Intermetallics 13 (2005) 1245–1254

www.elsevier.com/locate/intermet

Embedded atom method study of the interaction between point

defects in iron aluminides: Triple defects
Renata N. Nogueira, Cláudio G. Schön*
Computational Materials Science Laboratory, Department of Metallurgical and Materials Engineering, Escola Politécnica da
Universidade de São Paulo, Av. Prof. Mello Moraes, 2463—CEP 05508-900, São Paulo-SP, Brazil
Received 30 August 2004; received in revised form 23 March 2005; accepted 11 April 2005
Available online 20 June 2005

Abstract
In the present work (part 2 of 2), a follow-up of the investigation of the interaction between point defects (both vacancies and antisite
atoms) in Fe–Al compounds with A2 (Fe) and B2 (FeAl) structures is performed using Embedded Atom Method (EAM) molecular statics
atomistic simulations. This method is particularly useful in obtaining the self-energies of crystal defects characterized by strong local
relaxation strains, which generate long-range elastic fields. The methodology developed in the first part of this paper is applied here to the
case of triple defect clusters, which are essential to understand diffusion in iron aluminides, with emphasis to B2 alloys. Particular care was
taken to assure that all simulations for a given compound refer to the same ensemble.
q 2005 Elsevier Ltd. All rights reserved.

Keywords: A. Iron aluminides (based on FeAl); B. Bonding; D. Defects: point defects; E. Simulations atomistic; E. Defects, theory

1. Introduction For antisite-vacancy pairs, we found that their interactions

In the first part of the present investigation, a systematic
study of the interactions between pairs of point defects
(both antisite defects and vacancies) was performed [1]. In
those cases, long-range anisotropic interactions were
obtained, with variable strength and character (either
attractive or repulsive) depending of the particular kind
of pair. As general trends, divacancy complexes of nearest
and next-nearest vacancy pairs are characterized by
attractive bonds of the order of magnitude of K0.1 eV,1
while Al antisite atom pairs (i.e. two aluminium atoms in
iron lattice positions) present strong repulsive interactions
(of the order of magnitude of C0.2 eV) in the nearest
neighbourhood. Another relevant finding of the first part
investigation was a sort of ‘universality’ in the dependence
of the interactions of a vacancy pair with distance.
* Corresponding author. Tel.: C55 11 3091 5726; fax: C55 11 3091
5243.
E-mail addresses: rnogueir@usp.br (R.N. Nogueira), schoen@usp.br
(C.G. Schön).
1
With reference to the energy of a crystal containing the isolated defects.
0966-9795/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.intermet.2005.04.008
are mainly governed by the configuration of the first
coordination shell around the vacancy. This poses the
question whether a similar interaction can be found or not
in more extended defect complexes, consisting of three
point defects (i.e. triple defects). The present work handles
this problem using the same approach employed in the
first part.
Triple defects are postulated to exist in iron aluminides,
especially in the case of B2 near stoichiometric alloys. This
postulation is based on experimental observations that, due
to their formation self-energies, the dominant kind of defect
is different for under- and overstoichiometric alloys (antisite
FeAl atoms in the former and VFe vacancies in the later2): in
order to accommodate the two types of defects keeping the
stoichiometric ratio constant at equiatomic compositions,
two vacancies must be created for each antisite atom to be
formed [2]. It is interesting to observe that this rule is based
only on mass balance considerations and that it can be
fulfilled even if the three defects are not correlated (e.g. the
three defects may be formed at different and quite distant
2
This notation has been introduced in the first part of the investigation.
XY represents a defect of kind X (Fe, Al or VZvacancy), located in
sublattice Y.
1246 R.N. Nogueira, C.G. Schön / Intermetallics 13 (2005) 1245–1254

parts of the system and cannot be considered proper triple

defects, in the sense discussed in the present work).3 A
different situation, however, is found in the case of diffusion
atomistics. Here the defects must interact (in other words,
exchange positions) to produce mass transport, this leads
necessarily to configurations with defects located on a
nearest or next-nearest vicinity. All the three diffusion
mechanisms postulated to explain diffusion in near
stoichiometric B2 alloys [2], involve some kind of triple
defect in an intermediate stage in the diffusion path. This
can be easily demonstrated by considering two of these
mechanisms:

† The Antistructure Bridge (ASB) mechanisms and

† The ‘Triple Defect’ (TRD) mechanism.

In the ASB mechanism (schematically represented in

Fig. 1), a VAl vacancy exchange position with an iron atom
in the iron sublattice (i.e. FeFe) in the presence of an antisite
FeAl defect (Fig. 1(a)), forming the triple defect complex
FeAl–VFe–FeAl (Fig. 1(b)). In this particular figure, the three
defects are located along a [111] direction. After a next
jump, the vacancy exchange positions with the previous
antisite atom (Fig. 1(c)),

leading to a net transfer of the iron
along lattice vector 12 12 12 .
The TRD mechanism (Fig. 2), on the other hand,
involves the conversion of a divacancy, e.g. VFe–VAl
(Fig. 2(a)) into a triple defect like VFe–FeAl–VFe, by
reaction with an FeFe atom (Fig. 2(b)), resulting in the net
transport of iron along lattice vector [100]. The TRD
mechanism leads to the coupling of the diffusion fluxes for
both species [2].
The third mechanism quoted by Mehrer [2], the six-jump
cycle (6JC) mechanism, also includes the formation of triple Fig. 1. Schematic representation of the Antistructure Bridge Mechanism
defect complexes in intermediate steps in the diffusion path (ASB) of diffusion in iron aluminides: (a) initial configuration, (b)
(for example, in steps 3 and 5 of the path shown in Fig. 1 of intermediate configuration (containing a triple defect FeAl–VFe–Fe h Al), (c)
i

ref. [3]). The 6JC is supposed to play an essential role in the final configuration with a net transfer of iron along lattice vector 12 12 12 .
diffusion of highly ordered, near stoichiometric B2
intermetallics [3–5], but, as Mehrer points out [2], its The role of triple defects in the diffusion mechanisms of B2
relevance should decrease as antisite defects are produced FeAl is more controversial. Recent thermodynamic calcu-
either by large deviations from the ideal stoichiometry or by lations suggest that all four kinds of point defects are present
the decrease of the order parameter at high temperatures. in those alloys (i.e. VAl, VFe, FeAl and AlFe) [17], and that
Experimental evidences for the activity of triple defects there would be, therefore, no need to invoke the TRD
either by direct measurement (e.g. by Positron annihilation) mechanism to explain diffusion in iron aluminides. This
or in diffusion and recovery process investigations in B2
view agrees with the experimental results of Refs. ([18,19])
ordered compounds are found in CoGa [6], NiAl [7–9], PdIn
and is compatible with Mössbauer spectroscopy results [20].
[10], (Ni,Fe)Al [11] and FeAl [12,13]. Theoretical
From the above exposition it is clear that considerable
considerations also provide evidences for the existence
doubt still remains on the importance of triple defects in B2
of triple defects in B2 NiAl [14,15] and B2 CoGa [16].
alloys, in particular in the case of diffusion in FeAl. The aim
of the present work is to investigate, using the procedure
3
It is usual in the diffusion literature to reserve the term ‘triple defect’ to developed in the first part [1], the stable configurations
describe the VFe—FeAl–VFe defect here discussed. In the sense of the corresponding to triple defects in B2 FeAl and A2 Fe
present work, however, all combinations of three point defects are referred
to as triple defects. In all cases, where the term ‘triple defect’ is used in the
compounds, differing from stoichiometry only by the
present work with the usual meaning, this distinction will be made by existence of the point defects. As in the previous case, all
writing the term inside single quotes. simulations for each compound are performed containing
 R.N. Nogueira, C.G. Schön / Intermetallics 13 (2005) 1245–1254
Fig. 2. Schematic representation of the Triple Defect (TRD) diffusion
mechanism in iron aluminides: (a) initial configuration, (b) intermediate
configuration (containing the triple defect VFe–FeAl–VFe), and (c) final
configuration (with the net transfer of Fe along lattice vector [100]).
the same number and kinds of point defects, so that all
simulations for a given compound are performed with a
constant number of atoms in the crystal block, i.e. the
simulations are performed in the canonical ensemble.
2. Methodology
2.1. General
The procedure adopted in this work is the same we
described in Part 1 [1]: a set of point defects (both vacancies
and antisite atoms) is placed in a ‘computer crystal’ such
that their distances are large enough to avoid any interaction
between them. The EAM functional (Eq. (1) of Part 1 [1]) is
1247
minimized with respect to the atom positions and the
minimum energy is labelled E0. This corresponds to the
reference state of the calculation.
In the simulation of a given triple defect, three isolated
point defects (let us say x, z and j)4 are selected from those
present in the computer crystal and placed near the centre of
the atom block, such that they are now interacting. This
procedure guarantees that the reference block and all triple
defects contain the same number and kinds of atoms for a
given compound, which means that the simulations are done
in the canonical ensemble. The minimum energy corre-
sponding to this configuration is referred to as Exzj and the
interaction energy of the defect complex is calculated as:
DExzj Z Exzj K E0 (1a)
The triple defect, however, is built of three defect pairs,
for which the interaction energies have been determined in
Part 1 [1], therefore, Eq. (1a) may be rewritten as
DExzj Z 3xzj C DExz C DExj C DEjz (1b)
xz xj jz
where DE , DE and DE are the interaction energies of
the corresponding defect pairs and 3xzj corresponds to an
excess term of the interaction energy due to the formation of
the triple defect. Both quantities, the interaction energy,
DExzj, and the excess interaction energy, 3xzj, will be used
in the discussion of the triple defect configurations
investigated in the present work.
2.2. Configurations
The multiplicity of possible triple defect configurations is
too large and it does not allow an exhaustive study as
performed for the pair configurations in Part 1 [1].
Therefore, it was necessary to restrain the presentation of
the results using some criteria, in the hope that this choice
would allow to draw conclusions about the general
properties of the triple defects in the alloy. The following
criteria have been adopted:
1. configurations which are experimentally observed in
Fe–Al alloys will be discussed,
2. only configurations in the B2 FeAl compound and in the
A2 Fe disordered host will be shown,
3. all discussed defects are formed by two equidistant pairs,
which are used as reference to identify the given defect,
and
4. the upper bound of the length of the equidistant pairs
corresponds to the third neighbourhood.
These restrictions have been tested by single calculations
and will be discussed later on, when necessary, in the
present work.
4
As in Part 1 [1], lattice positions are labelled using greek letters, while
the species (or, in the present case, the defect) occupying the lattice site
using roman letters.
1248 R.N. Nogueira, C.G. Schön / Intermetallics 13 (2005) 1245–1254

The nomenclature of the defects also plays an important
role here. In Part 1 [1], each pair was identified by the kind
of point defects involved and by its size (i.e. the distance
between the point defects in terms of neighbourhood). For
triple defects, a third characteristic must be taken into
account: the defect geometry.
Fig. 3 shows six [110] projections of the bcc lattice, each
of them containing a different triple defect geometry
investigated in this work. It is clearly seen that the
configurations may be divided into two major groups:
those that are arranged in the projection in the form of a
triangle (Fig. 1(a)–(c)), and those that are arranged in the
form of a line (Fig. 1(d)–(f)). A second characteristic is the
size of the defect: it may be characterized by the distance
between the point defects in the equidistant pairs: nearest
neighbours (Fig. 1(a) and (d)), next-nearest neighbours

Fig. 3. [110] Projection of a bcc lattice showing the schematic representation of spatial configurations of triple defects considered in this work: (a) 1T, (b) 2T,
(c) 3T, (d) 1L, (e) 2L and (f) 3L.
 R.N. Nogueira, C.G. Schön / Intermetallics 13 (2005) 1245–1254
Table 1
Distance (in terms of neighbourhood) between the point defects in the bg
pair of the six cases of triple defects shown in Fig. 1 (ab and ag are the
equidistant pairs)
Triple 1T 2T 3T 1L 2L 3L
defect
bg 2 3 6 3 6 25
(Fig. 1(b) and (e)) and third neighbours (Fig. 1(c) and (f)).
The defect geometry will be identified primarily by these
two characteristics. For example, a 2L configuration
corresponds to a triple defect formed by two equidistant
pairs of next-nearest neighbour point defects which are in
line in the [110] projection (Fig. 1(e)); 1T, on the other hand
corresponds to a triangular arrangement of nearest
neighbour pairs (Fig. 1(a)). The geometries of the triple
defects considered in this study are identified in the legend
of Fig. 3. The individual defects are labelled a, b and g,
being a the defect that is common to the equidistant pairs
(i.e. the equidistant pairs correspond to ab and ag). Table 1
shows the corresponding distance of the third pair (bg) for
the six triple defects shown in Fig. 3.
The types of point defects composing the triple defects
are identified as antisite atoms,5 a, or vacancies; v, A triple
defect will be, thus, identified by its geometry (as described
above) and by the types of point defects in positions a, b,
and g; aaa, three antisite atoms; aav, antisite atoms at a and
b and a vacancy at g, and so on.
For B2 superlattices, one must notice that the considered
geometries lead to two classes of defects, depending on the
original occupancy of the a site. A first group corresponds to
a site in the Fe sublattice and the second, to a site placed in
the Al sublattice. Table 2 relates the occupancies of the
sublattices corresponding to each point defect for the six
cases shown in Fig. 1 in the B2 lattice, depending on the
original occupancy of the a sublattice.
3. Results and discussion
The results will be presented and discussed in two parts:
Section 3.1 presents the results of defects in the disordered
A2 Fe lattice and Section 3.2, those for the B2 FeAl
compound.
3.1. Defects in A2 Fe
Table 3 shows the results for the six classes of triple
defects investigated in the present work. The analysis of
5
As discussed in Part 1 [1], strictly speaking, one cannot refer to an
antisite atom in the case of the disordered A2 lattice since no preferred
occupation of sublattices exists. In this case this defect corresponds to a
solute aluminium atom in the iron host. For the sake of simplicity, however,
the defect will be referred to as an antisite atom to compare with the
behaviour of the triple defects in the B2 lattice.
1249
Table 2
Occupancy of the sublattices corresponding to sites b and g depending on
the occupancy of the a sublattice (X), with XZFe 0 YZAl and XZAl 0
YZ Fe
Triple defect b g
1T Y Y
1L Y Y
2T X X
2L X X
3T X X
3L X X
the table shows that the excess interaction energy term,
3xzj, is very small in modulus, and the magnitude of the
largest value is smaller than 0.05 eV. In most configur-
ations, it corresponds to about 10% of the interaction
energy for the individual pairs, which form that defect [1].
In other words, the interactions responsible for the
formation of pairs of defects are much more relevant that
the ones responsible for the formation of triple defects in
the disordered compound.
Since the excess interaction energy is very small, one
may, as a first approximation, perform the analysis
considering the individual pairs that form the triple defect.
As discussed in Part 1 [1], interactions between aluminium
atoms in the iron host are repulsive for nearest and next-
nearest pairs, but become attractive for distances above the
third neighbourhood. The interaction between vacancies
follows the inverse trend, with attractive interactions in the
nearest and next-nearest neighbourhood. On the other
hand, antisite atom–vacancy pairs tend to show attractive
interactions, but the magnitudes of these interactions are
lower than those observed for the other pairs [1]. This is
reflected in the interaction energies of the corresponding
triple defects. For instance, in the aav–1T configuration,
one of the three pairs is a nearest neighbour AlFe–AlFe
pair, which has a strong repulsive character (DExzZC
0.25 eV [1]) and the addition of a vacancy at position g
creates two Al Fe –V Fe pairs, which have moderate
attractive interaction. As a result, the repulsive character
of the interaction for the triple defect is reduced to
C0.11 eV, less than half the value of the isolated pair.
The other cases that also show similar behaviour are aaa–
2T, aav–1T, avv–2T and avv–2L.
The negligible excess interaction for all investigated
configurations shows that the formation of bound states
corresponding to the triple defects is unlikely in the
disordered alloy. Triple defects of statistical nature may
be formed in the alloy, and it is possible that entropic
contributions (either vibrational or configurational) could
stabilize triple defect configurations, especially in concen-
trated alloys at high temperatures. In other words, the
possibility of formation of entropically stabilized triple
defects in A2 Fe–Al with increasing temperature should not
be discarded.
1250 R.N. Nogueira, C.G. Schön / Intermetallics 13 (2005) 1245–1254

Table 3
Interaction energies and excess interaction energies (in eV) of the triple defects listed in Fig. 1 for the case of the A2 Fe compound

Defect 1T 1L 2T 2L 3T 3L
abg
aaa DE C0.51 C0.45 C0.06 C0.16 K0.14 K0.14
3abg K0.05 C0.02 C0.01 C0.03 0 0
aav DEabg C0.11 C0.14 C0.02 C0.04 K0.06 K0.07
3abg 0 K0.03 0 C0.02 0 0
avv DEabg K0.36 K0.08 K0.05 K0.07 C0.02 0
3abg C0.02 C0.04 0 0 0 0
vva DEabg K0.29 K0.24 K0.26 K0.26 C0.05 C0.04
3abg C0.01 0.01 0 0 0 0

Table 4
Interaction energies and excess interaction energies (in eV) for the six triple defects listed in Fig. 1 for the B2 FeAl compound in which the a position is in the
Fe sublattice

Defect 1T 1L 2T 2L 3T 3L
abg
aaa DE K0.34 K0.41 K0.09 K0.07 K0.06 K0.05
3abg K0.09 C0.02 K0.01 0 0 0
aav DEabg n.c. K0.58 K0.09 K0.04 K0.07 K0.08
3abg n.c. C1.86 C0.01 0.02 0 0
avv DEabg K1.41 K0.67 K0.02 K0.03 K0.06 K0.09
3abg C2.99 C3.77 K0.01 K0.01 0 0
vva DEabg C0.07 K0.18 K0.02 K0.16 K0.02 K0.01
3abg K0.05 K0.10 C0.01 0 0 0

Obs.: n.c.Znon-converged.

3.2. Defects in B2 FeAl
For sake of clarity, the results concerning the triple
defects in the B2 FeAl compound will be discussed in two
parts: Table 4 contains the results for the defects for which
the a position is in the Fe sublattice and Table 5 contains the
results for the defects for which the a position is in the Al
sublattice.
Comparing Tables 3 and 4, we observe that some
configurations in the later are characterized by very large
excess interaction energies, of the order of 1 eV: avv–1T,
aav–1L and avv–1L. These cases will be discussed
separately in section 3.4. The case aav–1T is also
troublesome: the minimization algorithm could not
converge to an equilibrium solution, since the distance
between some atoms during the simulation became too
small. The remaining configurations show only small excess
interaction energies (3abg%0.1 eV), and vanish for
configurations 2T, 2L, 3T and 3L. The range of the excess
interaction energy for triple defects in the ordered B2 lattice,
thus, is considerably smaller than the one characteristic of
defect pairs (which can extend up to the 5th neighbourhood
[1]). This was verified by single simulations, where one of
the defects is placed progressively closer to a pair of defects.
The isolated defect is unable to ‘sense’ the pair unless it is in
a close neighbourhood. This justifies the limitation to the
investigation of triple defects consisting of two equidistant
pairs in the present work.
Contrary to the case of defects in the disordered lattice,
some configurations, namely aaa–1T, vva–1T and vva–1L
show potential to form stable bound states at low
temperatures. These will be discussed in detail below.
The aaa–1T configuration corresponds to a FeAl–AlFe–
FeAl triple defect (the a position is the central one). As
discussed in Part 1 [1], such defect pairs show a large,
negative, binding energy due to the restoration of a Al–Fe

Table 5
Interaction energies and excess interaction energies (in eV) for the six triple defects listed in Fig. 1 for the B2 FeAl compound in which the a position is in the
Al sublattice

Defect 1T 1L 2T 2L 3T 3L
abg
aaa DE K0.36 K0.41 C0.18 C0.25 K0.08 K0.11
3abg K0.04 C0.01 K0.01 K0.02 0 0
aav DEabg n.c. K0.02 C0.20 C0.25 K0.11 K0.12
3abg n.c. C0.08 0 K0.01 0 0
avv DEabg C0.07 C0.15 C0.24 C0.29 K0.12 K0.12
3abg K0.07 K0.16 C0.01 C0.01 0 0
vva DEabg K2.33 n.c. C0.07 C0.13 K0.10 K0.10
3abg C0.04 n.c. 0 K0.01 0 0

Obs.: n.c.Znon-converged.
 R.N. Nogueira, C.G. Schön / Intermetallics 13 (2005) 1245–1254
Fig. 4. Schematic representation of the displacements in the aaa–1T (a) and
aaa–1L (b) triple defect configurations. The figure corresponds to the
projection of the bcc lattice along the [010] direction, the central atom (a
position) is located; therefore, half lattice parameter below the plane of the
remaining atoms. Dashed circles represent the atomic size of the aluminium
atoms, the replacement of the large aluminium atoms by smaller iron atoms
justify the observed defect core relaxations.
bond in relation to the configurations corresponding to the
two isolated antisite defects. Configuration aaa–1L, on the
other hand, presents a small positive excess interaction
energy, despite the fact that the FeAl–FeAl bg pair in the
third neighbourhood (configuration 1L) is energetically
more stable than the FeAl–FeAl bg pair in the next-nearest
neighbourhood [1], this last one being characteristic of the
1T defect. In this sense, aaa–1L is the anomalous
configuration. Fig. 4 shows schematically both cases.
Comparing both, one observes that the aaa–1T (Fig. 4(a))
is characterized by a large displacement of the AlFe antisite
defect towards the FeAl–FeAl pair, resulting thus in the
negative excess interaction energy. Such large displace-
ments, however, are not possible for configuration aaa–1L
(Fig. 4(b)), since the AlFe antisite defect lies in a mirror
symmetry plane relative to the FeAl–FeAl pair. This shows
that the anisotropy of the interactions, detected for the case
of pair of defects [1], is also important for the case of the
triple defects. This could be overlooked due to the small
excess interaction energy characteristic of these defects.
Configurations vva–1T and vva–1L correspond both to
defect VAl–VFe–FeAl. Essentially this is a nearest neighbour
divacancy with an antisite defect ‘attached’ to it. Nearest
neighbour divacancies have inherent attractive interactions
[1] and this tendency is amplified by the presence of the
antisite defect in the neighbourhood, with the largest energy
gain associated with the 1L configuration. These obser-
vations are quite relevant since experimental techniques like
positron annihilation and differential dilatometry are based
on the detection of the free volume associated with
vacancies [21]. Such triple defects would be, therefore,
observed as single divacancies and not as triple defects in
these experiments, leading to an effective concentration
dependence in the formation energy of divacancies as the
aluminium concentration is varied (and the amount of
configurational antisite defects changes).
Table 5 shows the results obtained for the triple defects in
the B2 compound which a position is in the Al sublattice.
The analysis of this table shows that most excess interaction
1251
energies are small in modulus (3abg%0.16 eV) as in
the previous cases (a position corresponding to the Fe
sublattice). The main features are also comparable: the
excess interactions are significant only for the triple defects
of the kind 1L and 1T (i.e. the interactions are short-range)
and some cases (namely aav–1T and vva–1L) presented
convergence problems in the simulation.
Comparing with Table 4, we observe that the magnitude
of the excess interaction corresponding to defect AlFe–FeAl–
AlFe (aaa–1T and aaa–1L) is decreased in relation with the
FeAl–AlFe–FeAl (cases aaa–1T and aaa–1L of Table 4). B2
alloys are usually characterized by large amounts of Fe
antisite defects, due to the deviation of the ideal
stoichiometry (most investigated alloys have less than 50
at.% Al), so triple defects containing two Fe antisite atoms
would be expected to prevail over the counterpart (triple
defects containing three Al antisite defects), the excess
interactions being weaker to the former indicate that such
kind of defect complexes (i.e. consisting of three antisite
defects) is unlikely to be observed in real alloys.
From the remaining configurations aav–1T and aav–1L
are worth mentioning, corresponding both to a VFe–FeAl–
VFe triple defect and characterized by positive interaction
energies, but with negative excess interaction energies of
similar magnitude. This shows that both configurations are
metastable with respect to the dissociation as individual
pairs in the compound. This is the ‘triple defect’, referred to
in the diffusion literature (see footnote 3), supposedly
responsible for keeping the stoichiometry ratio constant in
near stoichiometric alloys as the temperature increases. This
result suggests that bound states corresponding to these
defects are possible, but that the energy gain is not sufficient
to stabilize the ‘triple defect’ in the compound. A picture
corresponding to this affirmation is the following: suppose
that the alloy is dominated by a large number of pair of
defects (mostly divacancies and antisite defect-vacancy
pairs). As they diffuse through the alloy they eventually
merge with isolated point defects, forming a ‘triple defect’
(the activation barrier is quite small, and large populations
of such defects may be formed). As the excess interaction
energy is negative, this new defect presents some stability,
but they are eventually destroyed by thermal fluctuations. In
other words, these triple defects would present a finite
lifetime in the compound. As a matter of fact, this situation
is favourable to the action of such defect in diffusion
mechanisms (both ASB and TRD) since the ‘triple defect’
must be formed and destroyed during the diffusion of the
species: if the defects were too stable, the energy penalty
necessary to destroy the defect would probably play against
the realization of this diffusion path.
A remark about these discussions on diffusion in
intermetallics is necessary at this point. Both the ASB and
the TRD cases discussed here assume that VAl vacancies are
available in the alloy as a precondition for the diffusion to
take place. Ab initio results, in the framework of the density
functional theory (DFT), usually indicate that the formation
1252 R.N. Nogueira, C.G. Schön / Intermetallics 13 (2005) 1245–1254

energy of such defect is too high (see [22] and references
therein) and that, therefore, its equilibrium concentration
should be negligible in the alloy. Two points should be
discussed in this context: first of all, the applicability of the
DFT to Fe–Al alloys is still a controversial issue [23–28]
and particularly the influence of nearest neighbour
aluminium atoms on suppressing the magnetic moment of
iron seems to be underestimated by the actual implemen-
tations of the DFT [29,30]. This influence is likely to play a
significant role in the formation energy of VAl vacancies.
Second, it is not the aim of the present work to discuss
whether VAl vacancies exist or not in Fe–Al alloys; we are
here discussing the formation of triple defect complexes
provided the individual defects are already available.
3.3. Anomalous configurations
Comparing Tables 3–5, we observe that some configur-
ations in the later two are characterized by very large
interaction energies, of the order of 1 eV: avv–1T, aav–1L
and avv–1L in Table 4 and vva–1T in Table 5. All four
cases involve AlFe–VAl nearest neighbour pairs. As shown
in Part 1 [1], in this kind of pair the defects spontaneously
react and exchange place during the simulation, generating a
vacancy in the iron sublattice and annihilating the antisite
defect. Similar observations in a EAM/ab-initio modelling
of diffusion mechanisms in B2 NiAl have been published
recently by Mishin et al [31].
From the anomalous cases investigated in the present
work, two groups must be discussed separately.
In the cases of aav–1L (Table 4) and vva–1T (Table 5)
configurations, the exchange takes place between pair ag
and a contribution of the annihilation energy of the single
antisite defect (AlFe) is computed in the interaction energy
obtained in the simulation). So, in the final configurations,
the number and type of isolated defects are not the same as
in the initial state, violating one of the main conditions
imposed to the simulations. Therefore, the calculated
‘excess interaction energies’ contain an additional contri-
bution due to the annihilation of the defect and cannot be
compared with the normal cases.
In cases avv–1T and avv–1L, on the other hand, the
exchange may take place both for pairs ab and ag. Due to
the symmetry of the simulation, however, the reaction is
prevented and the calculation leads to a condition in which
the antisite defect converges to an intermediate frustrated
state. The significance of these frustrated states must be
questioned, since in the actual compound other excitations
(like phonons, for example) would eventually contribute to
the convergence to an equilibrium state, where the antisite

Fig. 5. Metastable equilibrium configuration corresponding to defect aav–1T, with an AlFe antisite defect at position a. Iron and aluminium atoms are denoted,
respectively, by light and dark grey spheres. Dots mark the position of the centre of the vacancies and a circle marks the original position of the antisite defect.
 R.N. Nogueira, C.G. Schön / Intermetallics 13 (2005) 1245–1254 1253

defect is annihilated by exchanging positions with one of the
two vacancies. Attempts to destabilize these frustrated states
in the simulation either by submitting the crystal block to a
stress state or by destroying the local symmetry introducing
a fourth defect in the neighbourhood of the complex were
unsuccessful.
Fig. 5 presents the metastable equilibrium configuration
for the aav–1T defect, with an AlFe antisite defect at a
position. The antisite atom moved away from the
equilibrium position, towards what seems to be an
interstitial site of the bcc structure. Self-interstitials usually
are characterized by very large formation energies, which
lead to very low equilibrium populations for these defects.
This is due, of course, to the absence of free space in the
crystal structure, which lead to very large relaxation strains
associated with the self-interstitials. The presence of the
divacancy in the neighbourhood, however, generates
enough free space in the structure to support the formation
of the interstitial defect. The formation of such defect as a
stable bound state, therefore, is possible and should be
experimentally investigated.
4. Conclusions
exchange place, resulting in the annihilation of the antisite
defect. For triple defect configurations containing two
nearest neighbour VAl–AlFe pairs, the annihilation is not
possible due to symmetry constraints of the lattice. At least
in one case, the final converged configuration is character-
ized by large displacements of the antisite defect, of the
order of the lattice parameter. The relative stability of this
configuration could not be determined in the present
simulations, but some indirect evidences suggest that it is,
at least, metastable.
Acknowledgements
The authors thank to the São Paulo State Research
Funding Agency (FAPESP) for financial support under
grants No. 99/07570-8 and 00/07299-1. The authors would
like to thank Prof. Dr Diana Farkas (Virginia Technological
Institute and State University, Blacksburg-VA, USA), Prof.
Dr Gerhard Inden (Max-Planck-Institut für Eisenforschung,
Düsseldorf, Germany) and Prof. Dr Hélio Goldenstein
(Dept. of Metallurgical and Materials Engineering, Escola
Politécnica da Universidade de São Paulo, São Paulo,
Brazil) for helpful discussions.

Triple defect complexes composed of antisite defects and

vacancies in both A2 Fe and B2 FeAl compounds have been
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