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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


are mainly governed by the configuration of the first
In the first part of the present investigation, a systematic coordination shell around the vacancy. This poses the
study of the interactions between pairs of point defects question whether a similar interaction can be found or not
(both antisite defects and vacancies) was performed [1]. In in more extended defect complexes, consisting of three
those cases, long-range anisotropic interactions were point defects (i.e. triple defects). The present work handles
obtained, with variable strength and character (either this problem using the same approach employed in the
attractive or repulsive) depending of the particular kind first part.
of pair. As general trends, divacancy complexes of nearest Triple defects are postulated to exist in iron aluminides,
and next-nearest vacancy pairs are characterized by especially in the case of B2 near stoichiometric alloys. This
attractive bonds of the order of magnitude of K0.1 eV,1 postulation is based on experimental observations that, due
while Al antisite atom pairs (i.e. two aluminium atoms in to their formation self-energies, the dominant kind of defect
iron lattice positions) present strong repulsive interactions is different for under- and overstoichiometric alloys (antisite
(of the order of magnitude of C0.2 eV) in the nearest FeAl atoms in the former and VFe vacancies in the later2): in
neighbourhood. Another relevant finding of the first part order to accommodate the two types of defects keeping the
investigation was a sort of ‘universality’ in the dependence stoichiometric ratio constant at equiatomic compositions,
of the interactions of a vacancy pair with distance. 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
* Corresponding author. Tel.: C55 11 3091 5726; fax: C55 11 3091
fulfilled even if the three defects are not correlated (e.g. the
5243.
E-mail addresses: rnogueir@usp.br (R.N. Nogueira), schoen@usp.br
three defects may be formed at different and quite distant
(C.G. Schön).
1
With reference to the energy of a crystal containing the isolated defects. 2
This notation has been introduced in the first part of the investigation.
0966-9795/$ - see front matter q 2005 Elsevier Ltd. All rights reserved. XY represents a defect of kind X (Fe, Al or VZvacancy), located in
doi:10.1016/j.intermet.2005.04.008 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 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
Fig. 2. Schematic representation of the Triple Defect (TRD) diffusion properties of the triple defects in the alloy. The following
mechanism in iron aluminides: (a) initial configuration, (b) intermediate
configuration (containing the triple defect VFe–FeAl–VFe), and (c) final
criteria have been adopted:
configuration (with the net transfer of Fe along lattice vector [100]).
1. configurations which are experimentally observed in
Fe–Al alloys will be discussed,
the same number and kinds of point defects, so that all 2. only configurations in the B2 FeAl compound and in the
simulations for a given compound are performed with a A2 Fe disordered host will be shown,
constant number of atoms in the crystal block, i.e. the 3. all discussed defects are formed by two equidistant pairs,
simulations are performed in the canonical ensemble. which are used as reference to identify the given defect,
and
4. the upper bound of the length of the equidistant pairs
2. Methodology corresponds to the third neighbourhood.

2.1. General These restrictions have been tested by single calculations


and will be discussed later on, when necessary, in the
The procedure adopted in this work is the same we present work.
described in Part 1 [1]: a set of point defects (both vacancies
and antisite atoms) is placed in a ‘computer crystal’ such 4
As in Part 1 [1], lattice positions are labelled using greek letters, while
that their distances are large enough to avoid any interaction the species (or, in the present case, the defect) occupying the lattice site
between them. The EAM functional (Eq. (1) of Part 1 [1]) is using roman letters.
1248 R.N. Nogueira, C.G. Schön / Intermetallics 13 (2005) 1245–1254

The nomenclature of the defects also plays an important investigated in this work. It is clearly seen that the
role here. In Part 1 [1], each pair was identified by the kind configurations may be divided into two major groups:
of point defects involved and by its size (i.e. the distance those that are arranged in the projection in the form of a
between the point defects in terms of neighbourhood). For triangle (Fig. 1(a)–(c)), and those that are arranged in the
triple defects, a third characteristic must be taken into form of a line (Fig. 1(d)–(f)). A second characteristic is the
account: the defect geometry. size of the defect: it may be characterized by the distance
Fig. 3 shows six [110] projections of the bcc lattice, each between the point defects in the equidistant pairs: nearest
of them containing a different triple defect geometry 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 1249

Table 1 Table 2
Distance (in terms of neighbourhood) between the point defects in the bg Occupancy of the sublattices corresponding to sites b and g depending on
pair of the six cases of triple defects shown in Fig. 1 (ab and ag are the the occupancy of the a sublattice (X), with XZFe 0 YZAl and XZAl 0
equidistant pairs) YZ Fe

Triple 1T 2T 3T 1L 2L 3L Triple defect b g


defect
1T Y Y
bg 2 3 6 3 6 25 1L Y Y
2T X X
2L X X
(Fig. 1(b) and (e)) and third neighbours (Fig. 1(c) and (f)). 3T X X
The defect geometry will be identified primarily by these 3L X X
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 the table shows that the excess interaction energy term,
line in the [110] projection (Fig. 1(e)); 1T, on the other hand 3xzj, is very small in modulus, and the magnitude of the
corresponds to a triangular arrangement of nearest largest value is smaller than 0.05 eV. In most configur-
neighbour pairs (Fig. 1(a)). The geometries of the triple ations, it corresponds to about 10% of the interaction
defects considered in this study are identified in the legend energy for the individual pairs, which form that defect [1].
of Fig. 3. The individual defects are labelled a, b and g, In other words, the interactions responsible for the
being a the defect that is common to the equidistant pairs formation of pairs of defects are much more relevant that
(i.e. the equidistant pairs correspond to ab and ag). Table 1 the ones responsible for the formation of triple defects in
shows the corresponding distance of the third pair (bg) for the disordered compound.
the six triple defects shown in Fig. 3. Since the excess interaction energy is very small, one
The types of point defects composing the triple defects may, as a first approximation, perform the analysis
are identified as antisite atoms,5 a, or vacancies; v, A triple considering the individual pairs that form the triple defect.
defect will be, thus, identified by its geometry (as described As discussed in Part 1 [1], interactions between aluminium
above) and by the types of point defects in positions a, b, atoms in the iron host are repulsive for nearest and next-
and g; aaa, three antisite atoms; aav, antisite atoms at a and nearest pairs, but become attractive for distances above the
b and a vacancy at g, and so on. third neighbourhood. The interaction between vacancies
For B2 superlattices, one must notice that the considered follows the inverse trend, with attractive interactions in the
geometries lead to two classes of defects, depending on the nearest and next-nearest neighbourhood. On the other
original occupancy of the a site. A first group corresponds to hand, antisite atom–vacancy pairs tend to show attractive
a site in the Fe sublattice and the second, to a site placed in interactions, but the magnitudes of these interactions are
the Al sublattice. Table 2 relates the occupancies of the lower than those observed for the other pairs [1]. This is
sublattices corresponding to each point defect for the six reflected in the interaction energies of the corresponding
cases shown in Fig. 1 in the B2 lattice, depending on the triple defects. For instance, in the aav–1T configuration,
original occupancy of the a sublattice. 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
3. Results and discussion creates two Al Fe –V Fe pairs, which have moderate
attractive interaction. As a result, the repulsive character
The results will be presented and discussed in two parts: of the interaction for the triple defect is reduced to
Section 3.1 presents the results of defects in the disordered C0.11 eV, less than half the value of the isolated pair.
A2 Fe lattice and Section 3.2, those for the B2 FeAl The other cases that also show similar behaviour are aaa–
compound. 2T, aav–1T, avv–2T and avv–2L.
The negligible excess interaction for all investigated
3.1. Defects in A2 Fe configurations shows that the formation of bound states
corresponding to the triple defects is unlikely in the
Table 3 shows the results for the six classes of triple disordered alloy. Triple defects of statistical nature may
defects investigated in the present work. The analysis of
be formed in the alloy, and it is possible that entropic
contributions (either vibrational or configurational) could
5
As discussed in Part 1 [1], strictly speaking, one cannot refer to an stabilize triple defect configurations, especially in concen-
antisite atom in the case of the disordered A2 lattice since no preferred trated alloys at high temperatures. In other words, the
occupation of sublattices exists. In this case this defect corresponds to a
possibility of formation of entropically stabilized triple
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 defects in A2 Fe–Al with increasing temperature should not
behaviour of the triple defects in the B2 lattice. 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 configurations 2T, 2L, 3T and 3L. The range of the excess
interaction energy for triple defects in the ordered B2 lattice,
For sake of clarity, the results concerning the triple thus, is considerably smaller than the one characteristic of
defects in the B2 FeAl compound will be discussed in two defect pairs (which can extend up to the 5th neighbourhood
parts: Table 4 contains the results for the defects for which [1]). This was verified by single simulations, where one of
the a position is in the Fe sublattice and Table 5 contains the the defects is placed progressively closer to a pair of defects.
results for the defects for which the a position is in the Al The isolated defect is unable to ‘sense’ the pair unless it is in
sublattice. a close neighbourhood. This justifies the limitation to the
Comparing Tables 3 and 4, we observe that some investigation of triple defects consisting of two equidistant
configurations in the later are characterized by very large pairs in the present work.
excess interaction energies, of the order of 1 eV: avv–1T, Contrary to the case of defects in the disordered lattice,
aav–1L and avv–1L. These cases will be discussed some configurations, namely aaa–1T, vva–1T and vva–1L
separately in section 3.4. The case aav–1T is also show potential to form stable bound states at low
troublesome: the minimization algorithm could not temperatures. These will be discussed in detail below.
converge to an equilibrium solution, since the distance The aaa–1T configuration corresponds to a FeAl–AlFe–
between some atoms during the simulation became too FeAl triple defect (the a position is the central one). As
small. The remaining configurations show only small excess discussed in Part 1 [1], such defect pairs show a large,
interaction energies (3abg%0.1 eV), and vanish for 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 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
Fig. 4. Schematic representation of the displacements in the aaa–1T (a) and of the excess interaction corresponding to defect AlFe–FeAl–
aaa–1L (b) triple defect configurations. The figure corresponds to the AlFe (aaa–1T and aaa–1L) is decreased in relation with the
projection of the bcc lattice along the [010] direction, the central atom (a FeAl–AlFe–FeAl (cases aaa–1T and aaa–1L of Table 4). B2
position) is located; therefore, half lattice parameter below the plane of the alloys are usually characterized by large amounts of Fe
remaining atoms. Dashed circles represent the atomic size of the aluminium
antisite defects, due to the deviation of the ideal
atoms, the replacement of the large aluminium atoms by smaller iron atoms
justify the observed defect core relaxations. 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
bond in relation to the configurations corresponding to the defects containing three Al antisite defects), the excess
two isolated antisite defects. Configuration aaa–1L, on the interactions being weaker to the former indicate that such
other hand, presents a small positive excess interaction kind of defect complexes (i.e. consisting of three antisite
energy, despite the fact that the FeAl–FeAl bg pair in the defects) is unlikely to be observed in real alloys.
third neighbourhood (configuration 1L) is energetically From the remaining configurations aav–1T and aav–1L
more stable than the FeAl–FeAl bg pair in the next-nearest are worth mentioning, corresponding both to a VFe–FeAl–
neighbourhood [1], this last one being characteristic of the VFe triple defect and characterized by positive interaction
energies, but with negative excess interaction energies of
1T defect. In this sense, aaa–1L is the anomalous
similar magnitude. This shows that both configurations are
configuration. Fig. 4 shows schematically both cases.
metastable with respect to the dissociation as individual
Comparing both, one observes that the aaa–1T (Fig. 4(a))
pairs in the compound. This is the ‘triple defect’, referred to
is characterized by a large displacement of the AlFe antisite
in the diffusion literature (see footnote 3), supposedly
defect towards the FeAl–FeAl pair, resulting thus in the
responsible for keeping the stoichiometry ratio constant in
negative excess interaction energy. Such large displace-
near stoichiometric alloys as the temperature increases. This
ments, however, are not possible for configuration aaa–1L
result suggests that bound states corresponding to these
(Fig. 4(b)), since the AlFe antisite defect lies in a mirror
defects are possible, but that the energy gain is not sufficient
symmetry plane relative to the FeAl–FeAl pair. This shows
to stabilize the ‘triple defect’ in the compound. A picture
that the anisotropy of the interactions, detected for the case corresponding to this affirmation is the following: suppose
of pair of defects [1], is also important for the case of the that the alloy is dominated by a large number of pair of
triple defects. This could be overlooked due to the small defects (mostly divacancies and antisite defect-vacancy
excess interaction energy characteristic of these defects. pairs). As they diffuse through the alloy they eventually
Configurations vva–1T and vva–1L correspond both to merge with isolated point defects, forming a ‘triple defect’
defect VAl–VFe–FeAl. Essentially this is a nearest neighbour (the activation barrier is quite small, and large populations
divacancy with an antisite defect ‘attached’ to it. Nearest of such defects may be formed). As the excess interaction
neighbour divacancies have inherent attractive interactions energy is negative, this new defect presents some stability,
[1] and this tendency is amplified by the presence of the but they are eventually destroyed by thermal fluctuations. In
antisite defect in the neighbourhood, with the largest energy other words, these triple defects would present a finite
gain associated with the 1L configuration. These obser- lifetime in the compound. As a matter of fact, this situation
vations are quite relevant since experimental techniques like is favourable to the action of such defect in diffusion
positron annihilation and differential dilatometry are based mechanisms (both ASB and TRD) since the ‘triple defect’
on the detection of the free volume associated with must be formed and destroyed during the diffusion of the
vacancies [21]. Such triple defects would be, therefore, species: if the defects were too stable, the energy penalty
observed as single divacancies and not as triple defects in necessary to destroy the defect would probably play against
these experiments, leading to an effective concentration the realization of this diffusion path.
dependence in the formation energy of divacancies as the A remark about these discussions on diffusion in
aluminium concentration is varied (and the amount of intermetallics is necessary at this point. Both the ASB and
configurational antisite defects changes). the TRD cases discussed here assume that VAl vacancies are
Table 5 shows the results obtained for the triple defects in available in the alloy as a precondition for the diffusion to
the B2 compound which a position is in the Al sublattice. take place. Ab initio results, in the framework of the density
The analysis of this table shows that most excess interaction 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 defect. Similar observations in a EAM/ab-initio modelling
therein) and that, therefore, its equilibrium concentration of diffusion mechanisms in B2 NiAl have been published
should be negligible in the alloy. Two points should be recently by Mishin et al [31].
discussed in this context: first of all, the applicability of the From the anomalous cases investigated in the present
DFT to Fe–Al alloys is still a controversial issue [23–28] work, two groups must be discussed separately.
and particularly the influence of nearest neighbour In the cases of aav–1L (Table 4) and vva–1T (Table 5)
aluminium atoms on suppressing the magnetic moment of configurations, the exchange takes place between pair ag
iron seems to be underestimated by the actual implemen- and a contribution of the annihilation energy of the single
tations of the DFT [29,30]. This influence is likely to play a antisite defect (AlFe) is computed in the interaction energy
significant role in the formation energy of VAl vacancies. obtained in the simulation). So, in the final configurations,
Second, it is not the aim of the present work to discuss the number and type of isolated defects are not the same as
whether VAl vacancies exist or not in Fe–Al alloys; we are in the initial state, violating one of the main conditions
here discussing the formation of triple defect complexes imposed to the simulations. Therefore, the calculated
provided the individual defects are already available. ‘excess interaction energies’ contain an additional contri-
bution due to the annihilation of the defect and cannot be
3.3. Anomalous configurations compared with the normal cases.
In cases avv–1T and avv–1L, on the other hand, the
Comparing Tables 3–5, we observe that some configur- exchange may take place both for pairs ab and ag. Due to
ations in the later two are characterized by very large the symmetry of the simulation, however, the reaction is
interaction energies, of the order of 1 eV: avv–1T, aav–1L prevented and the calculation leads to a condition in which
and avv–1L in Table 4 and vva–1T in Table 5. All four the antisite defect converges to an intermediate frustrated
cases involve AlFe–VAl nearest neighbour pairs. As shown state. The significance of these frustrated states must be
in Part 1 [1], in this kind of pair the defects spontaneously questioned, since in the actual compound other excitations
react and exchange place during the simulation, generating a (like phonons, for example) would eventually contribute to
vacancy in the iron sublattice and annihilating the antisite 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 exchange place, resulting in the annihilation of the antisite
two vacancies. Attempts to destabilize these frustrated states defect. For triple defect configurations containing two
in the simulation either by submitting the crystal block to a nearest neighbour VAl–AlFe pairs, the annihilation is not
stress state or by destroying the local symmetry introducing possible due to symmetry constraints of the lattice. At least
a fourth defect in the neighbourhood of the complex were in one case, the final converged configuration is character-
unsuccessful. ized by large displacements of the antisite defect, of the
Fig. 5 presents the metastable equilibrium configuration order of the lattice parameter. The relative stability of this
for the aav–1T defect, with an AlFe antisite defect at a configuration could not be determined in the present
position. The antisite atom moved away from the simulations, but some indirect evidences suggest that it is,
equilibrium position, towards what seems to be an at least, metastable.
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. Acknowledgements
This is due, of course, to the absence of free space in the
crystal structure, which lead to very large relaxation strains The authors thank to the São Paulo State Research
associated with the self-interstitials. The presence of the Funding Agency (FAPESP) for financial support under
divacancy in the neighbourhood, however, generates grants No. 99/07570-8 and 00/07299-1. The authors would
enough free space in the structure to support the formation like to thank Prof. Dr Diana Farkas (Virginia Technological
of the interstitial defect. The formation of such defect as a Institute and State University, Blacksburg-VA, USA), Prof.
stable bound state, therefore, is possible and should be Dr Gerhard Inden (Max-Planck-Institut für Eisenforschung,
experimentally investigated. Düsseldorf, Germany) and Prof. Dr Hélio Goldenstein
(Dept. of Metallurgical and Materials Engineering, Escola
Politécnica da Universidade de São Paulo, São Paulo,
4. Conclusions 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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