Corrosion Science 52 (2010) 33943404

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

High temperature oxidation of FeAl and FeCrAl alloys: The role of Cr

as a chemically active element
E. Airiskallio a,b, E. Nurmi a,b,c,*, M.H. Heinonen a,b, I.J. Vyrynen a,b, K. Kokko a,b, M. Ropo d,e,
M.P.J. Punkkinen a,b,f, H. Pitknen g, M. Alatalo g, J. Kollr h, B. Johansson f,i, L. Vitos f,h,i
a
Department of Physics and Astronomy, University of Turku, FI-20014 Turku, Finland
b
Turku University Centre for Materials and Surfaces (MatSurf), Turku, Finland
c
Graduate School of Materials Research, Turku, Finland
d
Department of Information Technology, bo Akademi, FI-20500 Turku, Finland
e
Fritz-Haber-Institut der Max-Planck-Gesellschaft, D-14195 Berlin, Germany
f
Applied Materials Physics, Department of Materials Science and Engineering, Royal Institute of Technology, SE-10044 Stockholm, Sweden
g
Department of Mathematics and Physics, Lappeenranta University of Technology, P.O. Box 20, FI-53851 Lappeenranta, Finland
h
Research Institute for Solid State Physics and Optics, P.O. Box 49, Budapest H-1525, Hungary
i
Department of Physics and Materials Science, Uppsala University, SE-75121 Uppsala, Sweden

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

Article history: Good high-temperature corrosion resistance of FeAl alloys in oxidizing environments is due to the a-
Received 20 April 2010 Al2O3 lm which is formed on the surface provided temperature is above 900 C and the Al-content of
Accepted 18 June 2010 the alloy exceeds the critical value. Ab initio calculations combined with experiments on Fe13Al, Fe
Available online 30 June 2010
18Al, Fe23Al and Fe10Cr10Al alloys show that the benecial effect of Cr on the oxidation resistance
is signicantly related to bulk effects. The comparison of experimental and calculated results indicates a
Keywords: clear correlation between the FeCr chemical potential difference and the formation of the protective
A. Alloy
oxide scales.
A. Steel
B. AES
2010 Elsevier Ltd. All rights reserved.
C. Oxidation
C. Passive lms

1. Introduction tom up picture of the physical phenomena responsible for the

FeCrAl alloys are often used as high-temperature corrosion
resistant materials [13] due to their ability to form a highly stable
and protective oxide scale on the open surface when exposed to
oxidizing environment. The physical properties and corrosion
resistance of FeCrAl as a function of the chemical composition
of the alloy has been studied quite extensively, see e.g. [420].
Although the overall effects and phenomena of the oxidation and
corrosion of metals has been well characterized [21,22], the atomic
processes at successive time steps of the oxidation or even the
chemical composition of the surface prior to the oxidation are less
well studied. The purpose of our investigation is to extend the
understanding of the FeCrAl surfaces towards the atomic scale.
The knowledge obtained can be used to shed more light on the
state of the surface prior to oxidation. This will help us build a bot-
* Corresponding author at: Department of Physics and Astronomy, University of
Turku, FI-20014 Turku, Finland. Tel.: +358 2 33 5661; fax: +358 2 333 5070.
E-mail address: eknurm@utu. (E. Nurmi).
excellent high temperature oxidation resistance of FeCrAl alloys.
The corrosion resistance of FeCrAl in oxidizing atmosphere is
due to the formation of a highly protective chromium and alumi-
num oxide layer on the surface, which effectively separates the
oxidizing atmosphere from the pure alloy. Because a-Al2O3 is very
stable at high temperatures it would be benecial to maximize its
content at the surface. Unfortunately, for most of the Fe-alloy
applications the most straightforward procedure of increasing
the Al-content in bulk is not an acceptable solution. This is due
to the fact that increasing Al content makes FeAl alloys brittle,
which poses a natural upper bound for the Al-content in these al-
loys regarding to most of the applications. [23] Fortunately, there
exist additional alloying elements that can boost the formation of
the Al-oxide scale on the surface up to such a level that the Al-con-
tent in bulk can be kept within the acceptable limits regarding to
the mechanical properties of the alloy. One of the most common
additional elements for this purpose is Cr. This phenomenon, called
the third element effect (TEE), is still considered a phenomenon
without generally accepted explanation [20,2428]. In the present
investigation we concentrate on the surface phenomena closely

0010-938X/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.06.019
 E. Airiskallio et al. / Corrosion Science 52 (2010) 33943404
related to TEE. To give an extensive account on the energetics of
the pure FeCrAl surfaces at the atomic resolution we have calcu-
lated the differences of the atomic chemical potentials of the com-
ponents in the bulk and at the (0 0 1) surface of FeCrAl.
The excellent corrosion resistance of FeCrAl in oxidizing envi-
ronments is based on the rapid formation of the oxide surface scale
of the right type. Iron oxide on the surface is quite vulnerable to
corrosion in most cases. Chromium oxide provides very good cor-
rosion protection, but only at low and intermediate temperatures.
At low temperatures Cr improves the oxidation resistance of
FeCrAl due to the fast formation of Cr2O3 compared to that of
a-Al2O3 [29,30]. Since at high temperature Cr2O3 transforms to
volatile compounds, e.g. CrO3 [31], the corrosion protection at ele-
vated temperatures requires the more stable aluminum oxide
scales on the surface.
Depending on the concentrations of the alloys, details of the oxi-
dizing environment, as well as criteria used for the oxidation resis-
tance, the literature references show marked variance in the upper
limits of the temperature allowing the protective oxide scales of
Cr2O3 and Al2O3 to form and sustain. The most often reported values
for the upper limits of the feasible temperature range are 900
1100 C for Cr2O3 and 12001400 C for Al2O3 [3,7,25,32,33,31,3436].
Depending on the composition of the FeCrAl ternary alloy dif-
ferent types of oxide scales are formed on the open surface when
exposed to the oxidizing environments. Because the right compo-
sition of the alloy is one of the key prerequisites for a good corro-
sion protection, we have calculated the chemical potential
differences of FeCrAl within a wide range of concentrations,
Cr: 025 at% and Al: 020 at%. Detailed understanding of the equi-
librium surface composition requires knowledge of various proper-
ties of a material, e.g. vacancy formation, migration, diffusion,
lattice relaxation, thermodynamics, kinetics, etc. From this diverse
eld of phenomena we concentrate here on the energetic driving
force for the surface segregation and its consequences on the for-
mation of the protective oxide scale on FeCrAl alloys.
To investigate experimentally the high temperature oxidation
resistance of FeCrAl alloys as a function of Cr- and Al-contents
four different alloys were prepared by induction melting. The al-
loys prepared, Fe13Al, Fe18Al, Fe23Al, and Fe10Cr10Al,
(at% used in alloy formulas) cover the interesting concentration
range including the Al threshold corresponding to the onset of
the high temperature oxidation resistance and the effect of Cr to
turn a non-resistant FeAl alloy to a high temperature oxidation
resistant alloy by enhancing the Al-oxide scale. The samples were
oxidized at 1000 C and the surfaces were investigated by Auger
Electron Spectroscopy (AES), Atomic Force Microscopy (AFM),
and Optical Microscopy. The experimental data are analysed in
the light of computational data to deepen the understanding of
the atomic view of the oxidation of FeCrAl.
2. Computational methods
The calculations are based on the density functional theory
[37,38] and performed using the Exact Mufn-Tin Orbitals (EMTO)
method [39,40]. The EMTO method is an improved screened Kor-
ringaKohnRostoker method [41], where the one-electron poten-
tial is represented by large overlapping mufn-tin potential
spheres. By using overlapping spheres, one describes the crystal
potential more accurately, compared with the conventional non-
overlapping mufn-tin approach [4245].
For the exchange-correlation density functional the generalized-
gradient approximation [46] was used. We have tested earlier that
this choice leads to the best overall equilibrium volume for the
component metals of FeCrAl [47,48]. The EMTO basis set in-
cluded s, p, d, and f orbitals. The one-electron equations were solved
3395
Fig. 1. The equilibrium WignerSeitz radius (rWS in units of Bohr radius) of FeCr
Al alloys as a function of Cr concentration with Al-content as a parameter. For bcc
alloys the lattice parameter (a) and the WS radius are related as a = (8p/3)1/3rWS.
within the scalar-relativistic and soft-core approximations. The
EMTO Greens function was calculated self-consistently for 32 com-
plex energy points distributed exponentially on a semi-circular
contour, which included states within 1 Ry (2  1018 J) below
the Fermi level. In the one-center expansion of the full charge den-
sity, we adopted an l-cutoff of 8 and the total energy was calculated
using the full charge density technique [43,40]. For each alloy the
calculated equilibrium volume was used. The optimized Wigner
Seitz radii are shown in Fig. 1. The convergence of the total energy
with respect to the number of k-vectors was tested. It was found
that 506 (for bulk) and 231 (for surfaces) uniformly distributed k-
vectors in the irreducible part of the 3D and 2D Brillouin zones were
enough for the present purposes. The alloys were described as sub-
stitutionally disordered ferromagnetic bcc alloys [49,50].
Since in the present investigation we map a large concentration
region of FeCrAl with Cr- and Al-concentrations approaching
zero the conventional supercell method would require enormously
large and numerous supercells. Here, we resolve this difculty by
employing the Coherent Potential Approximation (CPA) [51,52].
Within the CPA, the alloy components are embedded in an effective
medium, which is constructed in such a way that it represents, on
the average, the scattering properties of the alloy. In this way, the
original alloy problem reduces to the Schrdinger equation for the
effective medium plus the real space Dyson equations written for
each single impurity. In the present application, we adopt the
CPA implemented within the frameworks of the EMTO method
[39,40]. The EMTO approach has been applied successfully in the
theoretical study of various structural and electronic properties
of alloys and compounds [40], demonstrating the accuracy and
efciency needed for the present investigation.
The semi-innite bulk surface system is modelled by a slab con-
sisting of 8 atomic layers parallel to the surface. To retain the peri-
odicity of the model system an innite array of the slabs separated
by vacuum layers is constructed. The thickness of the vacuum lay-
ers is equivalent to 4 atomic layers. The differences of chemical
potentials of a ternary ABC alloy are calculated as

1 dU 
lA  lB xC constant; 1
N dxA 
where lA, lB, U, N, xA, and xC are the chemical potentials of A and B
components, the internal energy of the system, the number of
atoms in the system, and the atomic fractions of the components
A and C, respectively. One should note that since we require the
3396 E. Airiskallio et al. / Corrosion Science 52 (2010) 33943404

Table 1 Auger line energies used for the concentration determination

Calculated concentration prole of the surface at different temperatures. were: O 510 eV, Cr 530 eV, Fe 705 eV and Al 1395 eV. For alumi-
T (K) Fe5Al Fe5Cr5Al Fe10Cr5Al Fe15Cr5Al num, high energy line was used as there is no interference with
(at%) Fe Al Fe Cr Al Fe Cr Al Fe Cr Al other lines and also the effect of the chemical environment on
the peak shape is smaller. Sensitivity factors for the metallic com-
0 13 87 1 0 99 0 0 100 0 0 100
100 16 84 6 0 94 0 0 100 0 0 100
ponents were measured from pure Cr, Fe and Al samples. Oxygen
200 19 81 9 0 91 0 0 100 1 0 99 sensitivity factor was determined from an Al2O3 layer [29]. Calibra-
300 22 78 12 0 88 1 0 99 3 0 97 tion samples were rst sputter cleaned and then measured using
400 25 75 15 0 85 4 0 96 6 0 94 the same experimental parameters. For aluminum oxide, the sput-
500 27 73 18 0 82 7 0 93 9 0 91
tered surface concentration was supposed to be the same as in bulk
600 30 70 21 0 79 10 0 90 12 0 88
900 37 63 28 0 72 19 0 81 19 0 81 [56].
1200 43 57 34 0 66 27 1 72 26 0 74
1500 49 51 39 0 61 33 1 66 32 0 68
4. Results

4.1. Theoretical surface proles and chemical potentials of alloys

total number of atoms of the system considered to be conserved the
atomic fractions are related as xA + xB + xC = 1. The chemical poten-
tial differences are calculated for the bulk and for the surface. The
surface concentrations for the selected alloys as a function of tem-
perature T (Table 1) were obtained by minimizing the grand poten-
tial (X) of the system.
X tioned LEED measurements is about 57 at%. Our surface prole at
X U  TS  li Ni ;
i
where S is the entropy of the system, and Ni and li are the total
number and the chemical potential of particles of type i. In our cal-
culations only the congurational part was included in the entropy.
Details of the calculational method are published elsewhere [53
55]. While the surface proles shown in Table 1 are calculated by
varying the surface concentrations the rest of the surface calcula-
tions in the present paper refer to homogeneous bulksurface
systems.
3. Experimental procedure
The alloys were prepared by induction melting under argon.
Weighted amounts of pure metals (99.99%) were melted in an alu-
mina crucible. Nominal compositions were Fe13Al, Fe18Al, Fe
23Al and Fe10Cr10Al in atomic %. Ingots were slowly cooled to
room temperature. Atomic % checked with EDX are shown in Table
2. Slides of about 3 mm thick were cut from the ingots. Samples
were grounded with abrasive paper down to 1000 grit to atten
and remove the deformed layer of the surface. Final polishing
was done with 6 and 1 lm diamond suspensions. Samples were
then cleaned with acetone and methanol in ultrasonic bath, and
dried with air ow. Oxidation at 1000 C was performed under
oxygen ow in a quartz tube. Heating of the sample was done by
The calculated surface proles (Table 1) can be compared with
the LEED measurements of the top-layer concentration of
Fe1xAlx(1 0 0) [5759]. In these measurements the surfaces were
annealed not beyond about 1200 K before quenching. For the Fe
5Al alloy the surface Al-concentration according to the abovemen-
2
1200 K is in good agreement with these experimental results.
The difference of the chemical potentials of Fe and Cr (lFe  lCr)
as well as that of Fe and Al (lFe  lAl) were calculated using Eq. (1)
and they are shown in Figs. 2 and 3. The bulk data was calculated
with a dense concentration mesh (xCr, xAl) but since the computa-
tional cost increases considerably for surface calculations the sur-
face mesh is sparser. Due to the smaller number of surface
calculations (16 calculations for (lFe  lCr)surface and 15 calcula-
tions for (lFe  lAl)surface) the difference of the surface chemical
potentials was rst tted to a second order two-dimensional poly-
nomial. This polynomial with xed Al-concentrations (1, 5, and
10 at% Al) is shown as surface data in Figs. 2 and 3. Since at this
point our model system used for FeCrAl alloys is a homogeneous
slab the surface and bulk concentrations in Figs. 2 and 3 are the
same.
Comparison of Figs. 2 and 3 shows that for lFe  lCr the bulk
and surface curves intersect, as in the FeCr case [55], whereas
for lFe  l Al the surface curves are far above the bulk curves. Espe-
cially the (lFe  lCr)bulk curves have a steep slope within the range
45
bulk 1% Al
40
5% Al
35 10% Al
Fe- Cr [mRy]

30 surface
induction and temperature measured with infrared thermometer.
Reaching 1000 C took about 40 s. A PHI 610 spectrometer was 25
used for depth proling. Base pressure during the measurements
was 1  109 Torr. Electron gun was run at 5 keV and 80 nA. Sput- 20
tering was done with 3 keV argon ions at an angle of 40 deg and 15
rastered over 4  4 mm area. The sputtering rate was calibrated
10
using a 100 nm thick Ta2O5 oxide layer as a reference sample.
The estimated etching rate was 4 nm/min. Intensities were deter- 5
mined from the peak-to-peak heights of the differentiated spectra.
0
0 5 10 15 20 25
Table 2 Cr (at. %)
Concentrations of the alloys determined by EDX.
Fig. 2. Bulk and surface chemical potential differences (lFe  lCr) of FeCrAl, (Al
Alloy Fe (at%) Al (at%) Cr (at%) percentages for surface potentials from top to bottom: 1 at%, 5 at% and 10 at%).
Fe13Al 87.4 12.6 Surface data is taken from two-dimensional polynomial t and the calculated bulk
Fe18Al 82.1 17.9 values (shown by symbols) are connected by spline curves. The surface has the
Fe23Al 77.4 22.6 same composition as the bulk. The zero level of lFe  lCr corresponds to
Fe10Cr10Al 79.9 9.8 10.3 443.865 Ry in absolute scale. Atomic chemical potentials are presented, hence
atomic Rydberg units (Ry = 2.17987  1018 J) are used for convenience.
 E. Airiskallio et al. / Corrosion Science 52 (2010) 33943404 3397

70

60
Fe- Al [mRy]

50 bulk 1% Al
5% Al
40 10% Al
surface
30

20

10

0 5 10 15 20 25
Cr (at. %)

Fig. 3. Bulk and surface chemical potential differences (lFe  lAl) of FeCrAl, (Al
percentages for surface potentials from top to bottom: 1 at%, 5 at% and 10 at%). Fig. 4. AES surface depth proles of Fe18Al oxidized at 1000 C and 1 atm for
Surface data is taken from two-dimensional polynomial t and the calculated bulk 5 min.
values (shown by symbols) are connected by spline curves. The surface has the
same composition as the bulk. The zero level of lFe  lAl corresponds to
2059.943 Ry in absolute scale (Ry = 2.17987  1018 J).

of 010 at% Cr. This can be related to the transition from the
Cr-miscible to the Cr-immiscible region in the FeCr bulk phase
diagram [55]. It is also interesting to note that adding Al to the
alloy shifts the chemical potential difference curves down in Figs. 2
and 3. This can be related to the effect of increasing the volume of
the alloy with increasing Al-content (Fig. 1). Similar effect has been
obtained also in FeCrV alloys. [60] The trends of the bulk chem-
ical potentials in Figs. 2 and 3 are also consistent with the experi-
mentally observed Al partitioning in FeCrAl alloys which shows
the depletion of Al from the Cr-rich phases [6163].

4.2. Experimental Auger proles of oxidized surfaces

The prepared ingots of Fe13Al, Fe18Al, Fe23Al, and Fe

10Cr10Al were exposed to oxidizing atmosphere and the result-
Fig. 5. AES surface depth proles of Fe23Al oxidized at 1000 C and 1 atm for
ing oxide scales were investigated by repeated Ar sputtering and
5 min.
Auger measurements. Our Auger measurements of the surface
depth proles of oxidized Fe13Al, Fe18Al, Fe23Al, and Fe
10Cr10Al show that Fe13Al does not form the protective oxide
scale. Instead, the surface was almost entirely covered with a
rough and thick Fe-oxide layer without any traces of Al. In striking
contrast to this the other three alloys form thin protective oxide
layers consisting mainly of Al-oxides. Our experimental AES-re-
sults are shown in Figs. 46.
As shown in the gures the amount of Al (Fe) increases (de-
creases) in the oxide scale in the sequence of Fe18Al, Fe23Al,
and Fe10Cr10Al. This is also the sequence of the improved oxi-
dation resistance, since the Al-oxide gives better protection against
oxidation at high temperature compared with the Cr- and Fe-
oxides.

5. Discussion

5.1. Scaling losses

To take a full advantage of our electronic structure calculations

in the quest for veiled atomic phenomena related to the oxidation
of FeCrAl we rst survey the published data focusing on the for-
mation of oxide scales on the FeCrAl surfaces. The rates of the
scaling loss (weight lost by oxidation) of FeCrAl alloys at
1200 C, reviewed in Ref. [4], are rst converted into a two-dimen-
sional plot (Fig. 7). This representation shows in parallel how both
Fig. 6. AES surface depth proles of Fe10Cr10Al oxidized at 1000 C and 1 atm
for 5 min.
alloying components (Cr and Al) affect the formation of the oxide
lms. One should note that the experimental data that we have
used in our tting procedure, is limited to the region where the
3398 E. Airiskallio et al. / Corrosion Science 52 (2010) 33943404
contours at levels: 0.5, 1, 2, 5, 10, 50
40
35
30
25
Cr (at. %)
20
15
10
5 resistance domains is the 5 g/(m2h) scaling loss curve adapted from Fig. 7.
0 centrations of the alloys. For instance, if the 5 g/(m2h) contour from
0 5 10 15 20
Al (at. %)
Fig. 7. Experimental scaling losses (g/m2h) of FeCrAl alloys at 1200 C after 240 h
oxidation. The colour coding is from 0 to 200 g/m2h. To illustrate the groups of
alloys having similar oxidation rates ve equiscaling contours are shown in the plot.
The plot is obtained by tting to the data shown in Ref. [4].
oxidation rate is 10 g/(m2h) or less. Therefore, the data shown in
the lower left corner of Fig. 7 is a result of extrapolation. However,
one should note that at high temperatures (1000 C) J 10 at% Al
(p. 84 in [4]) or J 14 at% Cr (p. 126 in [2]) are reported to give suf-
cient protection against corrosion in FeAl and FeCr, respec-
tively. It is interesting to note that for these two threshold values
our tting function in Fig. 7 gives scaling losses approximately of
the same order in magnitudes. This clearly suggests that the tting
procedure works well and the obtained function can also be used
within extrapolated regions.
As Fig. 7 shows, at 1200 C in most cases Al is about 1.52 times
as effective oxidation retardant as Cr if scaling losses in FeAl and
FeCr are compared. Nevertheless, considering FeCrAl one can
dene a line in Fig. 7 where Al and Cr are equally effective, i.e.
the reduction in scaling loss is the same for the same amount of
added solute Al or Cr. This dividing line is obtained by joining
the points where the normal of an equiscaling contour is at
45 deg to the horizontal direction. This happens approximately
for the concentrations (cCr, cAl) satisfying
cCr  0:7cAl  2;
where at% are assumed for the concentrations. For alloys above this
line in Fig. 7 adding Al while keeping Cr content xed reduces scal-
ing losses more than doing vice versa (adding Cr with Al-content
xed). Below this line the effectivity of Al and Cr is reversed.
5.2. Protective oxide scales
The reported high temperature (P1000 C) data concerning the
rating of the oxidation resistance of FeCrAl as good or poor [4] is
shown in Fig. 8. Although the results scatter due to dissimilar
experimental conditions and rating criteria used in different inves-
tigations one can divide the diagram approximately into two parts,
showing good or poor oxidation resistance depending on the con-
40
200 threshold
35
180
30
160
140 25
Cr (at. %)
120 20
100 15
80
10
60
5
40
20 0
0 5 10 15 20 25
0 Al (at. %)
Fig. 8. FeCrAl alloys rated as good (lled symbols) or poor (open symbols) with
respect to the high temperature (P1000 C) oxidation resistance. The data is from
Ref. [4] (triangles pointing downward) and from Ref. [20] (triangles pointing
upward). The dividing threshold curve between the poor and good oxidation
Fig. 7 is replotted in Fig. 8 it approximately splits the alloys in two
groups possessing good or poor high temperature oxidation resis-
tance. According to the review article of Thomaszewicz and Wall-
work [4] the Al-concentration in bulk FeAl alloy should be at least
1015 at% in order to the oxidation resistance to be effective at
high temperatures. They also report that adding 10 at% Cr into
FeAl allows one to reduce the Al-content down to 3 at% without
weakening the corrosion resistance of the alloy. The abovemen-
tioned 5 g/(m2h) contour starts from the Fe15Al and goes to about
4 at% Al level when there is 10 at% Cr in FeCrAl. Therefore, the
5 g/(m2h) oxidation rate curve seems to give an approximate lower
limit for the combined Al and Cr concentrations in high-tempera-
ture corrosion resistant FeCrAl alloys. Correspondingly, we sug-
gest that for FeCrAl alloys to have good high temperature
oxidation resistance their concentrations should be chosen accord-
ing to the following relation, corresponding to the dividing thresh-
old curve in Fig. 8,
150
cAl > 4 ; 4
8 cCr
where concentrations are given in at%.
Additionally one should note that the oxidation resistance of
FeAl and FeCrAl alloys seems to correlate with the Al-concen-
tration in the surface layer. According to Fig. 8 the Fe10Cr5Al
and Fe15Al alloys have approximately similar oxidation resis-
tances. Table 1 shows that for the Fe10Cr5Al the calculated Al
3 concentration in the surface at 1200 K is 72 at% and the LEED mea-
surements [59] give about 74 at% Al for the top layer of Fe15Al,
annealed not beyond 1200 K and quenched.
5.3. Oxide type and chemical potentials
We are now at the point when we can compare the calculated
chemical potentials (Figs. 2 and 3) with experiments. For that
purpose we present the difference of the chemical potentials
(lFe  lAl)bulk  (lFe  l Al)surf and (lFe  lCr)bulk  (lFe  lCr)surf
in two-dimensional plots (Figs. 9 and 10). In these gures we also
show the results of the experimental characterization of the main
component of the surface oxides of FeCrAl alloys above 1000 C
[4] and at 800 C [64].
 E. Airiskallio et al. / Corrosion Science 52 (2010) 33943404 3399

-70 AlO dominance at about 5 at% Al, close to the saddle point of the
-68
-66 20 FeCr chemical potential difference plot. The reason for the sug-
-64
-62
gested importance of Cr on the oxidation of FeCrAl in general
-60
15 could be the fast formation of Cr2O3 on the surface, a phenomenon
-58

Cr (at. %)
-56 that would give more time for a-Al2O3 to form up, provided there
-54
-52
is enough Cr at the surface at the initial stage of the oxidation. This
CrO
10 is in line with the grazing angle X-ray diffraction (XRD) measure-
AlO
(Cr,Al)O ments of FeCrAl. In contrast to the commonly held view that
FeO 5 corundum-type oxides only form above 900 C [25], there is a clear
evidence in the XRD results of FeCrAl that a-Al2O3 forms even at
0 700 C [29]. This was proposed to be due to the fact that the corun-
0 5 10 15 20 25 dum nucleation is greatly facilitated on a surface consisting of the
Al (at. %) isostructural Cr2O3.

Fig. 9. Calculated chemical potential difference (lFe  lAl)bulk  (lFe  lAl)surf (in 5.4. Tuning the chemical potentials by Cr substitution
mRy) as a function of Cr- and Al-concentrations. The results of the experimental
characterization of the main component of the oxide scale grown on FeCrAl
Next we discuss how the substitution of Al and/or Fe by Cr in
above 1000 C [4] are shown by symbols. Gray triangle upward: Cr2O3, blue triangle
downward: Al2O3, green square: mixed Cr2O3 and Al2O3, black circle: Fe2O3. (For bulk FeCrAl affects the chemical potentials of the components
interpretation of the references to colour in this gure legend, the reader is referred and how this is expected to be reected in the state of the Fe
to the web version of this article.) CrAl surfaces. The Cr substitution in bulk has direct effects on
both bulk and surface quantities. Starting with bulk properties
we note that lFe  lAl and lFe  lCr both decrease steeply with
15
10 increasing Cr content, within the region from 0 up to 1015 at%
9 20 Cr (Figs. 2 and 3). In contrast to the situation in bulk the chemical
8 II IV
7 potential of the surfaces changes rather slowly within the same
6
5 15 concentration region. This implies increasing chemical potential
Cr (at. %)

4
3
2
10
1
0 the driving force of the Cr diffusion reverses from the surface to
1
2 5
3 in bulk FeCrAl. Summarising from above, the Cr addition to
4
5 I III
CrO 0 tain more Al than they would have otherwise and within a certain
AlO 0 5 10 15 20 25
(Cr,Al)O
FeO Al (at. %)
Fig. 10. Calculated chemical potential difference (lFe  lCr)bulk  (lFe  lCr)surf (in
mRy) as a function of Cr- and Al-concentrations. The results of the experimental
characterization of the main component of the oxide scale grown on FeCrAl
above 1000 C [4] are shown by symbols. Gray triangle upward: Cr2O3, blue triangle
downward: Al2O3, green square: mixed Cr2O3 and Al2O3, black circle: Fe2O3. The
major types of scaling behaviours fall into four regions IIV, separated by solid black
lines [64]. The latter data refer to 800 C and the major components of the oxide
scales are, I: Fe2O3, II: Cr2O3, III: Al2O3 with Fe2O3 nodules, IV: Al2O3. (For
interpretation of the references to colour in this gure legend, the reader is referred
to the web version of this article.)
Somewhat surprisingly, it is observed that although Al-oxide is
the protective component in the oxide scale, there is no correlation
between the calculated FeAl chemical potentials and the measured
composition of the oxide scale (Fig. 9). The reason for this result
could be that the chemical potential difference in Fig. 9 is within
the range from 70 to 50 mRy (1.5  1019 to 1.1  1019 J).
This means that the driving force for the Al diffusion between the
bulk and the surface regions due to chemical potentials is always di-
rected from the bulk to the surface and the relative variations in the
Al driving force are small within the concentration region consid-
ered. On the contrary, as Fig. 10 shows, the FeCr chemical potential
changes sign within the investigated region implying signicant
changes to the chemical potential induced driving force of the Cr dif-
fusion. The FeO dominated scales appear in the lower left corner of
the plot (Fig. 10), where the driving force for Cr is from the surface to
the bulk and there is practically no Cr at the equilibrium surfaces of
these alloys. The experimental borderline of the changing of the Fe
O dominance to CrO or AlO dominance lies approximately at the
line where the chemical potential difference, i.e. the driving force
of Cr diffusion changes its sign. The CrO dominance is changed to
induced driving force for Al atoms to diffuse from the bulk to the
surface, with increasing Cr content in bulk. Fig. 2 also shows that
bulk direction to the bulk to surface direction at about 10 at% Cr
FeAl has a double-edged effect: the equilibrium surfaces will con-
concentration region also Cr appears in the surface. This effect can
be clearly seen in Table 1 where the 10 at% increase in the bulk Cr
content increases the Al-concentration in the surface layer by
about 20 at%. Table 1 also shows that traces of Cr are expected to
be found in the surface at high temperature when the Cr concen-
tration in bulk reaches the 10 at% level. Increasing the Cr content
in FeCrAl up to 15 at% shows that the Cr-driven surface enrich-
ment with Al is saturated. This is due to the attening of the
lFe  lAl (Fig. 3) when the Cr content in bulk is increased beyond
10 at%.
Because the changes in the relative chemical potentials in the
bulk seem to be the key quantities in determining the surface con-
centrations of FeCrAl alloys at equilibrium conditions it is inter-
esting to analyse the mechanisms through which the substi
tutional Cr affects the chemical potentials in more detail. For that
purpose we calculated for FeCrAl the density of states (DOS) at
Fe, Cr, and Al sites as a function of Cr content. Comparing the site pro-
jected DOSs, relative to the common Fermi energy, reveals that the
peaks in the occupied part of the Fe DOS shift down with the increas-
ing Cr concentration. Therefore, the projected band energy in Fe sites
is reduced and since Fe, Cr, and Al sites have the same Fermi energy
this lowering of the Fe bands is consequently transferred to
(lFe  lAl)bulk and (lFe  lCr)bulk which decrease similarly with
increasing Cr content (Figs. 2 and 3).
To some extent it is also possible to relate the chemical poten-
tials to atomic pair energies. To compare our results with these
quantities we refer to investigations on FeAl with Cr impurities.
A study on the effect of Cr on the antiphase boundaries of FeAl al-
loy [65] reports the interatomic energies. The interatomic energies
of AlAl, CrAl, and FeAl pairs are of the same order of magnitude,
approximately from 0.4 to 0.6 eV. The FeFe interaction energy
is about from 1.2 to 1.3 eV and the CrFe interaction energy is
about 1.6 eV. This suggests that adding Cr into FeAl increases
3400 E. Airiskallio et al. / Corrosion Science 52 (2010) 33943404
the average bonding of Fe to the alloy matrix which is in line with
our result of lowering the band energy of Fe. The site resolved mix-
ing energies in FeAl show slight preference for Cr to substitute Al,
i.e. Cr prefers Fe neighbors [66] suggesting stronger bonding in Fe
Cr than in FeAl pairs. Comparing the Cr and Ni additions in FeAl, it
has been found that contrary to Cr, Ni prefers to substitute atoms
in the Fe sublattice [67] which is in line with the fact that Ni tends
to destroy the oxidation resistance of FeAl [4], quite an opposite
effect compared to that of Cr.
5.5. The role of Cr in the oxidation of FeCrAl
The Cr induced changes in the state of the FeCrAl surfaces
suggest important consequences on the formation of the protective
oxide scale on the surfaces of FeCrAl. The initial oxidation de-
pends of course on the state of the alloy surface prior to oxidation.
The Cr addition has both direct and indirect effects. The predicted
increased Al-content in the surface suggests direct improvement in
the formation of protective Al-oxide scales. On the other hand, Cr
itself in the surface may induce transient oxidation containing
Cr-oxide patches which act as oxidation retardants and nucleation
centers for a-Al2O3 [29]. Since the formation rate of Cr-oxide is
higher than that of Al-oxide [68] and Cr2O3 has the same crystal
structure as a-Al2O3 the above facts are suggested to be benecial
to the growth of the protective a-Al2O3 scale on the FeCrAl
surfaces.
5.6. Oxidation experiments
Now we are ready to analyse our experimental observations in
the light of our theoretical results and the published data. We start
with the characterization of the oxide scales of FeAl and FeCrAl
alloys. Analysing Fig. 4 we can distinguish four different zones
within the Auger prole of Fe18Al. Although the division of the
Auger proles into different zones is to some extent arbitrary it
is, however, a very useful concept in investigating the oxidation
mechanism in general and in comparing the oxidation of different
alloys. Here we omit the approximately 5 nm thick topmost sur-
face layer which we expect to have been affected by atmospheric
contaminants. Based on the observed atomic fractions of Fe, Al
and O we dene the different zones in sequence from the surface
to the base alloy as:
1. Surface zone. Within this about 75 nm thick zone the oxygen
content is practically constant while the Fe content decreases
from 5 at% to zero and the Al-content increases from 35 to
40 at% correspondingly.
2. Saturation zone. Here the Al-content reaches its maximum and
there is practically no Fe in this zone. The oxygen content is
at the same level as in the previous zone. The thickness of the
saturation zone is about 40 nm.
3. Inversion zone. In the next, about 60 nm wide section the Fe con-
tent increases and the Al-content drops down, both approach-
ing their bulk values. The right hand side end of the inversion
zone is dened here to be at the inexion point of the Al-con-
centration curve.
4. Deection zone. This about 50 nm thick zone is found below the
inversion zone. Within this zone the atomic concentrations are
still deected from their bulk values to some extent. One should
note that different sputtering yields of the chemical elements
may lead to somewhat biased values for the atomic fractions
in the proles. Especially the result for Al fraction might be
slightly underestimated. However, in our investigations we
used such Auger lines which are not very surface sensitive
[69]. Additional uncertainty to the atomic fractions in the alloy
side is expected to be due to the different sensitivity factors in
the oxide and metal matrices as already discussed in the exper-
imental procedure section.
The four zones described above are clearly discernible also in
the Auger proles of Fe23Al (Fig. 5). In this case the rst two
zones are almost identical to those found in the Fe18Al case. A
slight difference is found at the top of the surface zone: it suggests
that the Fe content decreases and correspondingly the Al-content
increases when the Al-concentration in the base alloy is raised
from 18 to 23 at%. The zones of Fe23Al are slightly thinner than
the zones of Fe18Al.
Compared to the Fe23Al case, the zone structure of Fe10Cr
10Al (Fig. 6) differs more from the zone structure of Fe18Al. From
top to bottom the thickness of the rst three zones in Fe10Cr
10Al are about 85, 50, and 80 nm. The thickness of the deection
zone cannot be determined reliably in this case because our mea-
surement does not extend to a depth which would show the Al-
content to have reached the bulk value. However, we estimated
this zone to be about 60 nm thick. In addition to the fact that the
thicknesses of the zones are somewhat larger in Fe10Cr10Al
compared to those in Fe18Al the heights of the concentration pro-
les within the zones differ from those of Fe18Al as well. The con-
centration variations between the surface and saturation zones in
Fe10Cr10Al are smaller than in Fe18Al. Another clear difference
is that in Fe10Cr10Al the Al-concentration does not have a dip in
the deection zone as it has in the Fe18Al and Fe23Al cases. This
is in line with our earlier prediction of the Cr-induced Al-pump
[70]. Furthermore, in Fe10Cr10Al there is a Cr contribution in
the inversion and deection zones. No Cr in the surface and satura-
tion zones were detected which is in agreement with the differ-
ences between the diffusion constants of the components. The
integrated interdiffusion constant of Cr is much lower than that
of Fe and Al. The approximate ratios are 1:4:5 for Cr, Fe, and Al
in (Fe, Cr)3Al2 [71]. The observed weak maximum in the Cr concen-
tration could be a trace of the initial surface since Cr-rich oxide has
been related to the position of the initial surface before oxidation
[28].
Comparing the Auger proles of Fe10Cr10Al with those of
Fe18Al and Fe23Al reveals that if the Fe and Cr proles are added
up the obtained sum prole within the inversion zone is very sim-
ilar to the Fe proles of Fe18Al and Fe23Al. Also the Al proles of
Fe10Cr10Al, Fe18Al, and Fe23Al are quite similar. One should
note that it is the Al-oxide that is considered to block the atomic
diffusion at high temperatures in these alloys. Therefore, substitut-
ing 1/9 of Fe by Cr in the Fe10Al alloy seems to raise the Al-con-
tent in the oxide scale to the same level as that found in the Fe
18Al and Fe23Al alloys.
5.7. Initial oxidation
So far we have not discussed much the important initial stage of
the oxidation [2,3] of FeAl alloys just at the oxidation resistance
borderline, i.e. alloys containing 1015 at% Al [4]. Therefore, we
now try to get better understanding of the high temperature oxida-
tion of Fe13Al alloys. For that purpose we re-examined our Fe
13Al sample at the initial stage of oxidation. Instead of 5 min oxi-
dation the sample was oxidized only 1 min at normal pressure and
1000 C temperature. After oxidation the surface was scanned by
AFM and a surface with nodules randomly scattered on an other-
wise smooth base was observed (Fig. 11). Our observation is in
agreement with earlier results, see e.g. [64,72], which show ran-
domly positioned Fe-oxide and Fe-sulde nodules on a smooth
Al-oxide surface of FeAl and FeCrAl alloys. Analysing the com-
position of the nodules reveals that they consist almost exclusively
 E. Airiskallio et al. / Corrosion Science 52 (2010) 33943404
Fig. 11. AFM image of an FeO nodule on the smooth surface oxide scale of Fe13Al
oxidized at 1000 C and 1 atm for 1 min.
of iron and oxygen. The nodular structure has been observed also
earlier for FeAl and FeCrAl alloy surfaces [20,27,73,64].
Between the nodules we found a smooth thin oxide scale con-
taining both Fe- and Al-oxides. A typical Auger prole measured
in this smooth surface region between the nodules is shown in
Fig. 12. Comparing Fig. 12 with Fig. 4 one realizes that the thin
smooth oxide scale in Fe13Al shows similar features as the pro-
tective scale in Fe18Al. The signicant differences between Fe
13Al and Fe18Al are found in the surface zone, i.e. in the topmost
part of the oxide scale. In Fe13Al the surface zone contains more
Fe than Al and also the oxygen content, compared to the metal
atoms, is higher than the ratio 3/2 which was found in Fe18Al.
Actually, the total iron content within the surface zone of Fe
13Al is several magnitudes higher than in the Fe18Al case. This
suggests that at the initial stage the Al-oxide scale in Fe13Al leaks
and there exists a substantial Fe ux from the base alloy to the sur-
face through the Al-oxide scale during the rst moments of the
oxidation.
Our investigations suggest that the surface of Fe13Al is par-
tially covered by the protective Al-oxide scale. This Al-oxide scale
shows two blocking fronts (Fig. 12). The blocking front for the Fe
diffusion from the bulk alloy to the surface is located about
125 nm below the surface and the blocking front for the O diffusion
from the surface to the bulk alloy is found about 50 nm below the
surface. However, the protective Al-oxide scale in Fe13Al is only a
transient feature. We already know from our earlier oxidation
experiments that after 5 min of oxidation most of the surface is
covered with a non-protective thick Fe-oxide scale. The protective
Al-oxide scale of Fe13Al can be destroyed principally in two ways.
The destructive Fe-oxidation may start from the Fe-oxide rich nod-
ules and proceed sideways along the surface into the protective
Fig. 12. AES surface depth proles of the smooth oxide scale of Fe13Al oxidized at
1000 C and 1 atm for 1 min.
3401
Fig. 13. Optical microscope image of FeO nodules at the surface of Fe13Al
oxidized at 1000 C and 1 atm for 1 min.
oxide scale, eventually breaking it. There can be also hidden de-
fects in the protective scale through which Fe atoms can gradually
diffuse from the bulk alloy to the surface and O atoms can diffuse
from the surface to the bulk alloy. This kind of leak process would,
however, trigger new Fe-rich nodules on the smooth oxide scale.
To obtain information on the large scale properties of the nod-
ular structure of the oxidized Fe13Al surface optical microscope
was used. As Fig. 13 shows the Fe-oxide nodules are randomly
scattered throughout the otherwise smooth surface. Since after
1 min of oxidation all the nodules have the same symmetrical cir-
cular shape and they all are of the same size, we conclude that they
all have emerged at the very rst moments of the oxidation from
point defects scattered randomly on the initial alloy surface. Dur-
ing the oxidation the nodules grow and after 5 min they practically
cover the whole surface. To improve the oxidation resistance of
low-Al Fe-alloys it is important to investigate what are those point
defects that nucleate the nodular growth of Fe-oxide and what are
the possibilities to inactivate them.
The main features of our Auger depth proles agree with those
of other similar measurements on FeAl and FeCrAl alloys [73
78]. Summarizing from above, the following conception of the oxi-
dation process of the investigated alloys is proposed.
(i) For FeAl alloys under oxygen ow at 1000 C and 1 atm the
threshold value of the Al-content for the protective Al-oxide
scale to form up and hold for a longer time is between 13
and 18 at% in the base alloy.
(ii) In the main part of the oxide scale the oxygen and metal
atom concentrations are 60 and 40 at%, respectively, cor-
responding to the atomic fractions in the stoichiometric oxi-
des Al2O3 and Fe2O3. This suggests that in the surface and
saturation zones practically all oxygen and metal atoms
are combined into oxides.
(iii) The building up of the Fe-free saturation zone can be under-
stood in the following way. At the early stages of oxidation
there presumably exist both Al- and Fe-oxides in the satura-
tion zone region. However, the oxygen ow from the gas
phase is decreased step by step as the oxide layer grows. If
there is no free oxygen available and the Al ux from the
base alloy brings more Al to this region the higher oxygen
afnity of Al [79], compared to that of Fe, leads to the pro-
cess 2Al + Fe2O3 ? 2Fe + Al2O3 which combined with the
subsequent Fe escape due to diffusion saturates this zone
with Al-oxide.
3402 E. Airiskallio et al. / Corrosion Science 52 (2010) 33943404
(iv) When the Al-concentration of an FeAl alloy is close to the
threshold value of the onset of the high temperature oxida-
tion resistance both protective and non-protective surface
oxide scales coexist at the surface. The non-protective oxide
scale grows by the rapid generation of the FeO nodules dur-
ing the rst moments of the oxidation. These nodules are
nucleated by the surface point defects. While the oxidation
continues the nodules grow at the expense of the protective
scale.
(v) Replacing Fe by Cr in the base alloy pushes more Al to the
surface region leading to the formation of the protective
Al-oxide scale with considerably reduced Al-content in the
base alloy. In the oxide scale of Fe10Cr10Al the concentra-
tion of Al is even higher than in the oxide scales of Fe18Al
and Fe23Al alloys.
5.8. Atomic scale mechanisms
To shed some light on the underlying mechanisms of the sur-
face oxidation of FeAl alloys we reconsider our experimental data
in the light of our computational results. The computational results
refer to the (0 0 1) surface. However, the oxidation experiments for
FeAl above 500 C lead to the formation of well-ordered Al2O3 lms
on all low-index surfaces (0 0 1), (0 1 1), and (1 1 1) [34]. Moreover
Al segregation is observed for all low-index surfaces [69]. We
therefore expect that the theoretical results for the (0 0 1) surface
can be justiably used in analysing our experimental data.
From the theoretical point of view we can describe two features
that affect the oxidation resistance of FeAl alloys at high temper-
atures. The rst one is a straightforward mechanism to improve
the oxidation resistance simply by increasing the Al-concentration
in the base alloy. This accelerates, in a natural way, the formation
of the protective Al-oxide scale which then reduces both internal
oxidation as well as the growth of the outer oxide scale.
However, there exists another, a more complex, mechanism
that is also benecial to the oxidation resistance of FeAl alloys.
This can be explained by considering the calculated chemical
potentials shown in Fig. 3. As seen in Fig. 3 there exists a strong
chemical potential induced driving force for Al to diffuse from bulk
to the surface which is in line with the surface energies of the com-
ponents [80,81] and the results of the surface segregation investi-
gations [82].
It is also useful to relate the data shown in Fig. 3 to the diffusion
coefcients in FeCrAl. Considering either direct or concerted
AlFe pair exchange process [83] the corresponding diffusion
coefcient for the Al moving towards the surface (Ds) or Al moving
towards the bulk (Db) are approximated as
Ds D0 eDEs =kB T ;
Db D0 eDEb =kB T ;
where T is the temperature and kB is the Boltzmanns constant, the
activation energies are
DEs Esp  EAln1;Fen ; 7 are approximately the same and also according to Fig. 7 the exper-
sp Aln;Fen1
DEb E  E : 8
Here D0 and Esp are the pre-exponential factor and the energy of the
system when the AlFe pair is in its saddle-point conguration
along its migration path, both assumed to be independent of the
direction of the exchange process. EAl(n + 1),Fe(n) and EAl(n),Fe(n+1) are
the energies of the system in the initial states corresponding to
AlFe pair having the Al end in the bulk side or in the surface side,
respectively. The index n refers to the atomic layer, n = 0 refers to
the surface layer and deeper layers towards the bulk are indexed
Ds
Eb Es
Energy
Db
0 1 2 3
n (Distance form the surface)
Fig. 14. Schematic gure of the energetics of the exchange processes of AlFe pairs.
The red wavy curve represents the energy of the system at different stages of the
pair exchange of an FeAl pair. The conguration Al at n = 1 and Fe at n = 2 is shown
by the green sphere on the left and the conguration Fe at n = 1 and Al at n = 2 is
shown by the green sphere on the right. On average Al atoms in FeCr matrix will
diffuse from right to left, i.e. from the high Cr region (bulk side, high potential) to
the low Cr region (surface side, low potential). (For interpretation of the references
to colour in this gure legend, the reader is referred to the web version of this
article.)
with successively increasing n. From Eqs. (5)(8) one obtains the ra-
tio of the diffusion coefcients
n n
Ds elFe lAl =kB T
n1 n1 : 9
Db elFe lAl =kB T
According to our calculations (Table 1) the Cr concentration at the
surface is lower than that in the bulk. Therefore, it is expected that
in the region between the bulk and the surface ln1 Fe  lAl
n1
is less
than lnFe  lnAl (in line with Fig. 3) leading to Ds/Db > 1, i.e. the above
model predicts the driving force of the Al diffusion to be towards
the surface. The energetics of the diffusion is illustrated in Fig. 14.
Due to the anisotropy of the Al diffusion, the Al-concentration in
the surface region is expected to exceed that in the bulk. This
enrichment of the surface with Al continues as long as the mini-
mum of the free energy has been achieved or the surface has be-
come saturated with Al. When this stage is reached there is no
net driving force for Al diffusion to any direction.
In Table 1 we show the calculated equilibrium surface concen-
tration of Fe5Al alloy as a function of temperature. We see that at
0 K the surface in the equilibrium state contains 87 at% Al. Using
the data in Fig. 3 we estimate that in the case of Fe13Al, Fe
18Al, and Fe23Al the equilibrium surface at 0 K would contain
5
about 94, 98 and 100 at% Al, respectively. However, at high tem-
6 peratures the entropy contribution in the free energy becomes sig-
nicant and consequently at about 1000 C the corresponding
equilibrium Al surface concentrations for Fe13Al, Fe18Al, and
Fe23Al are 67, 72 and 77, respectively. It is interesting to note that
the Al surface concentrations at 1000 C of Fe13Al and Fe5Cr5Al
imental scaling losses of these alloys are of the same order. An-
other similar pair of alloys is Fe18Al and Fe10Cr5Al suggesting
for a connection between the Al-concentration at the surface layer
and the scaling loss in oxidation atmosphere.
What is even more interesting here is the role of Cr in enhancing
the oxidation resistance of FeAl alloys. The effect of Cr on the driv-
ing force of Al diffusion is clearly seen in Fig. 3. The chemical poten-
tial difference (lFe  lAl)bulk decreases substantially when Cr
content in the base alloy is increased from 0 to 10 at%. This decrease
means that in the bulk the chemical potential of Al is raised com-
 E. Airiskallio et al. / Corrosion Science 52 (2010) 33943404
pared to that of Fe. Because the same Cr addition does not change the
chemical potential difference at the surface appreciably, the driving
force of Al from bulk to the surface is therefore considerably en-
hanced due to the Cr addition as veried computationally and shown
in Table 1. The Cr-enhanced oxidation resistance discussed above is
effective mainly at the initial stage of oxidation or during the healing
of a broken oxide scale, i.e. in cases where an open metal surface is
exposed to oxidizing environment. However, this is not the whole
story of the benecial effect of Cr in FeAl alloys. Cr improves the oxi-
dation resistance of FeAl alloys also during the steady state of the
oxide scale growth. Comparison of Figs. 5 and 6 shows that an Fe
10Cr10Al alloy has a better supply of Al in the oxide scale than an
Fe23Al alloy even though the Al-content in the latter is more than
twice of that of the rst one. In the oxide scale of Fe10Cr10Al
the Al-content is higher and correspondingly the Fe content lower
than in the oxide scale of the Fe23Al alloy. This can be understood
on the basis of the calculated chemical potentials shown in Fig. 3.
During the initial oxidation also Cr oxidizes leading to a Cr-depleted
zone [84,15] under the oxide scale. Due to the slow mobility of Cr
[71] this Cr-depleted zone is stable. If the Al-concentration in bulk
is below the critical level, then due to the high oxygen afnity of Al
[79] the exposure of the surface to oxygen results in a formation of
an Al-depleted zone under the oxide scale, which could eventually
lead to the breakdown of the protective oxide scale [4]. The impor-
tant issue within the maintaining of the protective oxide scale is
the recovery of the Al level in the depleted zone. At this point Cr plays
an important role. As seen in Fig. 3 the Cr depletion in FeCrAl raises
the chemical potential of Fe relative to that of Al and consequently
helps in restoring the Al to Fe ratio in the depleted zone to the level
that is needed to maintain the protective oxide scale.
Using the chemical potentials shown in Fig. 3 we can give a the-
oretical estimate, based on our calculations, on the effectivity of Al
and Cr on the improvement of the high temperature oxidation
resistance of FeCrAl alloys. To get the same improvement in
the oxidation resistance the Al addition should be about twice of
the amount of the Cr addition. This result is in line with our Auger
measurements since comparing Figs. 46 one observes that the
oxide scale of Fe10Cr10Al contains less Fe than that of Fe
23Al. Therefore, adding 10 at% Cr is effectively more than adding
13 at% Al. Also the experimental results of the scaling losses
(Fig. 7) show that if one considers, for instance, Fe10Al which
has the scaling loss of about 50 g/(m2h), there are two extreme
ways to improve its oxidation resistance. One can either substitute
Fe by Cr or Al. If the Cr concentration is increased from 0 to 5 at%
we arrive at the Fe5Cr10Al alloy which has the scaling loss of
about 2 g/(m2h). In order to achieve the same scaling loss level
by Al addition we have to add Al twice of the Cr amount, which
leads to the Fe20Al alloy having approximately the 2 g/(m2h) scal-
ing loss.
As Fig. 2 shows, adding Cr into FeAl alloys affects also lFe  lCr.
As above, also in this case the drop of lFe  lCr in the bulk is much
larger than at the surface. Therefore, considering FexCr10Al alloys
one observes that for small x the driving force for Cr (relative to that
of Fe) is from the surface to the bulk. Increasing the Cr concentration
this tendency gradually weakens and at about 10 at% Cr in the base
alloy there is no relative driving force anymore and Cr and Fe have
equal probabilities to occupy bulk and surface sites. This phenome-
non of the increasing of the probability of Cr, relative to that of Fe, to
occupy surface sites has also a benecial effect on the formation of
the protective oxide scale on the surface.
6. Conclusions
Ab initio electronic structure calculations have been performed
for Fe1xyCrxAly alloys, 0 6 x 6 0.25, 0 6 y 6 0.25. The measured
3403
AES surface depth proles are compared with the calculated atom-
ic chemical potentials and surface concentration proles. To con-
clude we list the main results found in our investigation.
1. Increasing the Al-content of FeAl from 13 to 18 at% makes the
alloy resistant to oxidation at 1000 C. Further increase of the Al
content to 23 at% slightly improves the protecting Al-oxide
scale on the surface. At the borderline of the onset of the oxida-
tion resistance in FeAl alloys the nodular growth of Fe-oxide is
nucleated at randomly scattered points along the surface. Dur-
ing the oxidation these nodules grow in size but not in number.
Further investigation of the nucleation and the early kinetics of
these nodules is expected to be useful in improving the quality
of FeAl surfaces.
2. Substituting Fe by Cr in FeAl alloys clearly increases the driv-
ing force of Al to diffuse from the bulk to the surface. Because
the increase of the Al driving force is mainly due to bulk prop-
erties, this increase is not very sensitive to the type of the sur-
face, whether it is metal or oxide, or the type of the oxide. A
driving force for the Al diffusion based on the Cr concentration
gradient in FeCrAl is predicted.
3. Comparing the measured chemical composition of the oxide
scales with the calculated chemical potentials of the atoms in
the bulk and at the surface of the alloy a correlation between
the composition of the oxide and the energetic balance between
Fe and Cr in the bulk and at the surface (namely (lFe  lCr)-
bulk
 (lFe  lCr)surf) can be seen. In the case of Fe and Al a sim-
ilar kind of correlation is not found.
4. With increasing Cr content the Fe bands shift down, relative to
the Cr and Al bands, which can be related to the calculated
changes in the chemical potentials in FeCrAl. Increasing the
Cr concentration in the bulk results in two effects on the surface
of the FeAl alloys: the Al-content at the surface increases and
Cr is also found at the surface.
5. Corrosion resistant surfaces of FeCrAl are quite robust
because their formation and self-healing properties are to a
large extent determined by the bulk part of the alloy.
Acknowledgements
The computer resources of the Finnish IT Center for Science
(CSC) and Mgrid project are acknowledged. Financial support from
the Academy of Finland (Grant No. 116317), Outokumpu Founda-
tion (E.A.), National Graduate School in Materials Physics (E.N.),
the Swedish Research Council, the Swedish Iron Ofce (B.J., L.V.),
and the Carl Tryggers Foundation (M.P.) are acknowledged.
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