Accepted Manuscript

Structural, elastic and electronic properties of B2-type modified by ternary additions

FeAl-based intermetallics: First-principles study

Yibing Zheng, Fen Wang, Taotao Ai, Chuang Li

PII: S0925-8388(17)31110-6
DOI: 10.1016/j.jallcom.2017.03.308
Reference: JALCOM 41346

To appear in: Journal of Alloys and Compounds

Received Date: 14 December 2015

Revised Date: 22 March 2017
Accepted Date: 26 March 2017

Please cite this article as: Y. Zheng, F. Wang, T. Ai, C. Li, Structural, elastic and electronic properties of
B2-type modified by ternary additions FeAl-based intermetallics: First-principles study, Journal of Alloys
and Compounds (2017), doi: 10.1016/j.jallcom.2017.03.308.

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 ACCEPTED MANUSCRIPT

Structural, elastic and electronic properties of B2-type modified

by ternary additions FeAl-based intermetallics: First-principles
study

Yibing Zhenga,b, Fen Wanga,∗, Taotao Aic, Chuang Lic

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a
School of Materials Science and Engineering, Shaanxi University of Science &

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Technology, Xi’an 710021, PR China

b
Xuchang Electrical Vocational College, Xuchang, 461000, PR China

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c
School of Materials Science and Engineering, Shaanxi University of Technology,

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Hanzhong, 723000, PR China
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ABSTRACT: The structural, elastic and electronic properties of FeAl (B2)

intermetallics modified by ternary additions have been investigated by first-principles

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calculations based on density functional theory (DFT). The calculations of the

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formation enthalpy indicate that Al atoms are more easily replaced by the alloying
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elements X (X= V, Sc, Mn, Si, Mg, Co, Zr, Cu, Zn, Nb, Cr, Mo, W, Ti, Ni). The ratio
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of the bulk modulus to shear modulus B/G and Poisson’s ratio v show that the

FeAl-Cr, FeAl-Ti, and FeAl-Co systems are ductile materials and FeAl-Co (B/G=1.92,
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v=0.28) is the most ductile phase among these alloy phases. The electronic structure
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calculations indicate that the doping by Cr, Ti and Co may lead to the charge

redistribution, the weakening of the Al-Al interaction, and strengthening of the Fe-Fe

and Fe-Al interactions. It can be concluded that Cr, Ti and Co form the most stable

FeAl-based intermetallics.

∗
Corresponding author. Tel.: +86 15114805183
E-mail address: Wangf@sust.edu.cn (Fen Wang).
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Keywords: First-principles; FeAl-based intermetallics; Elastic constants; Electronic

structure

1. Introduction

FeAl (B2) intermetallics have attractive properties including high hardness, low

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density, excellent oxidation and corrosion resistance [1, 2]. However, poor ductility at

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room temperature, the loss of strength when the temperature is more than 600 °C [3]

have limited their engineering applications. As an important method to improve the

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toughness of FeAl intermetallics, Solid solution strengthening [3] has been widely

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studied in the past decades. In the experiments, B, Cr, Ti, Ni, Mo, Zr etc. are common
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doping elements [4-8]. In the theoretical work, the first-principles study of the doping

rare earth elements (REEs) La, Ac, Sc and Y [9] and Cr, Mo and W [10] show positive
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effects on the elastic properties of FeAl. Bozzolo Ferrante Smith (BFS) method
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[11] was used to study the substitutional site preference of ternary alloying additions
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to B2 compounds (FeAl, NiAl, CoAl etc.). Medvedeva et al. [12] investigated the

ternary site preference energies, size misfits and solid solution hardening of NiAl and
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FeAl with the local density linear muffin-tin orbital (LMTO) method, the results
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demonstrate that the ternary additions might be able to improve the mechanical
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properties of these alloys by enhancing the M-M (M=Fe, Ni) and decreasing the Al-Al

interactions. Although a variety of theoretical studies have been carried out, there are

still many shortcomings. The unit cell size (16 atoms) used in Ref. [9, 10] is too small

to describe the influence of the impurity concentration on the mechanical properties,

and Ref. [11, 12] does not conduct the required research on the mechanism. To the
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best of our knowledge, the systematic theoretical investigation on the influence of

ternary additions on the mechanical/electrical properties of FeAl intermetallics has not

been reported.

In this contribution, density functional theory (DFT) calculations are performed

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to determine the elastic and electronic properties of FeAl-X (X= V, Sc, Mn, Si, Mg,

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Co, Zr, Cu, Zn, Nb, Cr, Mo, W, Ti, Ni) intermetallics. The effects of different X on

the mechanical response and stability properties of the FeAl-X intermetallics have

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been studied. The present work revealed that FeAl-X intermetallics with X=Cr, Ti and

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Co exhibit ductile characteristics.
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2. Simulation details
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All calculations were performed with Cambridge Serial Total Energy Package

(CASTEP) [13] code based on the density function theory (DFT) [14], employing
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ultra-soft pseudopotentials [15] and a planewave basis. The exchange correlation

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functional was described through the generalized gradient approximation (GGA) with
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the Perdew-Burke-Ernzerhof (PBE) parameters [16]. On the basis of the convergence

test, the cut-off energy value (Ecut ) of atomic wave functions was set to 360.0 eV, and
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the energy calculations were conducted in the first irreducible Brillouin zone (BZ)
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with a 10×10×10 regular k-point grid using the Monkhorst-Pack scheme [17]. The

Pulay scheme of density mixing [18] and a finite basis set correction [19] were

applied for the evaluation of energy and stress. To find the lowest energy structure, all

atomic positions in our models were fully relaxed according to the total energy and

force, using the Broyden-Fletcher-Goldfarb-Shanno (BFGS) technique [20]. The

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convergence tolerance of energy of 5.0×10-5 eV/atom was taken, and the maximal

allowed force and displacement were 0.01 eV/Å and 5.0×10-4 Å, respectively. The

self-consistent convergence precision of the total energy was less than 2.0×10-6

eV/atom. Moreover, due to the magnetism of the iron atoms, the electron spin was

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considered.

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FeAl has a cubic structure with the space group Pm-3m (NO.221), the lattice

parameter is a=b=c=2.909 Å [21] and the unit cell contains two atoms. Fe and Al

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atoms occupy the 1a (0, 0, 0) and 1b (0.5, 0.5, 0.5) sites, respectively. We used a

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2×2×2 supercell that contains 16 atoms for FeAl to calculate the site preference of
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ternary elements, and a 3×3×3 supercell that contains 54 atoms to calculate the elastic

constants and electronic properties. Fig. 1(a) shows that the impurity X is placed at
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the center of this supercell which corresponds to a 12.5% impurity concentration. The
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crystal structure with X atoms replacing Al atoms is not shown in Fig. 1(a) because of
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the symmetry of the Al atoms in the supercell. Fig. 1(b) displays the crystal structure

of the X atom substituting the Al atom in the 3×3×3 supercell, and Fig. 1(c) presents
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the Co atom substituting the Fe atom. Earlier, in studies of the microstructure of

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FeAl-Cr alloys it was established that the solubility of Cr in FeAl exceeds 5 at. % [22,
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23]. Moreover, it was found that the concentration of Mo in FeAl is less than 7

at. %[8]. Prymak and Stein [24] reported the solubility of Nb in FeAl to be nearly 3

at. %. Palm and Sauthoff found that the solubility of Ti in FeAl is 10 at. % when the

temperature reaches 1000 ºC [25]. It was noted in [26] that 11 at. % Si are dissolved

in the FeAl phase. The investigation [27] showed that the solubility of Zr in FeAl is
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below 0.1 at. % for all Al content based on the research on the phase diagram of the

ternary Fe-Al-Zr system between 800 and 1150 º C. With this in mind, a

concentration of 3.7 at. % X was chosen for the elastic and electronic structure

investigation.

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3. Results and discussion

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3.1 Lattice constants and stability

Table 1 lists the calculated lattice constants of FeAl-X. As a comparison, the

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lattice constants of the FeAl were calculated. The value of 2.857 is close to the

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experimental value (2.909) and the deviation of 1.788% is within the typical error
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range of 1%–2%. Furthermore, it can be found that the calculated lattice constants are

in good agreement with the other theoretical values [9, 10]. Therefore, the conditions
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and computation parameters that we selected in this paper are suitable.

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To further validate the thermodynamic stability of FeAl-X, their theoretical

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formation enthalpy (∆H) were calculated by the following formula [28]:

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∆H = [ Etotal − ( N Fe EFe(atom) + N Al EAl(atom) + N X EX(atom) )]
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(1)
N Fe + N Al + N X

where Etotal is the total energy of the bulk compound, and EFe(atom) , EAl(atom) and
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EX(atom) represent the energy of pure Fe, Al, and X atoms with equilibrium lattice
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parameters, and N Fe , N Al and N X are the number of atoms, respectively. EFe7Al8X

and EFe8Al7X represent the total energy of the bulk compound Fe7Al8X and Fe8Al7X,

in which the Fe atom or Al atom was substituted by an X atom, respectively. EFe and

EAl are the calculated results of Fe7Al8X and Fe8Al7X by formula (1), respectively.

Esite is defined as the substitution formation enthalpy, which is calculated by formula

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(2). If the value of Esite is positive, the X atom will replace the Al atom preferentially,

or the X atom will replace the Fe atom.

Esite = EFe − EAl (2)

In addition to the Co element, it is noted that almost all elements in Table 2

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exhibit positive values of Esite , suggesting that these ternary additions have stronger

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preference for the Al sites than Fe sites. The preference of Sc, Cr, Mo and W for Al

sites agree with theoretical results of [9] and [10]. Fu and Zou [29] found a Ti and Cr

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preference for Al sites and a Ni preference for Fe sites by using first-principles with

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local density functional theory. The work of Bozzolo [11] provided a comprehensive
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survey of additions to FeAl, indicating partitioning of Ni and Co to the Fe sites and Ti,

Cr, Ta, Hf, Mo and V to the Al sites. It was concluded in [12] that La, Zr, Mo, Ti, V,
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Mn and Cr must occupy the Al sites and Ni, Co the Fe sites. There is also agreement
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with the channeling-enhanced microanalysis (ALCHEMI) technique introduced by

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Anderson [30], which predicted Co preference for Fe sites and Ti preference for Al

sites. Moreover, our findings for the site preference of ternary elements are consistent
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with experimental result of Cr in FeAl [23], but disagree with [31] for Ti in FeAl in
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the experiment. To sum up, our calculated results are plausible.

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3.2 Elastic constants and mechanical properties

Elastic constants can quantify the response of materials to an applied macroscopic

stress and provide important information about the stability and stiffness of materials.

In this work, the elastic constants Cij were estimated theoretically by using the

stress-strain approach, which can be described with the following generalized

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Hooke’s law [32]:

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{σ i } = ∑ [Cij ]{ε j } (3)
j =1

where {σ i } is the stress, {ε j } is the strain vector, and [Cij ] are the elements of

elastic constants matrix C , which is expressed in 6×6 form [33].

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C11 C12 C12 0 0 0 
C 0 

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 12 C11 C12 0 0
C C12 C11 0 0 0 
[Cij ] =  12  (4)
 0 0 0 C44 0 0 

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 0 0 0 0 C44 0 
 
 0 0 0 0 0 C44 

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As shown in equation (4), there are three independent elastic constants (C11, C12
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and C44) in the matrix. Furthermore, these elastic constants can be used to judge the
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mechanical stability of a cubic system by employing the following restrictions [34]:

C11 0 C44 0 C11 + 2C12 0 C11 C12 , C11 B C12 (5)

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All the calculated results for elastic constants are listed in Table 3. Notably the
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obtained elastic constants all satisfy the aforementioned stability criteria, so all the
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FeAl-X compounds are mechanically stable systems at ground state. Moreover, the

calculated elastic constants of FeAl-Cr are close to the theoretical results of [10].
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The shear modulus G and bulk modulus B represent the resistance to plastic

deformation and fracture, respectively. Based on the obtained elastic constants, the

bulk modulus B, shear modulus G can be estimated via the Voigt-Reuss-Hill (VRH)

approach [35].
( Bv + BR ) (GV + GR )
B= G= (6)
2 2
For the cubic structure, the equations are as follows:
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(C11 + 2C12 )
BR = BV = (7)
3
C − C12 + 3C44
GV = 11 (8)
5
5(C11 − C12 )C44
GR = (9)
4C44 + 3(C11 − C12 )

Young’s modulus E is the ratio of stress and strain for measuring the stiffness of solids.

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Poisson’s ratio v is the ratio of lateral strain and vertical strain, which relates to the

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characteristics of the bonding forces rather than any of the other elastic constants. The

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Young’s modulus E and Poisson’s ratio v can be calculated from the Hill’s shear

modulus and bulk modulus. The formula for which is expressed as follows:

E=
9GH BH
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ν=
3BH − 2GH
(10)
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GH + 3BH 2(3BH + GH )

where the subscripts H, V and R refer to the Hill, Voigt and Reuss approximations,
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respectively. Our calculated values of elastic moduli are listed in Table 3. According
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to the Pugh criterion [36], the ratio of the bulk modulus to shear modulus (B/G) of a
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material is characterised as an indication of brittle versus ductile. If the value of B/G

is greater than 1.75, a material behaves in a ductile manner; otherwise, it behaves in a

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brittle manner. Moreover, when Poisson’s ratio v is more than 0.26, the material is
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ductile; otherwise, it is brittle. Based on the above criterion, we can find three stable
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FeAl-X structures, including FeAl-Cr (B/G=1.87, v=0.27), FeAl-Ti (B/G=1.80,

v=0.27) and FeAl-Co (B/G=1.92, v=0.28), which are considered in the following

discussion.

The Zener anisotropy factor Az is used to quantify the degree of anisotropy of a

solid [37], and thus to predicate the mechanical durability of materials, the
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corresponding formula can be given as follows:

2C44
AZ = (11)
C11 − C12

As the value of Az is equal to one, the material is elastically isotropic; otherwise,

it is elastically anisotropic, where a greater difference from the value of 1.0 would

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indicate a higher degree of elastic anisotropy. The results of the Zener anisotropy

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factor for FeAl-X at 0 GPa are listed in Table 3, and are in the range of 1.40 to 2.63,

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suggesting that the compounds are not an elastic, isotropic material.

3.3 Electronic structure

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Fig. 2(a) shows the band structure along the highly symmetrical direction in the
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Brillouin zone of FeAl, and Fig. 2(b), (c) and (d) display the partial band structure (-2
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to 2 eV) of FeAl-Cr, FeAl-Ti and FeAl-Co, respectively. The black and red curves

represent the band structure of spin-up and spin-down electrons, respectively. The
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horizontal dashed line represents the Fermi level (EF). It can be found that the valence
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band crosses the Fermi level, which indicates the presence of free electrons near the
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Fermi level. Moreover, the number of bands (near EF) of FeAl-X is more than that of

FeAl, which implies that the substitution by the elements X cause the FeAl
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compounds to have more metal characteristics.

Fig. 3 exhibits the total density of states (TDOS) and partial density of states

(PDOS) of FeAl (Fig. 3(a)) and FeAl-X (Fig. 3(b), (c) and (d)), which can reflect the

specific composition of the electronic states in the energy band structure [38]. As

shown in Fig. 3(a), the main bonding peak (-4.0~3.1 eV) originates from the

contribution of the Fe-3d state, but the main characteristic of the electronic structure
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of FeAl is dominated by the hybridisation between the Fe-3d state and Al-3p state. Fig.

3(b) shows that the main bonding peak is contributed by the hybridisation of Fe-3d

state, Al-3p state and Cr-3d state. Moreover, the two small bonding peaks of FeAl-Cr

are attributed to the contribution of the Cr-s state and Cr-3p state, respectively.

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Similarly, the bonding peaks of FeAl-Ti are derived from the Fe-3d, Al-3p, Ti-s, Ti-3p

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and Ti-3d states in Fig. 3(c), and the Fe-3d, Al-3p and Co-3d states formed the

bonding peaks of FeAl-Co in Fig. 3(d).

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Population analysis can provide a quantitative result and more insightful

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information on chemical bonding to determine some of the ground state properties.
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The results of Mulliken population are summarised in Tables 4–7. It can be seen that

there is a charge transfer for FeAl, i.e., the charge of Al atoms transfer to Fe atoms
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(4.05 e). The doping by Cr increased the amount of transferred charge to 4.15 e,
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which indicates that there are strong ionic interactions between Fe, Al and Cr atoms in
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FeAl-Cr. Similarly, a significant charge transfer in FeAl-Ti (4.65 e) and FeAl-Co

(4.06 e) shows that there are strong ionic interactions between Fe, Al and Ti atoms of
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FeAl-Ti and between Fe, Al and Co atoms of FeAl-Co. Table 8 exhibits the calculated
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bond length and bond population for the nearest neighbours in the crystals of FeAl
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and FeAl-X. According to Cheng’s paper [39], the positive (negative) values of the

bonds population represent the bonding (anti-bonding) states, and a zero value implies

a perfect ionic bond, while a value grater than zero indicates a covalent characteristic

of a bond. One can see from the table that the Al-Al and Fe-Al bonds of all FeAl

compounds are in a bonding state, and the Al-Al and Fe-Al bonds of FeAl-X show the
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opposite change (reduction or increase) of covalent characteristic. The Fe-X bonds of

FeAl-Cr and FeAl-Ti, Fe-Fe bond of FeAl, and Al-X bond of FeAl-Ti are in an

antibonding state. Although the Al-X bonds of FeAl-Cr and FeAl-Ti appear to be in a

different bonding state, all the values are close to zero, indicating that there is no

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significant interaction between the Al and X atoms in FeAl-Cr and FeAl-Ti.

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Furthermore, the doping of Cr, Ti and Co changes the Fe-Fe bond from the

antibonding state in FeAl to a bonding state in FeAl-X, and the Fe-Fe bond of FeAl-Ti

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have more covalent characteristic. It can be summarised that the addition of Cr, Ti and

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Co weakens the Al-Al interaction, and enhances the Fe-Fe and Fe-Al interactions.
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The electron density difference can further illustrate the bonding characteristics.

Fig. 4 gives the electron density difference maps of FeAl (Fig. 4 (a)) and FeAl-X (Fig.
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4 (b), (c) and (d)) along the (110) plane, where the density values are plotted from -0.7
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e/Å3 to 0.4 e/Å3. The red and blue colours represent the accumulation or depletion of
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electronic charge, respectively. Obviously, the Fe-Cr bond of Fig. 4(b) and the Fe-Ti

bond of Fig. 4(c) show stronger interaction compared with the Fe-Al bond of Fig. 4(a)
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because of the large charge accumulation between Fe and X atoms, which is in

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accordance with the analysis of the bond population. In Fig. 4(d), there is not an
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obviously higher charge density between Co-Fe and Co-Al atoms. Moreover, we note

that the charge density in the core regions of X atoms decreases in this order: Co Ti

Cr. The influence of the electronegativity difference on the electron transfer

between the X, Fe and Al components has been addressed by Hafner [40]. Combined

with the results of bond population, it is concluded that the interaction of antibonding
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state and bonding state in FeAl-Cr and FeAl-Ti systems has a negative impact on

toughness, and the bonding state of all the bonds in FeAl-Co system play a positive

role in strength. That is the main reason why the calculated value of B/G of FeAl-Co

is higher than FeAl-Cr and FeAl-Ti. For FeAl-Cr and FeAl-Ti, the doping Ti leads to

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a stronger antibonding state than that of doping Cr, so the B/G value of FeAl-Cr is

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higher than FeAl-Ti. This proves that the ductile characteristics are in the order Co

Cr Ti of FeAl-X.

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4. Conclusions

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In summary, we have performed first-principles calculations to study the
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structural stabilities, mechanical properties and electronic structures of FeAl-X

intermetallics. It is found that Al atoms are preferably replaced by the X elements.

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Based on the critical value for B/G and Poisson’s ratio v, we conclude that FeAl-X
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(X=Cr, Ti, Co) exhibit ductile characteristics decreasing in the order Co Cr Ti.
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The study of the electronic structure reveals that the addition of Co, Cr and Ti

increases the charge transfer, weakens the Al-Al interaction and strengthens the Fe-Fe,
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Fe-Al interactions.
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Acknowledgements

This work was supported by the National Foundation of Natural Science of China

(No. 51171096) and the Graduate Innovation Fund of Shaanxi University of Science

and Technology. We also acknowledge the support of the CASTEP software of Dr

Ping Peng’s research group at Hunan University.

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[30] I. M. Anderson, ALCHEMI study of site distributions of 3d-transition metals in
B2-ordered iron aluminides, Acta Mater., 45 (1997), pp. 3897-3909.

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[31] C. H. Kong, P. R. Munroe, The effect of ternary additions on the vacancy
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hardening of FeAl, Scripta Metall. Mater., 30 (1994), pp. 1079-1083.
[32] V. B. Deyirmenjian, V. Heine, M. C. Payne, et al, Ab initio atomistic simulation
of the strength of defective aluminum and tests of empirical force models,
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Phys. Rev. B, 52 (1995), pp. 15191-15207.

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[33] J. F. Nye, Physical Properties of Crystals, Oxford University Press, Oxford,

1985.
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[34] Y. Pan, W. M. Guan, K. H. Zhang, First-principles calculation of the phase

stability and elastic properties of ZrPt compounds at ground state, Physica B, 427
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(2013), pp. 17-21.

[35] R. Hill, The elastic behavior of a crystalline aggregate, Proc. Phys. Soc. A, 65
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(1952), pp. 349-354.

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[36] S. F. Pugh, XCII. Relations between the elastic moduli and the plastic properties
of polycrystalline pure metals, Philos. Mag., 45 (1954), pp. 823-843.
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Phys. Rev. Lett, 101(2008), p. 055504.
[38] C.M. Li, S. M. Zeng, Z.Q. Chen, et al, First-principles calculations of elastic and
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Cu alloys, Comput. Mater. Sci., 93 (2014), pp. 210-220.
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[39] Y. Cheng, Z. L. Lv, X. R.Chen, et al, Structural, electronic and elastic properties

of AlFe2B2: First-principles study, Comput. Mater. Sci., 92 (2014), pp. 253-257.

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Phys., 15 (1985), pp.1879-1893.

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Table 1
Lattice constants of FeAl-X (2a=2b=2c, in Å).

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Phase V Sc Mn Si Mg Co Zr Cu Zn Nb Cr Mo W Ti Ni

This work 5.709 5.795 5.701 5.683 5.769 5.719 5.811 5.720 5.733 5.768 5.688 5.735 5.738 5.743 5.695

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Reference _ 5.82[9] _ _ _ _ _ _ _ _ 5.683[10] 5.733[10] 5.736[10] _ _

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data

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Table 2
Total energy, formation enthalpy ∆H, substitution formation enthalpy Esite and
substituting atoms in FeAl-X (X=V, Sc, Mn, Si, Mg, Co, Zr, Cu, Zn, Nb, Cr, Mo, W,
Ti, Ni).
Phase EFe7Al8X(eV) EFe8Al7X(eV) EFe(eV) EAl(eV) Esite(eV) Site preference

V -8490.29 -9300.78 -6.84 -7.30 0.46 Al

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Sc -7791.17 -8600.30 -6.60 -6.97 0.37 Al
Mn -7167.85 -7976.81 -6.90 -7.26 0.36 Al

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Si -6621.35 -7431.87 -6.65 -7.11 0.46 Al
Mg -7487.58 -8295.75 -6.39 -6.71 0.31 Al

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Co -7558.61 -8365.72 -6.92 -6.71 -0.22 Fe

Zr -7794.61 -8604.55 -6.74 -7.17 0.43 Al

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Cu -7991.36 -8798.66 -6.62 -6.88 0.26 Al
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Zn -8224.22 -9032.38 -6.44 -6.76 0.31 Al

Nb -8065.04 -8875.69 -6.92 -7.39 0.47 Al

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Cr -8981.23 -9791.35 -6.91 -7.35 0.44 Al

Mo -8450.33 -9260.76 -6.97 -7.43 0.45 Al

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W -8447.02 -9258.09 -6.97 -7.47 0.50 Al

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Ti -8117.33 -8927.43 -6.76 -7.18 0.42 Al

Ni -7870.12 -8677.08 -6.86 -7.07 0.21 Al

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Table 3
Calculated elastic constants C11, C12 and C44, bulk modulus B, shear modulus G,

Young’s modulus E, Poisson’s ratio v, Zener anisotropy factor Az and ratio of bulk
modulus to shear modulus B/G of 3x3x3 FeAl-X intermetallics.

Phase C11 C12 C44 B G E v Az B/G

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(GPa) (GPa) (GPa) (GPa) (GPa) (GPa)

V 262.26 127.25 149.76 172.25 108.77 269.57 0.24 2.22 1.58

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Sc 371.67 145.56 143.25 220.93 130.30 326.68 0.25 1.27 1.70

Mn 262.76 136.15 149.57 178.35 105.93 265.28 0.25 2.36 1.68

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Si 266.09 130.74 151.84 175.85 109.79 272.63 0.24 2.24 1.60
Mg 325.02 125.69 147.70 192.13 126.16 310.51 0.23 1.48 1.52

Co 292.73 163.31 150.92

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206.45 107.44 274.68 0.28 2.33 1.92
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Zr 400.70 153.36 143.31 235.81 135.10 340.31 0.26 1.16 1.74

Cu 256.25 131.84 152.37 173.31 106.38 264.93 0.25 2.45 1.63

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Zn 244.82 133.00 147.30 170.28 99.90 250.68 0.25 2.63 1.70

Nb 349.84 141.27 146.30 210.79 127.75 318.83 0.25 1.40 1.65
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Cr 295.30 158.31 148.99 203.97 109.07 277.71 0.27 2.18 1.87

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Mo 277.56 139.38 149.11 185.44 109.50 274.48 0.25 2.16 1.69

W 266.33 128.50 151.11 174.44 110.27 273.23 0.24 2.19 1.58
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Ti 280.94 148.73 147.67 192.80 106.96 270.80 0.27 2.23 1.80

Ni 270.06 130.34 155.65 176.92 112.86 279.20 0.24 2.23 1.57
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Table 4
Mulliken populations of FeAl.
Species Number s p d Total Charge(e)

Fe 27 0.34 0.77 7.04 8.15 -0.15

Al 27 0.88 1.97 0.00 2.85 0.15

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Mulliken populations of FeAl-Cr.

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Species Number s p d Total Charge(e)

Fe 1 0.32 0.81 7.03 8.17 -0.17

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Fe 8 0.34 0.78 6.99 8.10 -0.10

Fe 5 0.33 0.81 7.02 8.16 -0.16

Fe 13 0.34 0.82 7.02
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Al 8 0.88 1.96 0.00 2.85 0.15

Al 12 0.88 1.95 0.00 2.84 0.16

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Al 6 0.88 1.95 0.00 2.82 0.18

Cr 1 2.59 6.49 4.97 14.04 -0.04
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Mulliken populations of FeAl-Ti.
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Species Number s p d Total Charge(e)

Fe 1 0.32 0.79 7.09 8.19 -0.19

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Fe 8 0.37 0.79 7.02 8.19 -0.19

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Fe 6 0.33 0.77 7.04 8.15 -0.15

Fe 12 0.35 0.80 7.02 8.17 -0.17

Al 8 0.88 1.97 0.00 2.86 0.14

Al 12 0.89 1.97 0.00 2.85 0.15
Al 6 0.88 1.97 0.00 2.86 0.14

Ti 1 2.39 6.11 2.65 11.15 0.85

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Table 7
Mulliken populations of FeA-Co.
Species Number s p d Total Charge(e)

Fe 8 0.33 0.77 7.04 8.15 -0.15

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Fe 12 0.34 0.78 7.04 8.15 -0.15
Fe 6 0.33 0.76 7.06 8.15 -0.15

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Al 27 0.88 1.97 0.00 2.85 0.15
Co 1 0.40 0.75 8.00 9.16 -0.16

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Table 8
The calculated bond length and bond population of FeAl and FeAl-X (X=Cr, Ti, Co).
Species Bond length
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Fe-Fe Fe-Al Fe-X Al-X Al-Al Fe-Fe Fe-Al Fe-X Al-X Al-Al

FeAl 2.858 2.474 — — 2.858 -0.19 0.10 — — 0.20

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FeAl-Cr 2.909 2.519 2.519 2.909 2.909 0.09 0.21 -0.27 0.02 0.07

FeAl-Ti 2.910 2.487 2.520 2.851 2.863 0.19 0.23 -0.38 -0.02 0.09
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FeAl-Co 2.860 2.470 2.865 2.472 2.863 0.10 0.17 0.09 0.19 0.11
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Captions

Fig. 1. Crystal structure of 2×2×2 FeAl supercell with X substituting Fe atoms; (b)
Crystal structure of 3×3×3 FeAl supercell with X substituting Al atoms; (c) Crystal

structure of 3×3×3 FeAl supercell with Co substituting Fe atoms.

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Fig. 2. The energy band structure of (a) FeAl; (b) FeAl-Cr; (c) FeAl-Ti; and (d)
FeAl-Co.

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Fig. 3. The calculated DOS and PDOS of (a) FeAl; (b) FeAl-Cr; (c) FeAl-Ti; and (d)

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FeAl-Co.

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Fig. 4. The electron density difference of (a) FeAl; (b) FeAl-Cr; (c) FeAl-Ti; and (d)
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FeAl-Co.
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Fig. 1

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(a) (b) (c)

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Fig. 2

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Fig. 4

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Highlights

•Ternary additions to FeAl were systematically investigated by first

principles calculations.

•Almost all of the alloying elements tend to replace Al atoms except the

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Co.

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• The doping by Cr, Ti and Co form the most stable FeAl-based

intermetallics.

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•The doping of Cr, Ti and Co weakens the Al-Al interaction and

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strengthens the Fe-Fe, Fe-Al interactions.
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