Materials Chemistry and Physics 126 (2011) 602–606

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Materials Chemistry and Physics

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Anomalous corrosion resistance behavior of Mo-containing SS in alkaline media:

The role of microstructure
Thiago J. Mesquita a,b , Eric Chauveau b , Marc Mantel b , Nicole Kinsman c , Ricardo P. Nogueira a,∗
a
UMR 5631 INP Grenoble-CNRS-UJF, LEPMI, BP 75, 38402 St. Martin d’Hères, France
b
CRU Ugitech, Av Paul Girod 73400 Ugine, France
c
International Molybdenum Asociation, IMOA W4 4JE London, United Kingdom

a r t i c l e i n f o a b s t r a c t

Article history: Electrochemical and microscopy techniques were used to investigate the role of the microstructure in
Received 21 May 2010 the corrosion behavior of Mo-containing stainless steel grades in alkaline chloride rich media. It is shown
Received in revised form 25 October 2010 that under certain conditions, Mo containing grades can be even less corrosion resistant than Mo free
Accepted 8 January 2011
ones. This anomalous behavior is straightforwardly related to the austenite phase. On the other hand,
results show that Mo confirms its clearly beneficial effect in ferritic and duplex steels. Current transient
Keywords:
analysis indicated that the protection mechanism in those cases appears to be related to an inhibited pit
Alloy
initiation rather than faster repassivation kinetics.
Corrosion
SEM © 2011 Elsevier B.V. All rights reserved.
Metals

1. Introduction Mo alloys for alkaline service conditions. It is worth noticing how-

In the last few years, strong fluctuations and a net increasing ten-
dency of the price of several important alloying elements yielded
much effort from the major stainless steel suppliers to propose new
technological solutions that minimize the use or even eliminate
those alloying elements (mainly nickel and molybdenum) in the
composition of special grades. This at least partially explains the
appearance of new less expensive alloys like lean duplex stainless
steels on the market [1,2]. In general the use of Mo-free or low
Mo content alloys is now sometimes extended into service con-
ditions for which formerly Mo-containing alloys would have been
used. This development is mostly due to economic reasons inas-
much as the role of Mo is still not fully understood. This lack of
scientific knowledge concerning the role of Mo can be illustrated
by a fundamental disagreement in the literature as to whether Mo
is a component of passive films [3,4] or not [5–7].
The consequences of a more widespread use of these alloys are
difficult to predict. Indeed, it is true that the positive role of Mo in
acidic media can be considered as generally accepted [8–10]. In the
case of alkaline media, however, the role of Mo is much less studied.
Some previous studies have pointed out that in certain conditions
Mo has no beneficial effect on the pitting corrosion resistance of
stainless steels [11,12], which could thus justify abandoning high
∗ Corresponding author at: LEPMI, 1130, rue de la Piscine, Domaine Universitaire,
BP 75, 38402 St. Martin dı̌Hères, France. Tel.: +33 04 76 82 65 93.
E-mail addresses: ricardo.nogueira@lepmi.grenoble-inp.fr,
ricardo.nogueira@enseeg.inpg.fr (R.P. Nogueira).
ever that those results were limited to austenitic steels in some
specific conditions [12] or were based upon preliminary laboratory
observations [11].
The aim of the present paper is to characterize the behav-
ior of different Mo-containing and Mo-free austenitic, ferritic and
duplex stainless steels exposed to chloride rich alkaline media.
These conditions are particularly relevant to coastal or off shore
rebar applications or alkali industries.
2. Experimental
In a first set of experiments, several industrial grades of stainless steel were
investigated in the present study: austenitic 304 and 316, ferritic 430 and 434 and
duplex 2304 and 2205, the nominal compositions of which are given in Table 1.
It can be seen that for each microstructure, the only major difference was the Mo
content (0.21 and 2.17 wt.% for the austenitic grades, and 0.05 and 0.92 wt.% for
the ferritic 0.28 and 2.78 wt.%for the duplex). The others elements for each grade
at most slightly varied so that the corrosion resistance difference for steels with
the same microstructure could only be reasonably attributed to this presence or
“absence” of Mo. Nevertheless, to reinforce this interpretation based on Mo content
differences, specially prepared laboratory duplex grades for which strictly only Mo
concentration varied (0.02 and 3.00 wt.%, see Table 2) were also investigated.
Samples (2.5 cm2 ) were polished till 1200 grid emery paper, degreased with
alcohol, washed with distilled water and dried with hot air. Electrochemical mea-
surements were performed in a classical three-electrode electrochemical cell with
a large surface Pt grid as the counter-electrode and a saturated calomel (SCE) as the
reference one. The anodic polarization curves were performed after 1 h of immersion
in the electrolyte at 1 mV s−1 scan rate from 30 mV below open circuit potential up
to 100 ␮A cm−2 current density. Metastable pit transients were acquired at 500 Hz
sample frequency after proper anti-aliasing filtering [13].
The base electrolyte was a 0.025 M NaHCO3 + 0.025 M Na2 CO3 ·10H2 O + 0.6 M
NaCl solution at 25, 50 and 75 ◦ C and at several pHs in the 0.6–12 range adjusted
with HCl or NaOH droplets. In what follows results will be presented at 25 ◦ C, only.
The other temperatures gave qualitatively equivalent results.

0254-0584/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2011.01.013
 T.J. Mesquita et al. / Materials Chemistry and Physics 126 (2011) 602–606 603

Table 1
Nominal composition of the industrial grades investigated.

Industrial material Elements (wt.%)

C Si Mn Ni Cr Mo Cu N Co Sa P

Austenitic 304 0.02 0.49 0.60 11.12 18.29 0.21 0.31 0.03 0.00 9 0.00
316 0.01 0.49 0.73 11.08 16.89 2.17 0.48 0.03 0.25 10 0.03
Ferritic 430 0.01 0.31 0.30 0.29 16.16 0.05 0.10 0.03 0.02 5 0.02
434 0.03 0.39 0.39 0.45 16.17 0.92 0.12 0.05 0.03 23 0.02
Duplex 2304 0.02 0.41 1.09 4.02 22.30 0.28 0.30 0.15 0.13 4 0.02
2205 0.02 0.4 1.61 5.45 22.91 2.78 0.22 0.15 0.07 3 0.02
a
S ppm.

Table 2
Nominal composition of the laboratory prepared duplex grades investigated.

Laboratory material Elements (wt.%)

C Si Mn Ni Cr Mo Cu N V Sa P

Duplex 2304 0.03 0.58 1.03 4.57 22.97 0.02 0.01 0.18 0.01 12 0.01
2205 0.03 0.56 0.98 4.56 22.97 3.00 0.01 0.19 0.01 13 0.01
a
S ppm.

3. Results and discussion
Fig. 1a and b shows typical polarization curves obtained for 304
and 316 SS at extreme pH conditions (0.6 and 12, respectively). As
largely accepted, the figure illustrates the huge positive effect of Mo
on the corrosion resistance of austenitic grades in acidic environ-
ments. Indeed, in those harsh conditions (pH 0.6), 304 steel shows
no passive behavior and corrodes already at open circuit potential
whilst 316 shows a clear passivation plateau and a pitting poten-
tial (Epit ) of about 200 mVsce (Fig. 1a). As the pH was made less
acidic both the 304 and the 316 showed the expected increase
of Epit values. In the alkaline domain, however, the Mo-free 304
becomes surprisingly more resistant than the 316 as seen in Fig. 1b
(Epit = 460 mVsce and 620 mVsce for 316 and 304, respectively). It
seems that, for these austenitic grades, there is a monotonic loss
of Mo effect as the pH increases as already pointed out in some
previous studies [11,12]. Indeed, the Epit difference between the
316 and 304, monotonically decreased with the pH increase from

Fig. 1. Polarization curves obtained for the different grades. (A) 304 () and 316 () at pH 0.6; (B) 304 () and 316 () at pH 12; (C) 430 () and 434 () at pH 10; (D) 2304
() and 2205 () at pH 10. The current increase up from ca. 840 mVsce for the 2205 grade is due to oxygen evolution and not pitting.
604 T.J. Mesquita et al. / Materials Chemistry and Physics 126 (2011) 602–606

Fig. 2. Polarization curves obtained for Mo-free 2304 () and Mo-containing 2205 () laboratory prepared samples at pH 4.0, 7.0 and 10.0 at 25 ◦ C. 2205 samples only showed
oxygen evolution and no pitting.

+450 (pH 0.6) to −160 mV (pH 12), negative values indicating that
the Mo-free alloy became more resistant than the Mo-containing
316 as seen in Fig. 1b. This anomalous behavior could be tenta-
tively related to the reaction mechanism associated to the effect of
Mo, for instance a pH dependent state of charge that could allow
Cl− trapping by Mo cations in acidic solutions [14] but not in alka-
line media. However, these mechanistic insights are still far from
being fully researched and understood, as mentioned before and
are beyond the aim of the present paper.
In a first glance, these first results seem to validate the idea
that Mo is not functional in alkaline media, at least not with
respect to localized corrosion resistance. Moreover, since austenite
is intrinsically more corrosion resistant than ferrite in most ser-
vice conditions, it could be assumed, that the effect discussed from
Fig. 1a and b equally applies to ferritic and duplex SS. This hasty con-
clusion is however incorrect. Indeed, at very acidic pH, the ferritic
steels corroded intensively, as did the 304. The main difference is
that, for neutral and alkaline media, the Epit difference between the
Mo-containing and the Mo-free ferritic grades does not decrease
with increasing pH but oscillated between +20 and +90 mV in the
pH range studied, whilst as mentioned before, the austenitic grade
difference monotonically decreased. Fig. 1c and d illustrates this
issue with the help of polarization curves obtained at pH 10 for the
ferritic and duplex alloys (at pH 12 duplex grades have shown no
pit at all). It clearly appears that, unlike in austenitic grades, Mo
has a positive effect on their corrosion resistance in alkaline envi-
ronments (all graphs in Fig. 1 are just typical examples of quite
reproducible behaviors: on average the presence of Mo increased
the pitting potential about 50 mV for the ferritic and more than
150 mV for the duplex grades). This seems to indicate that Mo does
have a protective role in alkaline media, but that it is mostly related
to the improvement of the corrosion resistance of the ferrite phase.
These results are indeed self-consistent in the sense that if ferrite
had also shown the anomalous behavior in alkaline media shown
by austenite, it would not be possible to understand why duplex
could still behave better in the presence of Mo if its two constituting
microstructures behaved in the opposite way. It is worth noticing
that in this sense, the present study brings a new insight that can
help understanding the beneficial role of Mo in the corrosion resis-
tance of different grades. Indeed, unlikely to Refs. [11,12] (limited
to austenitic [12] or austenitic and duplex [11] grades at different
pH values), the present paper dealt with different microstructures
and showed that Mo effects remain positive at alkaline media for
ferritic and duplex grades.
As mentioned before, the previous results have been obtained
from industrial grades, that, although having equivalent composi-
tions as shown in Table 1, could convey differences that could be
also at the origin of these distinct corrosion resistance behaviors
(there were indeed some small differences as for instance the Ni
content, even if not more than 1.5%). In this sense, we have also
proceeded to complementary tests on laboratory prepared duplex
alloys for which the effective compositions were fully controlled so
that absolutely only the Mo content varied, the others remaining
strictly constant as depicted in Table 2. Fig. 2 illustrates the typical
corrosion resistance behavior of the Mo containing and free grades
of the laboratory prepared SS, confirming the positive Mo role on
the pitting corrosion resistance of these alloys. Indeed, for the three
pH values studied, the Mo containing grades showed no pitting
whilst the Mo-free samples always presented localized attacks up
from potential values depending on the pH solution.
Fig. 3 shows SEM pictures of pits in industrial duplex SS under
different conditions. The left picture shows that in acidic media,
in the absence of Mo, pits are initiated and propagated mostly at
the ferrite phase from which grains appeared to be completely dis-

Fig. 3. Back scattered SEM images from corrosive attacks on different samples. Left: 2304 at pH 0.6 showing austenite (lighter) grains left after ferrite (darker) grains have
been dissolved. Middle: 2304 at pH 10; pit initiation at the ferrite (darker) phase. Right: 2205 at pH 10; pit initiation at the austenite (lighter) phase.
 T.J. Mesquita et al. / Materials Chemistry and Physics 126 (2011) 602–606
Fig. 4. Back scattered electrons SEM images from 2205 at pH 10. Left: ferrite (darker) phase pins down the pit growth that attacks preferentially the austenite (lighter) phase.
Right: zoom of pit propagation inside the austenite phase.
solved whilst austenite grains remained much less attacked. In the
presence of Mo, however, pit propagation is strongly hindered in
the ferrite phase and the attack appeared to split between the two
phases. Results are however more pronounced in alkaline media. In
the absence of Mo, pits are, as expected, initiated in the less resistant
ferrite phase (Fig. 3, middle). On the other hand, in the presence of
Mo, the scenario is reversed. The ferrite becomes much more resis-
tant and pits were now almost exclusively located at the austenite
grains, as seen in Fig. 3, right. After continuing corrosion attack, the
ferrite phase definitely shows better corrosion resistance as shown
in Fig. 4. Indeed, the periphery of the big pit reveals an attack pro-
file characterized by the preferential hammering of the austenite
phase whilst the ferrite grains seem to locally pin down the pit
propagation (Fig. 4, left). In the right side a more zoomed picture
clearly shows that the pit is not only initiated at the austenite but
also propagates inside it before eventually eating into the adjacent
ferrite. The same behavior has been observed in the case of the
laboratory prepared grades.
This indirect evidence of the role of Mo is confirmed by a met-
allurgical analysis. A calculation of each phase composition using
Thermocalc® software confirmed that for the 2205 steel, Mo is pref-
erentially dissolved into the ferrite phase (3.2%) that hence has its
corrosion resistance improved compared to the austenite phase
which contains less Mo (2.0%). More importantly, this better fer-
rite behavior cannot be ascribed to different Cr contents in 2304
and 2205 steel since their Cr contents were roughly the same (pre-
cisely 23.7 and 20.1 and 24.0 and 20.5 for ferrite and austenite and
2304 and 2205, respectively). Results obtained from Thermocalc®
have been complemented by both energy dispersive spectrome-
ter (EDS) and wavelength-dispersive spectrometer (WDS) as seen
in Table 3.Values are in full agreement with those obtained from
theoretical estimations and confirm the preferential Mo dissolu-
tion in ferrite. It is also worth noticing that the enhanced corrosion
resistance of the ferrite phase can of course drastically change in
the presence of sigma phase precipitates. The austenite phase is in
these conditions left at the rear of the corrosion front whilst the
ferrite phase is preferentially attacked [15].
Table 3
Thermocalc® calculations and EDS and WDS measurements of the Mo and Cr com-
position in austenite and ferrite for the industrial duplex grades.
Method Sample Phase Elements (wt.%)
Cr
Thermocalc 2304 ␣ 25.19
␥ 20.41
2205 ␣ 25.32
␥ 20.34
EDS 2304 ␣ 24.35
␥ 21.09
2205 ␣ 24.57
␥ 20.25
WDS 2304 ␣ 24.55
␥ 20.75
2205 ␣ 25.06
␥ 21.29
605
These results indicate that the Mo role is more likely to be
ascribed to some prior-to-the-attack metallurgical effects rather
than to post-attack interfacial kinetic processes, like those related
to Mo cations interactions with electrolyte anions. Indeed, if the
Mo effect was related to chemical or electrochemical interactions
of Mo cations with the electrolyte, pH changes should have more
or less the same impact regardless of the allotropic form, which
is clearly not the case as presented before. Those later interfacial
effects have been proposed to be at the origin of enhanced repas-
sivation kinetics [14], which can be expected to yield smaller time
constants of the repassivation transient after a metastable pit ini-
tiation, for instance. Fig. 5 shows two typical current transients
– shifted to have the same arbitrary time origin – associated to
metastable pits taking place at 430 and 434 surfaces at pH 12 and
polarized to +500 mV with respect to their open circuit potential.
The repassivation (represented by the current decay after reach-
ing a maximum) appears quite steep in both cases, thus illustrating
equivalent repassivation kinetic in the absence and in the presence
of Mo. On the other hand, the pit initiation (related to the current
increase) seems to be slowed down in the presence of Mo, showing
effectively a much less pronounced current increase profile (higher
time constant) represented by a rise time up to the maximum of
about 0.7 s for the 430 and 2.3 s for the 434 as well as a lower tran-
sient amplitude. This would effectively mean that the role of Mo
should not be related to the way it accelerates repassivation but
mostly to how it inhibits pit initiation. Another point deserving
specific mention is related to the wide use of the so-called pitting
resistance equivalent number, PREN, calculation to forecast local-
ized corrosion resistance. This strictly empirical formula does not
factor in microstructural or electrolyte variables, which, as seen in
Mo
0.36
0.23
3.40
2.16
0.27
0.00
3.32
1.95
0.36
Fig. 5. Time records of metastable pit transients taking place at 430 (, gray) and
0.24
434 (, black) grades at pH 10. Both samples polarized at +500 mV with respect to
3.46
their open circuit potential. Transients were shifted so as to coincide their initiation
2.16
at an arbitrary time origin. Sample frequency 500 Hz.
606 T.J. Mesquita et al. / Materials Chemistry and Physics 126 (2011) 602–606
the present paper, are of major concern in the corrosion resistance
of steels exposed to different media.
4. Conclusions
In summary it is shown that Mo has a strong beneficial effect
on the corrosion resistance of ferritic and duplex stainless steels
in chloride-rich alkaline environments. This is more likely due to
a hindered pit initiation than due to kinetic aspects related to the
modification of electrolyte composition as proposed in the case of
acidic solutions.
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