Electrochimica Acta 49 (2004) 4533–4542

www.elsevier.com/locate/electacta

Review article

A review of the electrochemical corrosion behaviour of iron aluminides

V. Shankar Rao*
Corrosion Science and Engineering Program, Indian Institute of Technology, Bombay, Mumbai-400076, India

Received 13 April 2004; received in revised form 24 May 2004; accepted 27 May 2004

Available online 2 July 2004

Abstract

The objective of this review is to outline the aqueous corrosion research activities being undertaken on iron aluminides. Key results are
extracted and reviewed from publications covering the past 25 years of research activity in aqueous corrosion behaviour of iron aluminides.
This review deals with phenomena, which are related with electrochemical corrosion such as passivation and repassivation kinetics,
breakdown of passivity, chemistry of the passive film and mechanism of passivation. The role of constituent elements and the effect of alloying
elements on the corrosion behaviour of iron aluminides have also been discussed. To assess corrosion resistance of iron aluminides a
comparative study was put up with that of stainless steels.
ß 2004 Elsevier Ltd. All rights reserved.

Keywords: Iron aluminides; Oxidation; Passivation; Repassivation; Electron microscopy

1. Introduction two reasons behind this. Firstly, to test durability of these

Development of iron aluminides in the field of high-
temperature applications has exploded over the past few
years. There has been an increase in the number of works on
iron aluminide every year and it is expected to continue in
future. This is because there is a race among researchers to
solve iron aluminide’s twin problems of poor room tem-
perature ductility and drop in strength above 550 8C, which
are the main impediments for commercialization of these
materials, either by different process routes or/and with
alloying element additions [1,2]. In short, these materials
are attractive to the researcher because of their excellent
properties such as high strength to weight ratio and good
oxidation resistance, which are prerequisite for a material to
be used in high temperature applications [2,3].
Though iron aluminides are mainly developed for the
structural applications at elevated temperatures, a number of
studies have been channelled on the aqueous corrosion
behaviour of these materials [4–11]. There are primarily
* Present address: Department of Materials Science and Engineering,
Korea Advanced Institute of Science and Technology, 371-1 KuSong-dong,
Yo-Song-gu, Taejon 305-701, Republic of Korea. Tel.: +82 428695326.
E-mail address: vshankarao@yahoo.co.in.
alloys when they are either stored ideally or during working
conditions in a corrosive atmosphere. Secondly, being low
cost compared to conventional stainless steels, these materi-
als are also considered for room temperature applications in
replacement of stainless steels such as pipes and tubes for
heating elements, and in distillation and desalination plants.
In addition to this, due to avoiding the use of strategic
elements such as Cr and Ni these materials are also con-
sidered for biomaterials applications for example bone joints
and surgical instruments. There are some excellent reviews
about these materials, which deal with material processing,
advantages and limitations of alloy developments, physical
properties [1,2], high temperature oxidation behaviour
[12,13], and hydrogen embrittlement [14]. But what is
known about the aqueous corrosion behaviour of iron alu-
minides is sparse in any of these reviews. Given all the
interest, it seems reasonable to present a review on the
aqueous corrosion behaviour of iron aluminides. In this
article we will first discuss the electrochemical corrosion
behaviour of iron aluminides and their constituent elements
followed by the effect of alloying elements on this beha-
viour, and then a comprehensive outline will be provided on
the chemistry and mechanism of passive films formed on

0013-4686/$ – see front matter ß 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2004.05.033
4534 V.S. Rao / Electrochimica Acta 49 (2004) 4533–4542
iron aluminides. At the end aqueous corrosion behaviour of
iron aluminides will be compared with that of stainless
steels/aluminium rich steels.
It is expected that the review presented here on the
aqueous corrosion behaviour of iron aluminides will be
helpful to the researchers working on these materials and
their consistent development.
2. Electrochemical corrosion behaviour of iron
aluminides
We will start reviewing this subject with the role of
constituent elements Fe and Al on the polarization behaviour
of iron aluminides. During the discussion we will also report
the corrosion behaviour of Fe–Al alloys along with iron
aluminide to get a coherent view of the subject.
Accordingly, Fig. 1 compares the polarisation curves of
Fe3Al based iron aluminide, pure Al (99.99%) and Fe
(Armco iron) obtained in 0.25 M H2SO4. All these three
alloys exhibit passivation behaviour, however, they differ in
nature of transition from active to passive state. Al forms
passivity just above its open circuit potential (OCP); Fe gets
sudden transition from active to passive after extensive
active dissolution whereas iron aluminide reaches to pas-
sivity in a typical active passive transition. Notably, the
current density in the passive region of Fe is lower than that
of Al, whereas the latter has a wide passive potential range
compared to the former. The combined effect of Fe and Al
seems to benefit iron aluminide over a wide potential range.
At low potential, close to the corrosion potential of the
aluminide, the spontaneous passivation tendency of Al helps
to reduce active dissolution of iron aluminide by formation
of an Al2O3 film, while at higher potential the presence of
iron oxide provides an additional resistance to the passage
of current with Al2O3. Thus the current density of iron
aluminide in the passive region is lower than that of pure
iron. Despite these beneficial facts of iron aluminide in
Fig. 1. Potentiodynamic polarisation curves of iron aluminide, pure Al and
Fe obtained in 0.25 M H2SO4.
passivation behaviour over Fe and Al, the difference
between corrosion potential (Ecorr) and passive potential
(Epass) is relatively high compared to the other passivating
alloys such as stainless steels. Plus, the anodic critical
current density (icrit
20 mA cm2) of aluminide is more
than its limiting current density for oxygen reduction
(0.1 mA cm2), which makes the aluminide difficult to self
passivate in aerated conditions. The polarization curve of
iron aluminide in the transpassive region appears to be
similar to that of pure iron and its transpassive potential
is well above the equilibrium potential for oxygen evolution
(0.96 VSCE for a measured pH of 0.6 and assuming partial
pressure of O2 as 1 atm). A more detailed discussion on this
aspect has appeared with Choe et al. [5], Frangini and
coworkers [8,10], and Shankar Rao et al. [15].
Frangini [4] and coworkers [8–10] made extensive
studies on the electrochemical corrosion behaviour of
iron aluminides. In one of their studies, they compared
the potentiostatic polarisation behaviour of B2 FeAl
(24.4%Al) with Fe in 0.5 M H2SO4 solution [10]. After
setting a potential in the passive region, the change in current
density with time during initial transient period follows a
similar trend in both cases, with a slope log(i) versus log(t)
of approximately 1. However, FeAl (4 mA/cm2 after 1 h)
attains the steady state more rapidly compared to Fe (7 mA/
cm2 after 20 h). They suggested that the linear current
transient during the passivation process follow the high-
field ion conduction and the place exchange mechanism for
the oxide growth, though not much discussion is available
on that.
To avoid the mechanism of preformed oxide film the
repassivation behaviour of Fe3Al along with pure Al and Fe
were investigated in 0.25 M H2SO4, using the rapid
scratched electrode technique [16]. Typical current transient
curves from the scratched surface of the passive film, which
were formed at 1 VSCE (see Fig. 1), are shown in Fig. 2. Once
a scratch breaks the passive film, the anodic current flown
from the scratched surface increases abruptly to a peak due
Fig. 2. Repassivation kinetics of iron aluminide, Fe and Al obtained in
0.25 M H2SO4.
 V.S. Rao / Electrochimica Acta 49 (2004) 4533–4542
to an anodic oxidation reaction, and thereafter decreases as
repassivation proceeds. In this perspective, the measured
current corresponds to the repassivation process follows in
the order of Fe3Al < Al < Fe. The peak current density of
iron aluminide is about two times lower than that of Al while
compared to Fe it is much lower, about seventeen times. The
current density measured during repassivation process is
primarily associated with the formation of a passive film
provided metal dissolution is not dominated by pitting
corrosion or general corrosion. Notably, the rate of anodic
current decay of Fe is much slower than that of Al and iron
aluminide. Not only that, Al and iron aluminide display
similar kinetics during repassivation, whereas Fe seems to
differ from them. A slower repassivation rate of iron despite
its low passive current density (over Al) casts doubt on the
stability and protectiveness of the passive film. Importantly,
the faster repassivation rate of iron aluminide substantiates
its superiority on the passivation behaviour over Fe and Al.
More studies related to the repassivation behaviour of Fe–Al
alloys with different (5–25)% Al (unless otherwise noted, all
composition will be given in weight percent) contents can be
found in the work of Madsen and Adler [17].
Meanwhile, keeping the kinetics of Fe and Al in mind we
will continue our discussion by reviewing the works related
to corrosion behaviour of Fe–Al alloys. Aqueous corrosion
behaviour of Fe–Al alloys was first published with Nachman
and Duffy in 1974 [18] but it was not an electrochemical
study. These authors evaluated corrosion behaviour of Fe–Al
alloys for different Al contents (6–16%) in sea water solu-
tion by weight loss measurement and then most promising
alloy was tested for erosion corrosion in a flow of sea water.
Their results show a minimum 10% Al should be there in
Fe–Al alloy for a good corrosion resistance and to maintain a
protective oxide film.
Electrochemical corrosion behaviour of Fe–Al was first
reported by Derfancq, as early as 1977 [19] and it was reported
that the addition of 25% Al in cast iron markedly changes
its polarisation behaviour. His results are shown in Fig. 3
Fig. 3. Potentiodynamic polarization curves of cast Fe–2Al and Fe–25Al
alloys obtained in 0.5 M H2SO4 [19].
4535
where he compares potentiokinetic polarisation behaviour
of the cast Fe–25.74Al alloy with that of Fe–2.25Al alloy
in sulphuric acid media. In the low-Al content alloy,
two anodic maxima peaks appeared at +250 mVSHE and
+650 mVSHE which are associated with iron dissolution,
while in the case of Al rich cast iron these peaks disappear.
This was attributed to the formation of a protective film of
aluminium oxide on the electrode surface during polarisa-
tion, which restricts the anodic iron dissolution even at
higher potential.
Electrochemical behaviour of iron aluminide is reported
to be pH dependent. Schaepers and Strehblow [11] have
investigated the passivation behaviour of Fe–Al alloys with
Al content of 4, 8 and 12% in acidic and alkaline electro-
lytes. Fig. 4a–c show cyclic voltammogram obtained in
borate buffer solution and H2SO4/Na2SO4 solution, respec-
tively. In the borate buffer solution there is no significant
difference in the polarisation behaviour of Fe–Al alloys with
variation of Al content (Fig. 4a). Owing to lower currents in
this electrolyte support for passivation by Al was not
detectable in the polarisation curves. Whereas, the polarisa-
tion curves in H2SO4/Na2SO4 solution display higher cur-
rent density than those obtained in alkaline solution and
pronounced changes are observed between low (Fig. 4b) and
high Al content alloys (Fig. 4c). The alloy with 4% Al shows
a large dissolution peak, which grows due to surface rough-
ening with increasing number of cycles, whereas the alloy
with 12% Al shows a lower anodic current. The decrease in
anodic current at 0.1 VSHE with increasing number of
scans suggests that a part of the oxide is not reduced and
that it remains at the surface and supports repassivation of
the alloy in the next cycle.
De Cristofaro et al. [6] have studied the passivity and its
breakdown of FeAl (24% Al) in sulphates and chlorides
containing borate buffer solution, in which it was reported
that the voltammogram response of iron aluminides is similar
to Fe. In agreement with Frangini et al. [9] the peaks in cyclic
voltammogram were suggested to be iron oxidation/reduc-
tion processes. Sulphate addition to the buffer solution makes
the passive film more stable. According to them a mixed iron
(II–III) oxide is responsible for passivation of FeAl in the
sulphate–borate solution in contrast to only iron (III) rich
oxide in the borate solution without sulphate. Moreover, iron
suffers from pitting corrosion in sulphate–borate solution,
while aluminide remains un-attacked. This implies that the
presence of Al in iron aluminide enables the formation of a
more protective passive layer. However, this does not apply
with the addition of Cl in buffer solution as well. In which
case, the pitting potential of iron aluminide increases linearly
with log Cl with a slope of 0.40 V/decade and produces
nucleation of pits on iron aluminide with addition of 6 
104 M NaCl in buffer solution. This shows the choice of
electrolyte and presence of ions in it has a critical influence
on the corrosion behaviour of iron aluminides.
Kim and Buchanan [20] tried to evaluate the effect of
change in structure (DO3 versus B2) on corrosion behaviour
4536 V.S. Rao / Electrochimica Acta 49 (2004) 4533–4542

Fig. 4. Cyclic voltammogramms of (a) Fe–(4–12)Al alloys in borate buffer solution, (b) Fe–4Al alloy in H2SO4/Na2SO4 solution and (c) Fe–12 Al alloy in
H2SO4/Na2SO4 solution [11].

of an Fe3Al alloy in aerated 200 ppm Cl at pH 4. In this sulphuric acid media but with increasing exposure time
study the alloy with the DO3 structure possesses low passive the corrosion rate of iron aluminide increases and becomes
current density and high breakdown potential compared to higher than that of iron. Later Shankar Rao et al. [15]
the B2 structure. A study similar to that by Kim and Buhman explained the high corrosion rate of iron aluminide over
[20] was conducted by Garcia Alonso et al. [21] where that of iron by taking into account their respective hydrogen
corrosion behaviour of Fe3Al with different crystal struc- exchange current density (iOHþ =H2 ) values. They found the
tures was evaluated in Hank’s solution. Their studies show iOHþ =H2 value in 0.25 M H2SO4 of the alloy Fe–16Al–0.05C
that corrosion rate of the aluminide is independent of the
crystal structure but the alloy with order states B2 as well as
DO3 possesses more pitting resistance than the disordered
states. The nature of attack in a Fe3Al based intermetallic
after subjecting it to anodic polarisation in 0.5 M NaCl is
illustrated in Fig. 5, which shows the crystallographic grain
features inside the pit.
So far we have seen the beneficial effect of Al on the
passivation behaviour of iron aluminide above its open
circuit potential and in the passive region. However, the
story seems to be the other way around at the potential below
open circuit and in the cathodic region. Frangini [4] revealed
the detrimental effect of Al on the corrosion behaviour of
iron aluminide who used linear polarisation resistance
method as an alternative method for determining the corro-
sion current density at the open circuit potential. According
to them the corrosion rate of FeAl aluminide remains Fig. 5. SEM micrograph of an ordered Fe3Al alloy shows the crystal-
equal to pure Fe during initial stage of corrosion in mild lographic nature of the pit formation after subjecting to 0.5 M NaCl.
 V.S. Rao / Electrochimica Acta 49 (2004) 4533–4542
(2.5  102 mA cm2) is higher than that of iron (2.0 
103 mA cm2). It is well known that the higher the
exchange current density of an alloy is the higher is its
corrosion rate. It is worth mentioning here that the diffu-
sivity of librated nascent hydrogen in the lattice of iron
aluminide is very low and generally decreases with increas-
ing Al content in intermetallics [22].
In the late eighties or so ac impedance technique emerged
as a most powerful source for providing information about
the protectiveness of the passive film and with the time it has
become a most common tool for corrosion researchers. It
was Frangini and Lascovich [23] who first employed this
technique to study the passive film properties grown on iron
aluminide. They measured impedance behaviour of FeAl
alloy in 0.5 M H2SO4 as a function of passive film thickness
and passive potential between 0.5 and 1.5 VSCE. Their
results show two overlapping time constants at lower fre-
quency, which were attributed, respectively to the charge
transfer processes at the film/solution interface and ion
conduction within the passive film. There was a decrease
in the capacitance value and the film thickness with increase
in potential above 1.0 VSCE. This was attributed to the
transformation of the initially formed compact passive
layer to a more porous passive structure. By evaluating iR
values as a function of the potential drop inside the film, it
was suggested that the transport of ions in the passive film
on FeAl occurs predominantly through low electric field
strength regions.
Generally, a thermally generated alumina layer (Al2O3)
on the iron aluminide surface provides excellent oxidation
resistance. Taking this into account some investigators tried
to improve the aqueous corrosion resistance of iron alumi-
nide. But some reservations have been observed from the
existing works, while reviewing this subject. Lopez and
Escudero [24] compared the corrosion behaviour of an FeAl
compounds in chloride containing solution by applying the
ac impedance technique, both in the as-received condition
and after a heat treatment at 1100 8C for 2 h. They calculated
the charge transfer resistance (Rt) and the apparent capaci-
tance (Cap) values of the oxidized state and the as received
state and found almost similar values in both cases. These
authors suggested that the alumina layer generated by heat
treatment is of low protecting capacity due to the presence of
additional oxides (iron oxide). In a recent work, Escudero et
al. [25] reported that by prior oxidation of Fe–40Al alloy its
corrosion resistance can be improved when subjected to the
Hank’s solution (8 g NaCl, 0.14 g CaCl2, 0.4 g KCl, 1 g
glucose, 0.1 g MgCl2, 0.35 g NaHCO3, 0.06 g Na2H-
PO42H2O, 0.06 g KH2PO4 and 0.04 g MgSO47H2O in
1 L distilled water). By impedance studies on a sample
oxidized in air at 1000 8C and on an unoxidized sample
they found a higher impedance value in the entire range of
frequencies of a Bode plot in the unoxidized sample com-
pared to the well-formed alumina sample. They noticed that
the protection given to the intermetallic was highly variable
from sample to sample and suggested that only a continuous
4537
and defect free thermal oxide layer can ensure the good
resistance for iron aluminide.
3. Effect of alloying elements on corrosion
behaviour of iron aluminides
Addition of third alloying elements in iron aluminides has
been an intelligent approach to improve their mechanical
properties and oxidation resistance. But at the same time this
can affect aqueous corrosion behaviour of iron aluminide as
well. In that respect, several researchers contributed to this
subject.
When it was proven that the addition of Cr in iron
aluminides improves their ductility as well as their oxidation
resistance, a number of studies were directed to test the
effect of Cr addition on aqueous corrosion behaviour of iron
aluminides [20,7,8]. Kim and Buchanan [20] studied the role
of Cr on pitting and crevice corrosion of iron aluminides
(28 at.% Al) in mild acid chloride solution. Their studies
indicate beneficial effects of Cr in terms of an increase in
breakdown potential of the passive film with increasing Cr
content in the alloy. In another study, Balasubramaniam [7]
reported that the corrosion rate of Fe–28A–5Cr alloy is
about two orders less than that of Fe–25Al in (pH 4) H2SO4
solution containing 200 ppm Cl. They tried to visualize this
difference in corrosion behaviour of both the alloys by
applying Evans diagram. The first formal presentation of
mixed-potential theory in case of iron aluminide is attributed
to this author [7,14]. But this theory has not gained much
thrust in published works related with corrosion behaviour
of iron aluminides after this. Frangini et al. [8] conducted
some experiments to determine the role of Cr in the passive
film by incorporation from the solution rather than from the
alloy. For this, Cr ions were incorporated into the passive
film of FeAl from alkaline chromate solution through repe-
titive oxidation–reduction cycles and its corrosion behaviour
was compared with Fe–(12–24)% Cr stainless steels in
0.5 M NaCl containing borate solutions. Their results show
that the pitting potential of this alloy after treatment is
comparable to those of stainless steels despite the fact that
the Cr enrichment in the passive film of FeAl was not as high
as in the passive film of the compared stainless steel. Based
on this finding the protective property of the passive film was
suggested to be the synergistic action of Cr and Al.
Addition of Mo in stainless steel is well known for
improving its pitting resistance and in iron aluminide it is
added generally to enhance the adhesion resistance of the
Al2O3 on the surface. Choe et al. [5] investigated the effects
of 1 at.% Mo along with 2–6 at.% Cr, in order to check its
effect on corrosion behaviour of Fe3Al (28 at.% Al). Their
results show the addition of Mo along with Cr in iron
aluminide increases the corrosion potential, pitting potential
and repassivation potential in 0.25 M H2SO4, whereas the
critical current density and passive current density are
decreased. In addition, Mo impeded Cl adsorption on
4538 V.S. Rao / Electrochimica Acta 49 (2004) 4533–4542

the surface. An advantage of Mo addition over Cr addition in

iron aluminide was seen during their cyclic polarisation tests
in 0.1 M HCl solution, in which pitting and repassivation
potentials of the aluminide increased with addition of Mo as
well as Cr, however, Mo has a much greater effect in this
regard than Cr. These authors also investigated the effect of
B on corrosion behaviour of iron aluminide and found that
like Mo and Cr it was not very beneficial in improving
passivation behaviour, but it was more beneficial in increas-
ing the activities at grain boundaries in aluminide compared
to the other two. Their electrochemical potentiokinetic
reactivation (EPR) studies in 0.5 M H2SO4 + 0.01 M
KCN solutions show that the degree of intergranular attack
on these alloys increases in the order of Mo > Cr > B. In
another work Choi and Kim [26] investigated the passive
film behaviour of 28Al–4Cr–xMo (at.%) aluminide in thio- Fig. 6. Potentiodynamic polarisation curves of Fe–16Al–(0.14–1)C alloys
sulfate–chloride solution (chloride 50 ppm and thiosulfate obtained in 0.25 M H2SO4 [15].
10 ppm) as a function of Mo 0.5–2 at.% using the ac
impedance technique, at three different states namely break-
down, passivation and repassivation. Their studies show that addition of C is related with the increase in the volume
the Mo bearing alloy possesses higher charge transfer values fraction of the carbide. At the same time in a complementary
(Rt) than that of the Mo-free alloy in all three states. study the effect of Al on the corrosion behaviour of Fe–Al–C
Furthermore, they suggested a synergistic effect of Mo was investigated in 0.25 M H2SO4 [29]. Like binary Fe–Al
and Cr in improving the pitting resistance of iron aluminides. alloys, lowering the Al content of the Fe–Al–C alloys
Babu et al. [27] experimented to see the effects of resulted deterioration of the passivation behaviour in terms
mischmetal (Mm: 43Ce, 23La, 18Nd, 5Pr, 3Sm and 8Fe of increase in ipass and icrit values though the corrosion rate of
in %) addition on the electrochemical corrosion behaviour of the alloy is not much affected. An important finding in these
the Cr-alloyed iron aluminide, as mischmetal are known for investigations is that in high Al content alloys the carbide
inducing passivity of an alloy like Cr. By comparing poten- phase preferentially attacked (Fig. 7) whereas in low Al
tiodynamic polarization behaviour of Fe–28Al–2Cr and Fe– content alloys the both matrix and carbides dissolve at
28Cr–0.15 Mm in 0.05 M l1 H2SO4 solution they found similar rate. This has been linked to the compositional
that the addition of mischmetal is beneficial on the passiva- variation in the phases with variation of Al and C in alloys.
tion behaviour only in terms of reducing the passive current As discussed in that work, a reduction of Al content causes
density, whereas there is no significant affect on other decrease in the Al of the matrix phase while composition of
electrochemical parameters such as icrit, passive range, zero carbides remains unchanged in order to maintain its stoi-
current potential and breakdown potential. chiometry. On low Al containing alloys the near uniform
It was not until the middle of the nineties that Fe3Al– attack was not due to rise in corrosion resistance of carbides,
Fe3AlC dual-phase iron aluminide reported to possess better but rather to the decreased corrosion resistance of the matrix.
hydrogen embrittlement resistance than single-phase Fe3Al
[28]; since then, investigations on the electrochemical cor-
rosion behaviour of these dual phase iron aluminide have
increased [15,29,30]. Plus, carbon a common alloy impu-
rities is believed to be present in iron aluminides which led to
affect their corrosion resistance. With such a motivation the
effect of C (0.14–1%) on the corrosion behaviour of Fe3Al
(16%Al) in 0.25 M H2SO4 solution is illustrated in Fig. 6.
The value of electrochemical parameters such as iOHþ =H2 ,
icrit, and current density in the passive region, which were
calculated by their polarisation curves found to be increase
with increasing C content. Microstructural and phase ana-
lysis of these dual-phase alloys reveal an increase in the
volume fraction of the carbide with C content. The nature of
attack on an Fe3Al–Fe3AlC alloy after immersion in acid
media which is shown in Fig. 7 reveals the preferential
dissolution of the carbide phase. Hence, deterioration in Fig. 7. SEM micrograph of an Fe–16Al–1C alloy after immersion in
corrosion resistance of iron aluminide with the increasing 0.25 M H2SO4 shows preferential dissolution of the carbide phase [15].
 V.S. Rao / Electrochimica Acta 49 (2004) 4533–4542 4539

4. Chemistry and mechanism of the passive film

formed on iron aluminide

Having gained an understanding of the electrochemical

kinetics of iron aluminides we set our eyes now on the
structure and chemistry of the passive film formed on these
alloys. Several studies were directed on this aspect with
different Al contents in the alloy, different electrolytes
concentration and pH, and different formation potentials
[8,10,11]. Despite these variations among the existing stu-
dies some common consensuses can be found from them,
which are as follow:

 an enrichment of Al in the form of Al (III) oxide/hydro-

xide on the surface during passivation. This enrichment is
even more than the Al bulk concentration of the alloy;
 Al content in the passive film increases with increasing Al
content in the alloy;
 co-existence of iron and aluminium oxides on the surface
during passivation;
 addition of alloying elements such as Cr and Mo facilitate
the formation of their respective oxides (Cr2O3 and
MoO3) in the passive film along with Al2O3.

Some investigators have intended to compare the chem-

istry of passive films with that of the air-oxidized films in
order to differentiate film properties in wet and dry condi-
tions [8,30]. Such a study is illustrated in Fig. 8a and b where
XPS spectra of the iron aluminide exposed to the 0.25 M
H2SO4 working solution at 1 VSCE (see Fig. 1) and iron
aluminide oxidized in O2 atmosphere at 800 8C for 10 min
are compared. In Fig. 8a, appearance of the peak in the
oxidized sample at 74.2 eV is assigned to the binding energy
(BE) of Al3+ in Al2O3 [31]. Notably, in the case of the
passivated sample there is a shift in the Al3+ peak towards
high BE, on deconvolution of the spectra, it revealed coex-
istence of Al3+ as Al2O3 and Al–OH at 74.49 and 75.29 eV,
respectively [31,32]. In Fig. 8b, the peaks of iron at 711 
2 eV correspond to Fe3+ [33]. After deconvolution of the Fig. 8. XPS spectra for (a) Al 2p3/2 and (b) Fe 2p3/2 spectra for thermally
passive spectra it reveals multiple peaks assigned to oxides oxidized elements at 800 8C (dotted lines) and passivated elements in
and sulfates [33,34]. Unlike in the case of Al, there is no 0.25 M H2SO4 at 1 VSCE.
difference in peak position of Fe3+ between the oxidized and
passivated samples. This shows that Al exists in the form of In another study, investigation of the passive layer by
an oxide as well as a hydroxide whereas the presence of Fe in elastic-ion scattering and XPS depth profiling shows max-
the passive film is only as an oxide. In a study similar to this, imum enrichment of Al(III) within the centre of the passive
Frangini et al. [8] reported that the Fe2+ concentration is film [11]. The initially formed Al(III)-rich film contains a
more in an anodically formed film than in an air formed film, large amount of hydroxide. However, like any other passi-
though after sputtering it disappears from both the films. vating alloy during longer passivation time and at more
From depth profile analysis they found that the Fe/Al ratio is positive potential the layer composition changes into a
high in the case of the anodically formed film compared to mixed oxide/hydroxide film with a larger amount of addi-
the air formed film, which indicates an enrichment of iron in tionally formed iron oxide.
the outer layer of the anodic film with respect to the air To get an idea about the mechanism behind the passiva-
formed film. Their work further shows that the outer part tion behaviour of iron aluminides we take a look at the
of the passive film predominantly consists of mixed Al–Fe precise chemical reactions which take place after its immer-
oxy-hydroxide whereas the inner part is of mostly an Al-rich sion in electrolyte. For this, anodic polarisation behaviour of
oxide phase. the iron aluminide in acid media will be discussed.
4540 V.S. Rao / Electrochimica Acta 49 (2004) 4533–4542

During active dissolution of the alloy the following

reactions are possible depending upon alloy compositions
whether it is FeAl or Fe3Al:

FeAl þ 6Hþ ¼ Fe3þ þ Al3þ þ 3H2

Fe3 Al þ 6Hþ ¼ 3Fe3þ þ Al3þ þ 3H2 þ 6e
Fe3 Al þ 6Hþ ¼ 3Fe2þ þ Al3þ þ 3H2 þ 3e
These reactions are balanced by the following reduction
reaction which consumes electrons:
2H2 O þ 2e ¼ H2 þ 2OH
Thermodynamically Al2O3 has more negative free energy
compared to iron oxide [11] and kinetically, the mobility of
Al3+ is also low compared with iron ions within the barrier
film [10]. Therefore, after active dissolution from iron
aluminide aluminium quickly converts into Al2O3 on the
surface by following reaction, whereas iron ions remain in
the solution:

2Al3þ þ 3H2 O ¼ Al2 O3 þ 6Hþ

This Al2O3 layer is expected to act as a diffusion barrier Fig. 9. Schematic model for passivation behaviour of iron aluminide in
similar to the case of pure Al for dissolution of iron from the acidic electrolyte.
surface. However, due to porosity in nature it allows some
iron to dissolve.
As the potential is moved from Ecrit towards the pre- 5. Comparative study between corrosion behaviour of
passive potential iron oxides start forming on the surface by iron aluminide and stainless steel
the following reactions:
This final section of the review compares the aqueous
2Fe3þ þ 3H2 O ¼ Fe2 O3 þ 6Hþ corrosion behaviour of iron aluminides with stainless steels.
Fe2þ þ H2 O ¼ FeO þ 2Hþ This is relevant because as mentioned during the introduc-
tion, a part of the research motivation behind the develop-
It is postulated that the formation of these iron oxides on
ment of iron aluminides is to replace stainless steels in
the surface of the passive film blocks the porosity of the
aqueous environment applications. But the amount of avail-
Al2O3 passive film. Plus the presence on iron oxides on the
able data on this issue is not much. It has been a decade since
surface provides additional resistance to protectiveness of
the first comparative study between 304 L stainless steel and
the passive film. Thus, a combined resistance of Al2O3 and
iron aluminide was reported by Kim and Buchanan [20]
Fe2O3 oxides drop the passive current density of iron
aluminide to its minimum value in the passive region.
As mentioned above with the shift of passive potential
towards the noble direction more Al–OH starts forming. This
can be explained by the following reaction:
Al2 O3 þ 3H2 O ! 2AlðOHÞ3
since the above-mentioned oxides and hydroxide remains
stable from their passive potential to the oxygen evolution
potential for a given pH. Therefore, the transpassive region
corresponds to the following reaction:

2H2 O ! O2 þ 4Hþ þ 4e

Based on this understanding a schematic model for the
passivation behaviour of iron aluminide is presented in
Fig. 9. However, the view presented in this model differs
from others as they reported the structure of the passive layer
as a bilayer [10,11] whereas in the present case it is a mixed Fig. 10. Potentiodynamic polarisation curves of Fe–16Al and Fe–18Cr
layer or blocking effect as described in the text. alloys obtained in 0.25 M H2SO4.
 V.S. Rao / Electrochimica Acta 49 (2004) 4533–4542
Table 1
Electrochemical parameters of Fe–16Al and Fe–18Cr alloys obtained from polarisation curves in 0.25 M H2SO4
icorr (mA cm2) Ecorr (VSCE) icrit (mA cm2)
Fe–16Al 1.7 0.573 20.3
Fe–18Cr 0.63 0.550 8.0
where the pitting and crevice corrosion behaviour of Fe3Al
(28 at.% Al) is reported to be the less resistance compared to
304 L stainless steel in mild chloride solution (200 ppm Cl
+ (6.25  105 M) H2SO4) with pH adjusted to 4. At about
the same time in an another communication Buchanan et al.
[35] reported a relatively high corrosion rate of an Fe3Al
(28 at.%Al) compared to 304 L stainless steel in acid and
sulfur-bearing environments, but in an alkali environment
(1 M/L NaOH) both the alloys were reported to have
equivalent corrosion resistance.
To provide one to one comparison between the corrosion
behaviour of iron aluminide and stainless steel potentiody-
namic polarization curves of iron aluminide (Fe–16Al) and
Fe–18Cr alloy (430 SS) obtained in 0.25 M H2SO4 are
compared in Fig. 10. Electrochemical data obtained from
the respective polarization curves are presented in Table 1.
These data show that there is no virtual difference in the
general corrosion behaviour of iron aluminide to that of 430
SS, as difference in the icorr values as well as in the Ecorr
values is very minimal. In this context, it is a surprise to see
the results from the work of Balasubramaniam [7] where a
wide difference in corrosion potential as well as in corrosion
current density between Fe–25Al and Fe–28Al–4Cr alloys
exist in (pH 4) H2SO4 solution containing 200 ppm Cl. The
addition of Cr causes a shift in corrosion potential of the
alloy towards noble direction by about 700 mV and at the
same there is a decrease in corrosion current density more
than three orders. Nevertheless, the data obtained from Fig.
10 are in good correlation with the results of Choe et al. [5]
where they compared polarization behaviour of a Fe–28Al
alloy with a Fe–28Al–6Cr alloy.
The critical current density, which is an important para-
meter to assess the dissolution tendency of an alloy, though
appears to be low in stainless steel compared to iron
aluminide but this difference can be ignored considering
relatively high Cr content in 430 SS (Fe–18Cr) compared to
Al content in Fe–16Al alloy. Frangini [4] remarked in his
study, which has been discussed in Section 1, that the rate-
determining step during active dissolution of FeAl is a
charge-transfer reaction of iron, similar to that of an
iron–Cr alloy. A pronounced difference in their anodic
polarisation behaviour appears in the pre-passive region,
where Cr-based alloy possesses clear advantage over Al-
based alloy. As the transition period from the active to
passive region in case of stainless steel is about 10 min
whereas for iron aluminide it is 30 min, for a sweep rate of
0.5 mV/s. This lends credence to the porous nature of the
Al2O3 oxide film. It should be pointed out that a remarkable
enrichment of Cr ions occurs in the passive film of Fe–Cr,
which is mainly attributed to its passivation [36], whereas, as
4541
ipass (mA cm2) Epass (VSCE) Etrans (VSCE)
37.1 0.460 1.550
5.5 0.190 0.830
brought out in Section 4, Fe and Al oxides co exist in the
passive film formed on iron aluminide. While comparing
both alloys in their passive regions we can find that the iron
aluminide has noble passive potential and at the same time
the passive region appears to be much wider compared to the
alloy 430 SS but its passive current density is about one
order higher than that of stainless steel. Coming to the
transpassive region the high transpassive potential of iron
aluminide leads this region to the oxygen evolution process
whereas in stainless steel it generally corresponds to
Cr-oxide dissolution from the passive film.
As previously shown in Section 3, that the substitution of
Cr for Al or Fe in iron aluminides improves their aqueous
corrosion resistance. At the same it would be interesting for
readers to know what happens to corrosion resistance of a
stainless steel when Al is substituted for Cr. With a similar
view Wolff et al. [37] investigated the corrosion behaviour of
Fe–40Cr and Fe–35Cr–5Al steels. Their results shows neg-
ligible difference in general corrosion behaviour between
both the steels in 10% H2SO4, whereas in 3.5% NaCl
aluminised steel led to inferior pitting resistance over stain-
less steel.
While for comparing the effect of alloying elements on
the corrosion behaviour of iron aluminide with that of
stainless steel on the whole we can draw a similar line in
both the cases from the discussion in Section 3 and existing
literature on stainless steel.
6. Summary
The foregoing review exposes the aqueous corrosion
behaviour of iron aluminide along with its alloying elements
in various corrosive environments. The results display that
the passivation behaviour of iron aluminide is better than its
alloying elements namely Fe and Al, whereas the corrosion
resistance of the alloy is inferior to their respective elements.
The addition of third alloying elements such as Cr and Mo
improve the corrosion resistance of iron aluminides. Though
these materials show good passivity, in order to make their
corrosion resistance equivalent to stainless steels, much
work needs to be done.
Acknowledgements
The author acknowledges Prof. V.S. Raja of Corrosion
Science and Engineering Program, Indian Institute of Tech-
nology, Bombay, India for discussion on the subject and
thanks to Dr. John Fisher of Department of Materials
4542 V.S. Rao / Electrochimica Acta 49 (2004) 4533–4542

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