9Cr-4Ni-xCe (x = 0.0, 0.18, 0.42, 0.96) was determined by anodic
Cerium
Electrochemical techniques
potentiodynamic polarization and EIS in simulated pore solution, with 0.6 M NaCl. Results revealed that cerium
is responsible for an improvement in corrosion properties, although there is a threshold where this element
begins to be detrimental.

1. Introduction
Several metallic alloys present the so-called “Shape Memory Effect”
(SME), that is the capability of a body macroscopically deformed in
specific conditions recovering its original shape after heating above a
critical temperature or when exposed to a certain magnetic field [1].
This unique characteristic has driven the scientific community to a
natural interest in expanding their knowledge in these special alloys in
order to promote different applications in various technological areas.
Two well-known shape memory alloys (SMA) commonly used in in­
dustrial applications are the nickel-titanium (Ni-Ti) and copper
(Cu)-based alloys. The first one is the most consolidated and it is able to
recover up to 8% of strain [2]. It is regularly used in many segments from
aerospace to medical devices, because of its high fatigue and corrosion
resistance and because of its high biocompatibility respectively [3,4].
Nevertheless, its high cost is a barrier for some possible applications. On
the other hand, Cu-based alloys present up to 5% of strain recovery [5],
advantages in electrical and thermal conductivities [6], relatively good
corrosion behavior [7] and good processability [8,9]. As drawbacks, one
can mention their usual brittleness and coarse grains [9,10].
The Fe-Mn-Si alloys were developed by Sato and co-workers in the
early 1980’s and it has been greatly improved ever since [11–13]. After
significant development of metallurgical knowledge in these alloys,
chromium (Cr) and Ni are now used to improve the corrosion resistance
of such materials [14–16]. The strain recovery attributed to this family
of alloys is about 4%, which is far lower than NiTi for example [17].
However, the cost of Fe-based SMA is much lower than that of nitinol,
because of their chemical composition and less complex processing
routes, allowing their application in heavier pieces and larger scale. One
example of Fe-based SMA application, still under development, occurs in
reinforcement strands and rebars for concrete prestressing [18–21].
In general, the steel used as concrete reinforcement is resistant to
corrosion as it works in a passive state, in agreement with Pourbaix
diagram’s prediction for iron in alkaline environment, over a wide range
of potential. This means that a stable oxide scale is formed on the steel
surface and protects the bulk metal against the alkaline concrete envi­
ronment [22]. However, when chloride ions are present in the system,
this passivation is quickly degraded, because they promote localized
corrosion by attacking the oxide film, accelerating the corrosion process.
This kind of failure is one of the most important with respect to service
life reduction of concrete structures, considering there are several
chloride sources, i.e. deicing salt, chlorine containing chemical prod­
ucts, contamination of concrete raw material, direct contact with sea
water, etc. [22].
The feasibility of the employing Fe-based SMA as rebars was pre­
sented by Soroushian et al. [23] when applying compressive forces to
minimize the damage caused by cracks in a bridge structure. After that,
many other studies have been carried out and new chemical

* Corresponding authors.
E-mail addresses: luisbaroni@gmail.com (L.F.S. Baroni), carlosdrovere@gmail.com (C.A.D. Rovere).

https://doi.org/10.1016/j.mtcomm.2020.101649
Received 27 April 2020; Received in revised form 24 July 2020; Accepted 7 September 2020
Available online 10 September 2020
2352-4928/© 2020 Elsevier Ltd. All rights reserved.
L.F.S. Baroni et al. Materials Today Communications 25 (2020) 101649

Table 1 was identified.

Chemical composition (wt%) of the experimental SMA. In this work, anodic polarization curves and electrochemical
Mn Si Cr Ni Ce C S Fe impedance spectroscopy (EIS) were used to analyze the effect of Ce
addition on the electrochemical behavior of Fe-14Mn-4Si-9Cr-4Ni in a
Ce-Free 13.50 3.98 9.54 4.51 – 0.029 0.006 68.44
Ce-0.18% 13.47 3.99 9.46 4.57 0.18 0.023 0.007 68.30 pH 13 simulated concrete pore solution, with and without the presence
Ce-0.42% 13.54 4.01 9.50 4.53 0.42 0.019 0.005 67.98 of chloride ions. The electrochemical response of Ce-containing Fe-SMA
Ce-0.96% 13.56 3.95 9.57 4.56 0.96 0.022 0.004 67.37 in alkaline media has not been reported elsewhere, therefore the pur­
pose of the present study is to explore the influence of this rare-earth
element in a wide concentration range. Three different Ce content
compositions, metallurgical mechanisms and applications have been
were studied, 0.18 wt%, 0.42 wt% and 0.96 wt% and the results were
proposed ever since. Dong et al. [24] developed an alloy composition
compared with a Ce free base alloy. This range of Ce content was chosen
containing vanadium and carbon, aiming the austenitic matrix hard­
based on previous positive results from other authors related to its re­
ening by precipitating vanadium carbide (VC). The authors were suc­
ported benefits in shape memory properties [32,33], corrosion behavior
cessful on their premise and the value of the recovery stress for the new
[34] and second phase particle modification [35].
alloy (~500 MPa) was much higher than that of existing Fe-SMA (~200
MPa). Lee et al. [25] developed the usage of VC in Fe-SMA even further,
2. Materials and methods
enabling its application in concrete structures. Practical applications
have also been demonstrated, e.g. the application in “Near Surface
The alloys were prepared in a vacuum induction melting furnace, in
Mounting” [26,27] and “Shotcrete” techniques [28].
an argon saturated atmosphere. The alloy was casted from AISI 304
Nevertheless, some points are still to be clarified in order to make the
stainless steel bars and high purity Fe, Mn, Si, Ni and Ce. Table 1 de­
application of SMA as concrete reinforcement feasible, including the
scribes the chemical composition of the alloys determined by induc­
corrosion behavior of these alloys in alkaline and chloride-containing
tively coupled plasma optical emission spectrometry (ICP-OES). The
environments. The high Mn content leads to the formation of Mn-
ingots were hot rolled at 1200 ◦ C in 2 mm passes and subsequently
containing oxides inclusions (including manganese sulfide), which in
solution-treated at 1050 ◦ C for 2 h followed by water quenching.
turn is responsible for a major increase in localized corrosion suscepti­
The cylindrical samples for microscopy and X-ray diffraction (XRD)
bility [29,30]. The introduction of cerium (Ce) in the bulk chemical
were taken with a wire cutting machine, mounted in polyester resin,
composition intends to reduce this negative effect, and it was substan­
grounded up to #1200-grit silicon carbide abrasive paper and polished
tiated on the benefit that this element exerts on the corrosion resistance
with 1 μm alumina suspension. Etching was performed with Villela’s
of stainless steels. These benefits are due to the formation of a more
Reagent (5 mL HCl +1 mL Picric Acid +100 mL ethanol) to expose the
compact, adhered passive film, and the morphology modification of MnS
microstructure.
from needle to globular shape, reducing the localized attack promoted
For electrochemical evaluation, samples were cold mounted in
by pitting [31]. Moreover, grain refinement, matrix hardening and
polyester resin after an electrical contact was established through a
stacking fault energy reduction are also advantages promoted by Ce
copper wire soldered with tin to the specimen. They were grounded with
addition that will increase SME [32]. So far, no register of usage of Ce in
abrasive paper up to #600-grit. Special attention was taken to avoid
Fe-based SMA for concrete reinforcement application in the literature
crevices between the sample and the resin.

Fig. 1. Microstructure of the experimental SMA captured by optical microscope: (a) Ce-Free (b) Ce-0.18%, (c) Ce-0.42% and (d) Ce-0.96%.

2
L.F.S. Baroni et al.
Fig. 2. Microstructure of the experimental SMA captured by SEM: (a) Ce-Free (b) Ce-0.18%, (c) Ce-0.42% and (d) Ce-0.96%.
The microstructural characterization was performed through XRD to
determine the phases comprising the studied alloys, in a D5005 equip­
ment (Siemens - Germany) operated with Cu Kα at 40 kV and 100 mA and
the sweep angle range (2θ) from 30◦ to 90◦ with scanning speed of 2
◦
/min. The spectrum peaks were determined with an extensive literature
study. Optical microscopy (Olympus BX41M-LED - Japan) and scanning
electron microscopy (Inspect S50 FEI - USA) were performed afterwards.
In the latter case, analyses were made both with and without etching, in
order to observe the phase distribution and precipitated inclusions
characteristics, respectively. Finally, Energy Dispersive Spectroscopy
(EDS) was performed to characterize the chemical composition of the
microstructural constituents.
For testing the shape memory properties, wire samples with 1 mm
diameter were prepared by electro discharge machining and subjected
to bending test using a cylinder tool with 24 mm diameter to deform the
samples. This arrangement results in a 4% strain and the bending was
done at room temperature. The shape recovery ratio was determined by
measuring the returning angles after heating at 600 ◦ C for 10 min.
As previously mentioned, the main purpose of this study is to
determine the electrochemical behavior of Fe-based SMA in alkaline
environment, thus the electrolyte was a buffer solution with pH 13,
composed by 10 mM Na2SO4 + 400 mM KOH + 1 mM Ca(OH)2 [36].
Additionally, another solution was prepared with the same buffer, yet
with the introduction of 3.5% (0.6 M) NaCl, which is an aggressive
condition that can cause the alloy to be susceptible to localized corrosion
[37], specially when sulphate is present in the electrolyte [38]. A con­
ventional three-electrode cell was assembled with Ag/AgCl reference
electrode and a platinum flat plate counter electrode. The exposed area
was 0.3 cm2 and the measurements were taken at room temperature in a
naturally aerated, non-stirred solution. The electrochemical cell was
connected to a potentiostat Reference 3000 (Gamry - USA). The speci­
mens were immersed in solution and subjected to open circuit for one
hour, until stabilization was reached.
3
Materials Today Communications 25 (2020) 101649
The potentiodynamic polarization tests were performed immediately
after one hour of open circuit potential (Eoc) monitoring and carried out
with a sweep rate of 1 mV/s, starting from a potential 300 mVAg/AgCl
below Eoc until film degradation was observed [either by trans­
passivation (absence of Cl− ) or by pitting initiation (presence of Cl− )].
The results were then analyzed using Tafel slope [fitted at ±200 mVAg/
AgCl from corrosion potential (Ecorr)], and electrochemical parameters
were calculated. To observe the pitting formation after potentiodynamic
polarization in chloride containing solution, all surfaces were polished
to a mirror-finish before running the last polarization test and SEM
images were captured.
EIS measurements were performed with a frequency range of 105 to
10− 2 Hz, the sinusoidal potential variation was 10 mVAg/AgCl around Eoc
and the acquisition rate was 10 points per decade. To ensure good
reproducibility, at least three measurements were taken for each sample
and the values presented are the average results.
3. Results and discussion
3.1. Microstructural characterization
Fig. 1 (optical microscope images) and Fig. 2 (SEM images) show the
microstructure of the Fe-SMA samples and one can note a major dif­
ference among the experimental alloys with a reduction of the average
grain size and an increase of second phase particles density as the Ce
content increases in the chemical composition. According to the litera­
ture both microstructural changes influence the pitting corrosion
behavior of ferrous alloy [39,40]. However, besides being ambiguous,
the effect of grain size on corrosion behavior only becomes increasingly
evident with decreasing grain size to values lower than 1 μm (i.e. in
ultrafine-grained structure materials) [41], which is not the case in the
present study. Therefore, our discussion will mainly focus on the effect
of secondary phase particles.
L.F.S. Baroni et al.
Fig. 3. SEM micrographs of oxides, sulfides and intermetallic inclusions along the grain boundaries of ε-martensite and austenite in (a) Ce-0.18%, (b) Ce-0.42% and
(c) Ce-0.96%.
Fig. 4. XRD spectrum of experimental SMA.
With respect to second phase particles, there is an apparent change in
morphology from a round shape to clusters with stretched aspect as a
result of the path of propagation along grain boundaries. Interesting to
observe that for Ce content over 0.18 wt% there is a combination of two,
or even three different compositions in the same cluster. According to
the EDS results presented in Fig. 3, these particles correspond to in­
clusions mainly composed by intermetallic phases and mixed (Fe, Mn,
Si, Ni, Ce) oxides in different stoichiometry, with the brighter structures
in Fig. 3 being richer in Ce. Fe and Ce were the main elements in most
cases. Mixed (Fe, Mn, Si, Ni, Ce) oxy-sulfides were also detected, but in
much lower amount. Different types of inclusions have been reported in
Ce-containing SMA and stainless steels, with the presence of several
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Materials Today Communications 25 (2020) 101649
Fig. 5. Potentiodynamic polarization curves for all SMA samples in simulated
pore solution in the absence of chlorides ions.
alloying elements in chemical composition, either in the form of in­
termetallics, oxides and/or sulfides [42].
Besides the precipitated inclusions, the microstructural composition
is formed mainly by ε-martensite, γ-austenite and α’-martensite, as
shown in the XRD results in Fig. 4. It has been reported that martensite is
more active than austenite phase [43], but since it was not visually
observed a significant discrepancy of phase amounts in the alloys
microstructure, the presence of inclusions should be the main respon­
sible for the electrochemical difference among the alloys.
The differences presented in the microstructures naturally leads to
distinct behaviors regarding shape memory effect. Bending test results
indicate that Ce-0.42% presented the most effective SME with 92% of
L.F.S. Baroni et al. Materials Today Communications 25 (2020) 101649

Table 2 Table 3
Electrochemical parameters obtained in simulated pore solution without chlo­ Electrochemical parameters obtained in the chloride containing pore solution.
ride addition. icorr (μA/ Ecorr (mVAg/ ipass (μA/ Epit (mVAg/
icorr (μA/ Ecorr (mVAg/ ipass (μA/ Etransp (mVAg/ cm2) AgCl) cm2)* AgCl)
cm2) AgCl) cm2)* AgCl)
Ce-Free 0.365 ± − 217 ± 42 10.463 ± 435 ± 46
Ce-Free 0.272 ± − 211 ± 9 2.20 ± 0.10 695 ± 13 0.128 1.728
0.074 Ce- 0.282 ± − 224 ± 20 2.086 ± 0.170 507 ± 50
Ce- 0.284 ± − 217 ± 20 1.77 ± 0.19 698 ± 10 0.18% 0.022
0.18% 0.049 Ce- 1.999 ± − 258 ± 24 8.745 ± 1.252 426 ± 50
Ce- 0.347 ± − 205 ± 15 2.17 ± 0.20 679 ± 13 0.42% 0.149
0.42% 0.059 Ce- 1.142 ± − 206 ± 11 12.760 ± 445 ± 44
Ce- 0.335 ± − 195 ± 8 2.05 ± 0.13 685 ± 3 0.96% 0.777 1.751
0.96% 0.031 *
ipass values were taken at 300 mVAg/AgCl.
*
ipass values were taken at 300 mVAg/AgCl.
electrochemical parameters obtained by Tafel fittings. The anodic po­
larization curves show a transpassive potential (Etransp) around 690
mVAg/AgCl and a passive range (Etransp - Ecorr) of 900 mVAg/AgCl. This
potential is defined by a sudden current increase most probably caused
by the oxygen evolution, according to Pourbaix diagram for water-iron
system, as a result of water decomposition at high anodic potentials [36,
50]. It is also noteworthy in Table 2 that Ce addition is not responsible
for any important changes in icorr and Ecorr, with a total difference of 75
nA/cm2 and 22 mVAg/AgCl respectively. These small differences strongly
imply that the substantial passivation of the metal is the main respon­
sible for the high corrosion resistance in this case. Lee et al. have done
anodic polarization measurements in equivalent simulated pore solution
of an iron-based SMA with the addition of 1 wt% of VC and found Etransp
to be around 500 mVSCE (520 mVAg/AgCl) and Ecorr around -500 mVSCE
(-480 mVAg/AgCl) [36].
The polarization curves analyses obtained with the samples in the
same buffer solution, yet containing 0.6 M of NaCl, is shown in Fig. 6 and
indicates that only Ce-0.18% still presented a high passive behavior,
Fig. 6. Polarization curves for experimental Fe-SMA in pore solution with the suggesting a good stability and high protection property of the surface
addition of chloride ions. film. This fact is supported by the numerical results of the electro­
chemical parameters, shown in Table 3, where it is clear that Ce-0.18%
shape recovery. Ce-Free and Ce-0.18% achieved 72 % and 83 %, shows a significantly lower ipass compared to other samples. It is
respectively, and the results are in agreement with other similar studies important to mention that ipass was arbitrarily taken from the poten­
in the literature [32,33]. However, Ce-0.96% did not present the same tiodynamic curves at 300 mVAg/AgCl. Moreover, Table 3 also reveals an
satisfactory shape memory, with only 67% of recovery. This lower value increase of icorr for Ce-0.42% and Ce-0.96%, suggesting a higher
is assumed to be due to the excess of second phase particles, resulting in corrosion activity in comparison with the solution without chloride ions.
an inhomogeneous microstructure that affects negatively the SME. The highest value of pitting potential (Epit), defined as the break­
down potential of the passive film in chloride containing environment
[51], was obtained from Ce-0.18% sample with 507 mVAg/AgCl, followed
3.2. Potentiodynamic polarization
by Ce-0.96% (445 mVAg/AgCl), Ce-Free (435 mVAg/AgCl) and Ce-0.42%
(426 mVAg/AgCl), being the values of the last three samples quite similar.
Fig. 5 presents the potentiodynamic polarization curves obtained in
It indicates that Ce-0.18% presented a better result, although the overall
solution in the absence of chloride. It is possible to observe that all
difference between the samples is around 80 mVAg/AgCl, which is not
experimental alloys present very similar spontaneous passive behavior
high considering the probabilistic nature of pitting occurrence [52].
because of the high passivity observed for steel in pH 13. This passivity
These results suggest that the addition of 0.18% of Ce enhances corro­
provides an extreme corrosion resistant property as a result of the for­
sion protection, presumably by changing MnS particles morphology and
mation of a protective film, which is an inherent mechanism of corrosion
improving surface film protection, but it is not high enough to constitute
protection of steel in concrete [22]. Although there are different ap­
the particle type that could promote localized corrosion attack. This fact
proaches regarding the formation of such surface film in carbon steel
would explain the similarity in Epit and ipass for Ce-Free, Ce-0.42% and
rebars in alkaline environments, it is rather accepted that it is composed
Ce-0.96%. Indeed, the presence of higher amounts of intermetallics in
by a three-dimensional double layered structure with the inner part of Fe
Ce-0.42% and Ce-0.96% may already be a reason for a decrease in
(OH)2 and mixed iron oxides, such as magnetite (Fe3O4) and the outer
corrosion properties itself [43], since a possible micro galvanic corro­
layer composed of different oxy-hydroxy Fe(III) species, e.g. Fe(OOH)
sion may take place as the inclusions act as micro-cathodes and the
[44,45]. Thus, the degradation of the film should be given with disso­
matrix as micro-anode [39].
lution of Fe(III) in the film-solution interface. When Cr is used as
The obtained values of pitting potential are considerably higher than
alloying element, even in low amount, this surface film becomes more
those found in the literature for carbon steel, such as reported by Moreno
efficient regarding corrosion protection [46–48] due to the presence of
et al. [53]. The authors studied an AISI 1010 in a pH 13.9 with 3.0% Cl−
Cr(III) in the form of oxy-hydroxydes, mostly in the inner layer of the
concentration and stated an Epit of 200 mVSHE (− 22 mVAg/AgCl).
film [49].
Regarding the behavior of an austenitic stainless steel in similar pH but
Both anodic and cathodic behavior, as well as the corrosion potential
higher chloride content (pH = 13; [Cl− ] = 10%), the values of Epit of the
(Ecorr) of all alloys are virtually the same. Fig. 5 shows a slight difference
shape memory alloys are considerably lower, as Freire et al. reported
in the passive current density of Ce-0.18% in relation to other samples,
values of around 520 mVSHE (540 mVAg/AgCl) for an AISI 304 steel [46].
as it can be seen numerically in Table 2, which also contains the

5
L.F.S. Baroni et al.
Fig. 7. SEM micrographs of the pits formed on the experimental Fe-SMA after potentiodynamic polarization tests in pore solution with the addition of chloride ions:
(a) Ce-Free; (b) Ce-0.18%; (c) Ce-0.42% and (d) Ce-0.96%.
Fig. 8. Nyquist plots obtained from electrochemical impedance spectroscopy
for the experimental alloys without chloride addition. Dashed lines represent
the fitting results obtained from EEC.
Since Ce has high affinity with oxygen, it forms a more stable anodic
film reducing its reactivity by obstructing active surface sites [54,55].
Additionally, it promotes the formation of Ce-sulfides in the bulk metal,
changing the distribution and shape of MnS inclusions [56,57]. Few
studies have assessed the effect of small amounts of cerium and other
rare-earth metals (REM) addition in the oxide film of high alloyed steels,
e.g. Jinzhu et al. (0.015 < REM wt% < 0.1) [58], Kim et al. (0.011 < Ce
wt% < 0.14) [59] and Kim et al. (0.005 REM wt%) [56]. It was a
consensus that it has a benign effect on corrosion properties, caused by a
significant reduction in inclusions size and number, decreasing the
interface between the substrate and the inclusions, which are prefer­
ential sites for pitting initiation. Moreover, inclusions containing REM, i.
e (Mn, Cr, Si, Ce)-oxides, have higher corrosion resistance than the in­
clusions of alloys without REM, namely (Mn, Cr) sulfides, (Mn, Cr, Fe,
Si)-oxides and (Mn, Cr, Fe) oxy-sulfides [56].
Fig. 7 presents the surface morphology of the experimental Fe-SMA
after the potentiodynamic polarization test. It can be observed that
pits in Ce-0.42% and Ce-0.96% were initiated in the inclusion interfaces
that behave as active sites for Cl− local attack. In Ce-Free and Ce-0.18%
alloys the pits were mainly located on ε-martensite stacks or grain
6
Materials Today Communications 25 (2020) 101649
Fig. 9. Nyquist plots obtained from electrochemical impedance spectroscopy
for the experimental alloys with chloride addition. Dashed lines represent the
fitting results obtained from EEC.
boundaries, and it is possible to notice the martensitic structure on the
pit bottom walls, indicated by arrows.
3.3. Electrochemical impedance spectroscopy
The results from EIS confirm the corrosion properties obtained from
anodic polarization measurements. The Nyquist plots in Figs. 8 and 9
show the capacitive semi-arcs for all Fe-SMA in both solutions, without
and with the addition of chloride ions, respectively. It is possible to
observe that the presence of Cl− is responsible for a reduction in the
impedance values for all samples. Ce-0.18% showed once again the best
result, with only a small drop in impedance, whilst Ce-0.42% and Ce-
0.96% showed a very pronounced reduction. Ye et al. [60] have studied
the Cl− threshold concentration of reinforcement carbon steel on
simulated pore solution at which the corrosion starts to increase at
significant levels. The authors reported that above 0.01 M of NaCl in
solution the semi-arcs of the studied alloys shrunk rapidly. This con­
centration is considerably inferior to the one used in the present work
(0.6 M) and Ce-Free and Ce-0.18% did not show such an extreme
reduction, demonstrating a good local corrosion resistance even in high
chloride containing environments.
L.F.S. Baroni et al. Materials Today Communications 25 (2020) 101649

Fig. 10. Electrical equivalent circuit used to analyze the EIS plots of the experimental alloys.

Table 4
EIS parameters obtained from EEC for the studied alloys in solution without chloride ions.
Rs (Ω.cm2) Rf (103 Ω.cm2) Qf (10¡6(S.sa)/cm2) af Rct (103 Ω.cm2) Qdl (10¡6(S.sa)/cm2) adl X2
4
Ce-Free 39.5 ± 0.3 146.2 ± 33.2 32.7 ± 0.42 0.91 ± 0.00 81.1 ± 43.1 39.1 ± 54.5 0.82 ± 0.30 3.91⋅10−
4
Ce-0.18% 30.2 ± 0.2 83.4 ± 22.4 26.7 ± 0.6 0.90 ± 0.00 129.6 ± 29.1 35.8 ± 33.9 0.80 ± 0.17 5.10⋅10−
4
Ce-0.42% 31.3 ± 0.2 86.3 ± 18.6 33.1 ± 0.6 0.90 ± 0.00 80.4 ± 23.7 43.9 ± 42.7 0.83 ± 0.19 3.37⋅10−
4
Ce-0.96% 31.1 ± 0.2 67.9 ± 17.4 27.8 ± 0.7 0.89 ± 0.00 116.2 ± 22.4 34.7 ± 26.1 0.79 ± 0.13 3.39.10−

Table 5
EIS parameters from EEC for the studied alloys in solution with chloride ions.
Rs (Ω.cm2) Rf (103 Ω.cm2) Qf (10¡6(S.sa)/cm2) af Rct (103 Ω.cm2) Qdl (10¡6(S.sa)/cm2) adl X2
4
Ce-Free 3.5 ± 0.0 2.7 ± 2.5 37.5 ± 2.8 0.90 ± 0.01 140.6 ± 5.7 9.2 ± 2.6 0.75 ± 0.03 2.7⋅10−
4
Ce-0.18% 3.6 ± 0.0 83.5 ± 44 30.7 ± 0.42 0.93 ± 0.00 132.4 ± 5.7 11.7 ± 1.1 0.64 ± 0.19 3.3⋅10−
4
Ce-0.42% 3.4 ± 0.0 7.9 ± 5.4 29.8 ± 1.1 0.93 ± 0.00 31.6 ± 6.9 23.4 ± 8.4 0.424 ± 0.08 2.5⋅10−
4
Ce-0.96% 3.6 ± 0.0 7.9 ± 9.8 30.1 ± 1.4 0.93 ± 0.01 42.9 ± 11.9 17.5 ± 8.4 0.421 ± 0.08 3.8⋅10−

The reduction in impedance corresponds to a proportional decrease
in Rp [45], which could be explained by a loss of protectiveness of the
passive film resulting from chloride ions activity, making it unstable
with local breakdowns through pitting formation. In the case of
Ce-0.42% and Ce-0.96%, it was demonstrated that the inclusion-matrix
interface is a potential pit initiation site, making it more susceptible to
local corrosion. In Fig. 9 it is also possible to observe a pronounced
destabilization of Ce-0.42% and Ce-0.96% samples curves at lower fre­
quencies. This part of the impedance curves corresponds to the charge
transfer reactions occurring in the interface between the infiltrated
electrolyte through the film defects and the uncovered metal surface
[61], confirming the worse protective effect of the passive film on these
experimental alloys.
The quantitative evaluation of the film-electrolyte interface was
carried out by choosing an equivalent electrical circuit (EEC), proposed
by extensive literature of analogue systems [60–62] and presented in
Fig. 10. The fitting results are given in Figs. 8 and 9 as dashed lines in the
respective curves.
Two time constants were used to describe the double layered struc­
ture of the interface since the alloys are in passive state. Many authors
addressed this EEC to describe steel rebars in simulated pore solutions,
but the physical description of the individual elements is still in con­
troversy considering that more than one approach can be stated [46]. In
the present work, the high frequency time constant (Qf,Rf) describes the
external oxy-hydroxy Fe(III) layer-electrolyte interface, related with
redox reactions. The low frequency time constant (Qdl,Rct) is associated
to the barrier property of the passive film and its related defects, where
Qdl stands for the double layer capacitance and Rct for the charge
transfer resistance. A constant phase element (CPE) was used
alternatively to the capacitor on the EEC, owing to the heterogeneities of
the non-ideal surface. Its impedance may be described as ZCPE = [Q
(jω)a]− 1 where Q is a parameter related to capacitance, j is the imaginary
unit, ω is the frequency and a is the parameter indicating the deviation of
capacitive linearity [63]. If a = 1, CPE should describe an ideal capac­
itor, while if a = 0.5 it indicates a Warburg impedance with diffusional
attribute. Finally, Rs represents the solution resistance.
The results originated from the fitting of EIS spectra are presented in
Tables 4 and 5 and corroborate with the electrochemical potentiody­
namic outcomes. Considering that Ce-Free and Ce-0.18% exhibit higher
charge transfer resistance and lower double layer capacitance, they
should present higher overall corrosion resistance.
Table 5 shows that Ce-0.42% and Ce-0.96% presents a≈0.5, sug­
gesting a diffusional process of ions and oxygen vacancies in the passive
film [62,64], affecting the redox reactions occurring in the film-solution
interface.
Hence, in what regards the corrosion results presented in this work, it
is possible to state that the addition of 0.18% of Ce in the chemical
composition of Fe-Mn-Si-Cr-Ni stainless steel should bring advantages in
the passivity when used as concrete reinforcement.
4. Conclusions
Based on the microstrucuture observation and the results of the
electrochemical tests of the Fe-based SMA in alkaline solution with and
without the addition of chlorides, the following conclusions can be
drawn:

7
L.F.S. Baroni et al.
• There is an important similarity in the electrochemical behavior
among all studied alloys in the alkaline solution in the absence of
chloride, indicating a complete spontaneous passivation in high pH
solution.
• In the solution containing 0.6 M of NaCl, the corrosion current
density increased in one order of magnitude for samples Ce-0.42%
and Ce-0.96%. Moreover, pitting potential of Ce-0.18% was consid­
erably higher than the other samples.
• Epit of Ce-Free, Ce-0.42% and Ce-0.96% were similar because the
benefits of Ce addition are no longer present over 0.42%, and the
sample with 0.18% presents the best results.
• Regarding pitting formation, the inclusion-matrix interface is a po­
tential initiation site, so the alloys with higher amounts of Ce (0.42%
and 0.96%) are thus more susceptible to localized corrosion.
• Potentiodynamic polarization and impedance measurements
confirm that among the selected Ce content alloys, Ce-0.18% is the
best one regarding corrosion properties in chloride containing
simulated pore solution. The electrochemical parameters indicate
that it presents the best results considering icorr, Epit and Rp.
• Still some points must be clarified before application tests, such as
stress corrosion cracking behavior as well as long-term immersion
tests taking into account the concrete carbonation process. These
issues should be verified by our research group on future works.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
This study was financed in part by the Coordenação de Aperfeiçoa­
mento de Pessoal de Nível Superior - Brasil (CAPES) – Finance Code 001.
Also, the authors gratefully acknowledge the Brazilian research funding
agencies CAPES (Federal Agency for the Support and Improvement of
Higher Education) and CNPq (National Council for Scientific and
Technological Development – grant no. 140233/2015-6 and 311163/
2017-3), as well as the Postgraduate Program in Materials Science and
Engineering of the Federal University of São Carlos (PPGCEM/UFSCar),
for their financial support of this work.
References
[1] J. Mohd Jani, M. Leary, A. Subic, M. Gibson, A review of shape memory alloy
research, applications and opportunities, Mater. Des. 56 (2014) 1078–1113,
https://doi.org/10.1016/j.matdes.2013.11.084.
[2] J.N. Lemke, A. Coda, DSC and microstructure analysis of high temperature Ni-Ti-
Hf, low hysteresis Ni-Ti-Cu and conventional super-elastic and shape memory Ni-Ti
alloy ingots and wires, Mater. Today Commun. 21 (2019), 100666, https://doi.
org/10.1016/j.mtcomm.2019.100666.
[3] C. Maletta, E. Sgambitterra, F. Furgiuele, R. Casati, A. Tuissi, Fatigue properties of
a pseudoelastic NiTi alloy: strain ratcheting and hysteresis under cyclic tensile
loading, Int. J. Fatigue 66 (2014) 78–85, https://doi.org/10.1016/j.
ijfatigue.2014.03.011.
[4] W. Huang, Shape Memory Alloys and Their Application to Actuators for
Deployable Structures, Ph.D. Thesis, University of Cambridge, 1998, http://www.
ntu.edu.sg/home/mwmhuang/cambridge/Phd2side.pdf.
[5] L. Huijun, The Development of New Iron Based Shape Memory Alloys, Ph.D.
Thesis, University of Wollongong, 1996, http://ro.uow.edu.au/theses/1523.
[6] T. Tadaki, Cu-based shape memory alloy. Shape Memory Materials, 1st ed.,
Cambridge University Press, Cambridge, UK, 1999, pp. 97–116.
[7] S.N. Saud, E. Hamzah, T. Abubakar, Correlation of microstructural and corrosion
characteristics of quaternary shape memory alloys Cu-Al-Ni-X (X = Mn or Ti),
Trans. Nonferrous Met. Soc. China. 25 (2015) 1158–1170, https://doi.org/
10.1016/S1003-6326(15)63711-6.
[8] T. Gustmann, J.M. dos Santos, P. Gargarella, U. Kühn, J. Van Humbeeck, S. Pauly,
Properties of Cu-Based shape-memory alloys prepared by selective laser melting,
Shape Mem. Superelasticity 3 (2017) 24–36, https://doi.org/10.1007/s40830-016-
0088-6.
[9] R. Dasgupta, A.K. Jain, P. Kumar, S. Hussain, A. Pandey, Role of alloying additions
on the properties of Cu-Al-Mn shape memory alloys, J. Alloys. Compd. 620 (2015)
60–66, https://doi.org/10.1016/j.jallcom.2014.09.047.
[10] S.N. Saud, E. Hamzah, T. Abubakar, S. Farahany, A. Abdolahi, M.M. Taheri,
Influence of Ag nanoparticles addition on the phase transformation, mechanical
8
Materials Today Communications 25 (2020) 101649
properties and corrosion behaviour of Cu-Al-Ni shape memory alloys, J. Alloys.
Compd. 8388 (2014) 471–478, https://doi.org/10.1016/j.jallcom.2014.05.173.
[11] A. Sato, E. Chishima, K. Soma, T. Mori, Shape memory effect in g-e transformation
in Fe-30Mn-1Si alloy single crystals, Acta Metall. 30 (1982) 1177–1183, https://
doi.org/10.1016/0001-6160(82)90011-6.
[12] A. Sato, Y. Yamaji, T. Mori, Physical properties controlling shape memory effect in
FeMnSi alloys, Acta Metall. 34 (1986) 287–294, https://doi.org/10.1016/0001-
6160(86)90199-9.
[13] A. Sato, E. Chishima, Y. Yamaji, T. Mori, Orientation and composition
dependencies of shape memory effect in Fe-Mn-Si alloys, Acta Metall. 32 (1984)
539–547, https://doi.org/10.1016/0001-6160(84)90065-8.
[14] H. Otsuka, H. Yamada, T. Maruyama, H. Tanahashi, S. Matsuda, M. Murakami,
Effects of alloying additions on Fe-Mn-Si shape memory alloys, ISIJ Int. 30 (1990)
674–679, https://doi.org/10.2355/isijinternational.30.674.
[15] K. Tsuzaki, Y. Natsume, Y. Tomota, T. Maki, Effect of solution hardening on the
shape memory effect of Fe-Mn based alloys, Scr. Metall. Mater. 33 (1995)
1087–1092, https://doi.org/10.1016/0956-716X(95)00337-U.
[16] C. Zhao, Improvement of shape memory effect in Fe-Mn-Si-Cr-Ni alloys, Metall.
Mater. Trans. A. 34 (1999) 2599–2604, https://doi.org/10.1007/s11661-999-
0299-y.
[17] W.J. Lee, B. Weber, G. Feltrin, C. Czaderski, M. Motavalli, C. Leinenbach, Phase
transformation behavior under uniaxial deformation of an Fe-Mn-Si-Cr-Ni-VC
shape memory alloy, Mater. Sci. Eng. A 581 (2013) 1–7, https://doi.org/10.1016/
j.msea.2013.06.002.
[18] A. Cladera, B. Weber, C. Leinenbach, C. Czaderski, M. Shahverdi, M. Motavalli,
Iron-based shape memory alloys for civil engineering structures: an overview,
Constr. Build. Mater. 63 (2014) 281–293, https://doi.org/10.1016/j.
conbuildmat.2014.04.032.
[19] L. Janke, C. Czaderski, M. Motavalli, J. Ruth, Applications of shape memory alloys
in civil engineering structures - Overview, limits and new ideas, Mater. Struct. 38
(2005) 578–592, https://doi.org/10.1617/14323.
[20] L. Kang, D. Zhizhong, L. Yongchang, Z. Lin, A newly developed Fe-based shape
memory alloy suitable for smart civil engineering, Smart Mater. Struct. 22 (2013),
45002, https://doi.org/10.1088/0964-1726/22/4/045002.
[21] A. Cladera, E. Oller, C. Ribas, Pilot experiences in the application of shape memory
alloys in structural concrete, J. Mater. Civ. Eng. 26 (2014), 04014084, https://doi.
org/10.1061/(ASCE)MT.1943-5533.0000974.
[22] J.P. Broomfield, Corrosion of Steel in Concrete: Understanding, Investigation and
Repair, 2nd ed., Taylor and Francis, Oxfordshire, 2006 https://doi.org/10.4324/
9780203414606.
[23] P. Soroushian, K. Ostowari, A. Nossoni, H. Chowdhury, Repair and strengthening
of concrete structures through application of corrective posttentioning forces with
shape memory alloy, Transp. Res. Rec. 1770 (2001) 20–26.
[24] Z. Dong, U.E. Klotz, C. Leinenbach, A. Bergamini, C. Czaderski, M. Motavalli,
A novel Fe-Mn-Si shape memory alloy with improved shape recovery properties by
VC precipitation, Adv. Eng. Mater. 11 (2009) 40–44, https://doi.org/10.1002/
adem.200800312.
[25] W.J. Lee, B. Weber, G. Feltrin, C. Czaderski, M. Motavalli, C. Leinenbach, Stress
recovery behaviour of an Fe–Mn–Si–Cr–Ni–VC shape memory alloy used for
prestressing, Smart Mater. Struct. 22 (2013), 125037, https://doi.org/10.1088/
0964-1726/22/12/125037.
[26] C. Czaderski, M. Shahverdi, R. Brönnimann, C. Leinenbach, M. Motavalli,
Feasibility of iron-based shape memory alloy strips for prestressed strengthening of
concrete structures, Constr. Build. Mater. 56 (2014) 94–105, https://doi.org/
10.1016/j.conbuildmat.2014.01.069.
[27] M. Shahverdi, C. Czaderski, M. Motavalli, Iron-based shape memory alloys for
prestressed near-surface mounted strengthening of reinforced concrete beams,
Constr. Build. Mater. 112 (2016) 28–38, https://doi.org/10.1016/j.
conbuildmat.2016.02.174.
[28] M. Shahverdi, C. Czaderski, P. Annen, M. Motavalli, Strengthening of RC beams by
iron-based shape memory alloy bars embedded in a shotcrete layer, Eng. Struct.
117 (2016) 263–273, https://doi.org/10.1016/j.engstruct.2016.03.023.
[29] C.A.D. Rovere, J.H. Alano, R. Silva, Pa P. Nascente, J. Otubo, S.E. Kuri, Influence of
alloying elements on the corrosion properties of shape memory stainless steels,
Mater. Chem. Phys. 133 (2012) 668–673, https://doi.org/10.1016/j.
matchemphys.2012.01.049.
[30] K. Park, H. Kwon, Effects of Mn on the localized corrosion behavior of Fe-18Cr
alloys, Electrochim. Acta 55 (2010) 3421–3427, https://doi.org/10.1016/j.
electacta.2010.01.006.
[31] A.J. Sedriks, Corrosion of Stainless Steels, 2nd ed., John Wiley & Sons, New York,
1996.
[32] C. Zhao, G. Liang, C. Li, Z. Jin, Influence of cerium, titanium and nitrogen on shape
memory effect of Fe-Mn-Si-Cr-Ni alloys, Scr. Mater. 38 (1998) 1163–1168, https://
doi.org/10.1016/S1359-6462(98)00019-0.
[33] X. Huang, Y. Lei, B. Huang, S. Chen, T.Y. Hsu, Effect of rare-earth addition on the
shape memory behavior of a FeMnSiCr alloy, Mater. Lett. 57 (2003) 2787–2791,
https://doi.org/10.1016/S0167-577X(02)01375-7.
[34] X. Huang, S. Chen, T.Y. Hsu, X. Zuyao, Corrosion behavior of Fe25Mn6Si5Cr shape
memory alloys modified with rare earth in a NaCl solution, J. Mater. Sci. 39 (2004)
6857–6859, https://doi.org/10.1023/b:jmsc.0000045620.49206.6a.
[35] Y. Qu, J. Xing, X. Zhi, J. Peng, H. Fu, Effect of cerium on as-cast mictrostructure of
a hypereutectic high chromium cast iron, Mater. Lett. 62 (2008) 3024–3027,
https://doi.org/10.1016/j.matlet.2008.01.129.
[36] W.J. Lee, R. Partovi-Nia, T. Suter, C. Leinenbach, Electrochemical characterization
and corrosion behavior of an Fe-Mn-Si shape memory alloy in simulated concrete
L.F.S. Baroni et al.
pore solutions, Mater. Corros. 67 (2016) 839–846, https://doi.org/10.1002/
maco.201508701.
[37] R.R. Hussain, A. Alhozaimy, A. Al-Negheimish, D.D.N. Singh, Time-dependent
variation of the electrochemical impedance for thermo-mechanically treated versus
plain low alloy steel rebars in contact with simulated concrete pore solution,
Constr. Build. Mater. 73 (2014) 283–288, https://doi.org/10.1016/j.
conbuildmat.2014.09.099.
[38] G. Liu, Y. Zhang, Z. Ni, R. Huang, Corrosion behavior of steel submitted to chloride
and sulphate ions in simulated concrete pore solution, Constr. Build. Mater. 115
(2016) 1–5, https://doi.org/10.1016/j.conbuildmat.2016.03.213.
[39] Y. Liu, Z. Dong, L. Yu, Y. Liu, H. Li, L. Zhang, Influence of aging on shape memory
effect and corrosion resistance of a new Fe–Mn–Si-based alloy, J. Mater. Res. 29
(2014) 2809–2816, https://doi.org/10.1557/jmr.2014.363.
[40] K.D. Ralston, N. Birbilis, Effect of grain size on corrosion: a review, Corrosion 66
(2010) 0750051–07500513, https://doi.org/10.5006/1.3462912.
[41] H. Miyamoto, Corrosion of ultrafine grained materials by severe plastic
deformation, an overview, Mater. Trans. 57 (2016) 559–572, https://doi.org/
10.2320/matertrans.M2015452.
[42] C. Liu, R.I. Revilla, Z. Liu, D. Zhang, X. Li, H. Terryn, Effect of inclusions modified
by rare earth elements (Ce, La) on localized marine corrosion in Q460NH
weathering steel, Corros. Sci. 129 (2017) 82–90, https://doi.org/10.1016/j.
corsci.2017.10.001.
[43] B.C. Maji, C.M. Das, M. Krishnan, R.K. Ray, The corrosion behaviour of Fe-15Mn-
7Si-9Cr-5Ni shape memory alloy, Corros. Sci. 48 (2006) 937–949, https://doi.org/
10.1016/j.corsci.2005.02.024.
[44] M. Sánchez-Moreno, H. Takenouti, J.J. García-Jareño, F. Vicente, C. Alonso,
A theoretical approach of impedance spectroscopy during the passivation of steel
in alkaline media, Electrochim. Acta 54 (2009) 7222–7226, https://doi.org/
10.1016/j.electacta.2009.07.013.
[45] E. Volpi, A. Olietti, M. Stefanoni, S.P. Trasatti, Electrochemical characterization of
mild steel in alkaline solutions simulating concrete environment, J. Electroanal.
Chem. 736 (2015) 38–46, https://doi.org/10.1016/j.jelechem.2014.10.023.
[46] L. Freire, M.J. Carmezim, M.G.S. Ferreira, M.F. Montemor, The electrochemical
behaviour of stainless steel AISI 304 in alkaline solutions with different pH in the
presence of chlorides, Electrochim. Acta 56 (2011) 5280–5289, https://doi.org/
10.1016/j.electacta.2011.02.094.
[47] M.C. García-Alonso, M.L. Escudero, J.M. Miranda, M.I. Vega, F. Capilla, M.
J. Correia, M. Salta, A. Bennani, J.A. González, Corrosion behaviour of new
stainless steels reinforcing bars embedded in concrete, Cem. Concr. Res. 37 (2007)
1463–1471, https://doi.org/10.1016/j.cemconres.2007.06.003.
[48] I.G. Ogunsanya, C.M. Hansson, The semiconductor properties of passive films and
corrosion behavior of stainless steel reinforcing bars in simulated concrete pore
solution, Materialia 6 (2019), 100321, https://doi.org/10.1016/j.
mtla.2019.100321.
[49] C.M. Abreu, M.J. Cristóbal, R. Losada, X.R. Nóvoa, G. Pena, M.C. Pérez,
Comparative study of passive films of different stainless steels developed on
Materials Today Communications 25 (2020) 101649
alkaline medium, Electrochim. Acta 49 (2004) 3049–3056, https://doi.org/
10.1016/j.electacta.2004.01.064.
[50] Marcel Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions, 2nd ed.,
National Association of Corrosion Engineers, Michigan, 1974.
[51] S.H. Jeon, S.T. Kim, M.S. Choi, J.S. Kim, K.T. Kim, Y.S. Park, Effects of cerium on
the compositional variations in and around inclusions and the initiation and
propagation of pitting corrosion in hyperduplex stainless steels, Corros. Sci. 75
(2013) 367–375, https://doi.org/10.1016/j.corsci.2013.06.020.
[52] K.V. Akpanyung, R.T. Loto, Pitting corrosion evaluation: a review, J. Phys. Conf.
Ser. 1378 (2019), 022088, https://doi.org/10.1088/1742-6596/1378/2/022088.
[53] M. Moreno, W. Morris, M.G. Alvarez, G.S. Duffó, Corrosion of reinforcing steel in
simulated concrete pore solutions effect of carbonation and chloride content,
Corros. Sci. 46 (2004) 2681–2699, https://doi.org/10.1016/j.corsci.2004.03.013.
[54] Y.C. Lu, M.B. Ives, Chemical treatment with cerium to improve the crevice
corrosion resistance of austenitic stainless steels, Corros. Sci. 37 (1995) 145–155,
https://doi.org/10.1016/0010-938X(94)00126-Q.
[55] Y.C. Lu, M.B. Ives, The improvement of localized corrosion resistance of stainless
steel by cerium, Corros. Sci. 34 (1993) 1773–1785, https://doi.org/10.1016/0010-
938X(93)90015-9.
[56] S.T. Kim, S.H. Jeon, I.S. Lee, Y.S. Park, Effects of rare earth metals addition on the
resistance to pitting corrosion of super duplex stainless steel - Part 1, Corros. Sci. 52
(2010) 1897–1904, https://doi.org/10.1016/j.corsci.2010.02.043.
[57] C.K. Gupta, N. Krishnamurthy, Extractive metallurgy of rare earths, Int. Mater.
Rev. 37 (1992) 197–248, https://doi.org/10.1179/imr.1992.37.1.197.
[58] G. Jinzhu, F. Paixian, L. Hongwei, L. Dianzhong, Effects of rare earth on the
microstructure and impact toughness of H13-Steel, Metals (Basel) 5 (2015)
383–394, https://doi.org/10.3390/met5010383.
[59] S.M. Kim, J.S. Kim, K.T. Kim, K.T. Park, Y.S. Park, C.S. Lee, Effect of Si and Ce
addition on the microstructure and pitting corrosion resistance of hyper-duplex
stainless steels, Corrosion 71 (2015) 470–482, https://doi.org/10.5006/1380.
[60] C.Q. Ye, R.G. Hu, S.G. Dong, X.J. Zhang, R.Q. Hou, R.G. Du, C.J. Lin, J.S. Pan, EIS
analysis on chloride-induced corrosion behavior of reinforcement steel in
simulated carbonated concrete pore solutions, J. Electroanal. Chem. 688 (2013)
275–281, https://doi.org/10.1016/j.jelechem.2012.09.012.
[61] Y.H. Yoo, Y.S. Choi, J.G. Kim, Y.S. Park, Effects of Ce, La and Ba addition on the
electrochemical behavior of super duplex stainless steels, Corros. Sci. 52 (2010)
1123–1129, https://doi.org/10.1016/j.corsci.2009.12.016.
[62] M. Sánchez, J. Gregori, C. Alonso, J.J. García-Jareño, H. Takenouti, F. Vicente,
Electrochemical impedance spectroscopy for studying passive layers on steel rebars
immersed in alkaline solutions simulating concrete pores, Electrochim. Acta 52
(2007) 7634–7641, https://doi.org/10.1016/j.electacta.2007.02.012.
[63] C.A.D. Rovere, J.H. Alano, R. Silva, Pa P. Nascente, J. Otubo, S.E. Kuri,
Characterization of passive films on shape memory stainless steels, Corros. Sci. 57
(2012) 154–161, https://doi.org/10.1016/j.corsci.2011.12.022.
[64] K. Darowicki, S. Krakowiak, P. Ślepski, Evaluation of pitting corrosion by means of
dynamic electrochemical impedance spectroscopy, Electrochim. Acta 49 (2004)
2909–2918, https://doi.org/10.1016/j.electacta.2004.01.070.