Intermetallics 18 (2010) 2083e2089

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Intermetallics
journal homepage: www.elsevier.com/locate/intermet

Link between structural and mechanical stability of fcc- and bcc-based ordered
MgeLi alloys
M.J. Phasha a, b, *, P.E. Ngoepe a, b, H.R. Chauke a, D.G. Pettifor c, D. Nguyen-Mann d
a
Materials Modelling Center, School of Physical and Minerals Sciences, University of Limpopo, Private Bag x1106, Sovenga, South Africa
b
Materials Science and Manufacturing, CSIR, Meiring Naude, Brummeria, P.O. Box 395, Pretoria 0001, South Africa
c
Materials Modelling Laboratory, Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH, UK
d
UKAEA, Culham Science Centre, Oxfordshire OX14 3DB, UK

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

Article history: The first principles pseudopotential calculations based on the PerdeweBurkeeErnzerhof (PBE) form of
Received 7 May 2010 generalized gradient approximation (GGA) within density functional theory (DFT) have been utilized to
Received in revised form investigate the structural and elastic properties of cubic-based MgeLi alloys. The heats of formation and
17 June 2010
elastic moduli were used in predicting structural stability profile, and their results are consistent with
Accepted 18 June 2010
Available online 14 July 2010
each other. In terms of phase stability, an interesting correlation between the calculated tetragonal shear
modulus (C0 ) and formation energy of corresponding bcc and fcc ordered compounds relative to hcp Mg
and Li lattices is drawn. The predicted stability trend due to structural energy difference was further
Keywords:
E. ab initio calculations
confirmed by electronic structure calculations based on Jones-type analysis.
B. Elastic properties Ó 2010 Elsevier Ltd. All rights reserved.
B. Brittleness and ductility
E. Phase stability, prediction

1. Introduction between 15 and 35 atomic percent (at.%) Mg has been predicted in

the past, at least at very low temperatures [3].
Magnesium is one of the readily available metals, constituting Currently, the development of Mg alloys with desirable physical
about 2.7% of earth’s crust, offers several advantages including and mechanical properties with remarkable weight saving appli-
excellent machinability, recyclability, good castability, good weld- cation remains a challenge. If the development of these alloys
ability, good creep resistance, high thermal conductivity, and follows a path similar to Al alloys [4], using traditional trial and
extreme lightness [1]. These features render magnesium alloys error methods and techniques, it would require a similar level of
suitable and ideal for use in applications where lightweight to effort of many years. However, ab initio density functional theory
specific strength ratio is vital. At a density of 1.74 g/cm3, magnesium (DFT) methods provide an opportunity to drastically accelerate
(Mg) is amongst others the lightest structural metal. However, due materials research by efficiently predicting new phases and accu-
to hexagonal close-packed (hcp) crystal structure, Mg and Mg alloys rately describing their ground states [5]. Recently, ab initio calcu-
have undesirable mechanical properties at room temperature, lations have concentrated on gaining a detailed knowledge of the
including difficult workability. Fortunately, the addition of at least electronic structure of materials and its effects on microscopic and
11 weight percent (wt.%) lithium does not only reduce the density of macroscopic behaviours [6,7]. Considering these simulation
magnesium but also transforms the hcp Mg into more workable advantages, the theoretical ab initio studies on MgeLi system
body-centered cubic (bcc) phase [2]. The resulting magne- remain surprisingly scarce [8e10]. The work by Uesugi et al.
siumelithium (MgeLi) alloys exhibit good formability and becomes focused only on hcp Mg7Li alloy [8,9], while the more recent
the lightest metallic alloys with promising technological applica- investigation by Counts et al. emphasized the mechanical proper-
tions in transport (automotive and aerospace) and communication ties of only bcc MgeLi alloys using the supercell approach [10].
(portable electronic equipments) industries, due to their good In this paper, the ab initio calculations based on pseudopoten-
strength-to-weight ratio and improved ductility. Furthermore, the tials plane wave method were used to investigate existence of fcc
existence of metastable fcc (face-centered cubic) at concentrations and bcc binary MgeLi alloys at 0 K for various concentrations, using
ordered crystal structures. In order to avoid unworkable hcp Mg
alloys, the current work attempts to find suitable alternative stable
* Corresponding author. Tel.: þ27 12 841 3196; fax: þ27 12 841 3378. or metastable cubic low temperature formable MgeLi alloys, from
E-mail address: [email protected] (M.J. Phasha). heats of formation. Furthermore, we investigate if these cubic

0966-9795/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.intermet.2010.06.015
2084 M.J. Phasha et al. / Intermetallics 18 (2010) 2083e2089

phases possess desirable mechanical properties and are easily the full Brillouin zone, the selected sufficient cut-off energy and k-
malleable. More recently, similar approach has been successfully points were converged to within 1 meV/atom and 5 meV/atom for
used to study the phase stability [11] and mechanical properties pure elements and superstructures, respectively.
[12] of other Mg-based binary alloys, and yielded results that are The second set of calculations was performed to obtain elastic
good agreement to experiments. The current work focuses on cubic coefficients of MgeLi alloys using CASTEP on Materials Studio
MgeLi ordered structures within 3:1 (L12 and DO3) and 1:1 (L10 version 3.0 interface [20]. We used six different values of the strain
and B2) stoichiometries, while the end elements were taken as fcc 0.0008, 0.0024 and 0.004 for each structure. The application of
and bcc for both Mg and Li. In order to study small additions of Mg strain on the lattice implies a lowering of symmetry from that of the
and Li to pure Li and Mg metals respectively, we also examine the crystal, therefore very accurate total energy calculations are
7:1 and 15:1 stoichiometry in the fcc and bcc lattice, respectively. required, since the energy differences involved are of the order
We will find which phases are more stable based on the predicted 10e1000 meV/atom. In addition, this condition requires the use of
negative heats of formation and the structural formation difference slightly denser k-points to be utilized than in geometry optimiza-
(DHf (bcc  fcc)). Furthermore, the mechanical stability for cubic tion of crystals. The current set of calculations was considered
crystals will be determined from tetragonal shear modulus, while converged when the maximum force on atoms was below 0.01 eV/Ǻ,
elastic moduli and ratio of bulk to shear modulus (measure of the total energy change per atom was less than 4  104 eV/atom
ductility) will also be reported. Moreover, we will note the corre- and the displacement of atoms was below 4  104 Ǻ. The value of
lation on the trend of structural formation difference (DHf the stress was automatically computed for each strain, and resulted
(bcc  fcc)) and change in shear modulus (DC0 ). In order to validate in a stressestrain linear fit curve, from which each component of
the phase stability in terms of structural energy differences, the the stress was computed, and respective gradients provided the
electronic structure (ES) calculations due to electron band filling values of the corresponding elastic constants. Based on three
(electron per atom ratio) spanning the entire concentration range independent single crystal elastic constants of a cubic crystal, C11,
of fcc and bcc phases will be determined. ES was based on rigid- C12, C44 the elastic moduli of polycrystalline material were calcu-
band model formalized by Jones-type analysis, and therefore lated following averaging schemes of Voigt (upper bound) and
provides composition ranges in which cubic phases are stable. Reuss (lower bound) as follows [21]:
This paper is organized as follows, in Section. 2, the computa-

tional details followed to solve the electronic structure are briefly 9BG 1 C11  C12 þ 3C44 5C44 ðC11  C12 Þ
E ¼ ; G ¼ þ
outlined. The trends in cohesive and elastic properties are respec- 3B þ G 2 5 4C44 þ 3ðC11  C12 Þ
tively analysed and discussed in Section. 3. Finally, Section. 4
presents the conclusion of the paper.  
C11 þ 2C12 C11  C12 ð2C44 þ C12 Þ
B ¼ ; C’ ¼ ; A ¼
3 2 C11
2. Computational details
where E is the Young’s modulus, G shear modulus, B bulk modulus,
The equilibrium lattice parameters and electronic structure C0 tetragonal shear modulus and anisotropic factor A.
calculations were optimized using the ab initio plane wave (PW)
pseudopotential method, embodied in the CASTEP code [13]. The
HohenbergeKohneSham density functional theory (DFT) [14] was 3. Results and discussions
used within the GGA formalism [15] to describe the electronic
exchangeecorrelation interactions. We used the recent PBE form of 3.1. Structural stability
the GGA [16], which was designed to be more robust and accurate
than the original GGA formulation. The Vanderbilt ultrasoft pseu- The equilibrium lattice parameters, a0, of the geometrically
dopotentials [17] were employed for MgeLi structures. Calculations optimized structures are listed in Table 1. In calculations where the
were carried out on ordered fcc-based phases, L12 (MgLi3, Mg3Li, ordered superstructures were used, resulting to twice the value of
and (MgLi7, Mg7Li) and the bcc-based phases B2 (MgLi), B32 (MgLi), a0, the calculated a0 values listed in Table 1 were normalized, for
DO3 (MgLi3), Mg3Li) and (MgLi15, Mg15Li). In addition, the structural comparison purposes. With increasing Li concentration, the lattice
energetics of tetragonal L10 (MgLi) and DO22 (MgLi3, Mg3Li) phases parameter decreased to its minimum at 50:50 equi-atomic
are reported. The first set of calculations were performed at our compositions, after which a slight increase in a0 is observed. The
theoretically determined (equilibrium) lattice constants for each observed trend, which deviates slightly from Vegard’s law for solid
structure [18], with a plane wave basis set defined by an energy cut- solutions, is similar in both bcc and fcc MgeLi alloys considered in
off of 500 eV for all considered superstructures. Furthermore, the this study. This behaviour was also realised in earlier theoretical
minimum and maximum Guassian smearing width were respec- [3,22] as well as experimental [23,24] studies. Although the lattice
tively set at 0.4 and 0.1 eV for superstructures, and at 0.1 and parameter of bcc Li is underestimated by current and other calcu-
0.01 eV for elemental metals, since the lattices of the latter involve lations [25,26], in general our predicted lattice parameters are in
energy differences of the order 1e100 meV/atom than is required in good agreement with available experimental and theoretical results.
the former. In addition, this condition requires the use of denser The heat of formation, Hf, of the alloy is computed according to
MonkhorstePack [19] sets of k-points and a little alteration to the the relation [11,25]
defaulted setting within the code, especially in case of Li, than it is
Mg1x Lix 1 Mg1x Lix h Mg Li
i
averagely and adequately acceptable, respectively, for Mg and Hf ¼ Etotal  ð1  xÞEsolid þ xEsolid (1)
alloyed compounds. These parameters are essential since the Fermi n
Mg Li Mg Li
energy, and hence the total energy depends quite sensitively on where Etotal1x x is the total energy of the alloy, Esolid and Esolid are the
them. The convergence criterion of less than 2  105 eV on total total energies of the stable structures of elemental Mg and Li, n is
energy per atom, 103 Ǻ on the displacement of atoms, 0.05 eV/Ǻ on the total number of atoms in the superstructure, x and ð1  xÞ refer
the residual forces, and 0.1 GPa on the residual bulk stress was used. to the fractional concentrations of the constituent elements.
Uncommonly, a special care was taken when treating Li element, We note that the heat of formation curve shown in Fig. 1 makes
only during structure relaxations to avoid emanating stable phase a V-shape, with its minimum at the equi-atomic concentration of
disagreements with experiments. With our choice of mesh grid in MgeLi compound. At 50e50 concentration, the B2 structure is
 M.J. Phasha et al. / Intermetallics 18 (2010) 2083e2089 2085

Table 1
Predicted elastic constants of MgeLi alloys at equilibrium lattice parameters. The bulk moduli determined from elastic constants are compared with the ones calculated from
equation of states. Asterisks denote the results generated from this work. For comparison, theoretical and experimental results are shown in parentheses, normal and square
brackets, respectively.

Comp. Phase a0 (Å) C11 (GPa) C12 (GPa) C44 (GPa) B (GPa) C’ (GPa) G (GPa) B ¼ V0 ðd2 E=dV 2 Þ B/G E (GPa) A
(GPa)
Mg fcc* 4.530 42.8 31.0 23.1 34.9 5.9 13.4 34.1 2.60 35.7 1.8
fcc 4.520(27) 46.0 27.4 30.0 33.6 9.3
4.516(26)
bcc* 3.585 25.6 39.4 36.0 34.8 6.9 5.4 37.6 6.44 1.7 4.3
3.571(26)
*
Mg15Li bcc 3.568 55.8 24.7 50.9 35.1 15.5 31.7 32.9 1.11 73.1 1.7
Mg7Li fcc* 4.495 22.2 29.5 24.2 27.0 3.6 0.6 34.0 45.00 1.8 3.5
Mg3Li L1*2 4.458 25.8 29.9 24.5 28.5 2.1 2.9 27.2 9.83 9.0 3.1
29.4(22)
35%Li DO*3 3.512 40.0 25.6 41.0 30.4 7.2 20.9 32.8 1.45 51.0 2.7
bcc[37] 35.1 24.4 26.4 28.0 25.0[37]
30.5(22)
MgLi B2* 3.420 37.5 19.7 25.9 25.6 8.9 16.9 22.1 1.51 41.6 1.9
3.458(25) 27.5(25)
20.2(22)
Exp.[38] 55% 32.2 19.8 26.6 23.9 e
Exp.[38] 45% 28.5 20.5 19.4 23.2 e
B32* 3.474 31.0 24.6 28.6 26.7 3.2 12.6 25.2 2.12 32.7 2.5
L1*0 4.820 25.4 29.2 24.8 22.3 1.9 15.0 25.2 1.49 36.7 39.7
c/a ¼ 0.72 C33 ¼ 15.3 C13 ¼ 19.1 C66 ¼ 27.0 24.2(22)
14.2
MgLi3 L1*2 4.309 25.8 15.9 18.7 19.2 4.9 11.0 19.1 1.74 27.7 2.1
18.8(22)
DO*3 3.423 19.4 17.8 15.4 18.3 0.8 5.7 18.0 3.21 15.5 2.5
75%Li bcc[37] 15.7 15.0 13.6 15.2 15.0[37]
18.8(22)
MgLi7 fcc* 4.305 15.8 16.9 11.7 16.6 0.6 2.7 16.4 6.15 8.2 2.5
MgLi15 bcc* 3.421 18.2 13.2 11.5 14.9 2.5 6.3 23.1 2.36 16.5 2.0
Li fcc* 4.307 17.5 11.4 9.3 13.4 3.0 6.0 13.9 2.23 15.7 1.7
Cal fcc 4.321(26) 19.8(32) 13.6 10.9 15.7 e 14.0 2.7
bcc* 3.424 19.6 10.9 16.1 13.8 4.4 9.6 12.0 1.44 23.4 2.2
Cal bcc 3.442(26) 17.7(31) 13.4 10.0 14.8 2.0 e 15.2
Cal bcc 16.8(32) 13.0 11.0 14.3
Exp.[29] bcc[29] 3.491 14.8 12.5 10.8 13.3 e

clearly the most stable phase, since it has the lowest formation relaxed from c/a ¼ 1, collapses to c/a ¼ 0.72. This is because the
energy amongst its competing counterparts. The calculations predict tetragonal system is not stationary by symmetry for c/a ¼ 1 but
the B2 structure to be 26.0 meV/atom lower in energy compared to collapses down to B2 with c/a ¼ 0.707. The frozen L10 with c/a ¼ 1 lies
B32 phase. Our predicted heat of formation for the B2 structure of 29.25 meV/atom higher in energy compared to B2 phase.
73.4 meV/atom is in excellent agreement with Skriver’s DFT result The heat of formation for Mg3Li alloy composition was calcu-
of 73.5 meV/atom [22], and is thus consistent with earlier experi- lated for three equivalent ordered crystal structures (DO3, L12,
mental observations regarding tendency towards B2 (CsCl) type DO22) as shown in Fig. 1. It clearly shows the preferred stability of
ordering at low temperatures [23,24]. The L10 structure, which was the DO3 phase over the L12 and DO22 phases, with formation
energies of 38.32, 23.96 and 18.82 meV/atom, respectively.
Our predicted phase stability ordering is the same as that of Skriver
20
[22]. However, in the MgeLi3 compound, the DO22 structure has the
fcc-based Mg15Li lowest formation energy (37.43 meV/atom) with the L12 and DO3
bcc-based
phases lying only 0.82 and 6.32 meV/atom higher, respectively,
0
MgLi15 Mg7Li in contrast to Skriver. We see that Skriver predicts the DO3 phase to
be more stable than DO22. This is probably because their c/a axial
ΔHf (meV/atom)

-20 MgLi7 DO22 ratio was not relaxed from its ideal value of 2.00, as compared to
L12 our relaxed equilibrium value of 2.02. The slight difference between
DO3 L12 and DO22 indicates a strong stability contest between these
(DO22, L12) L10
-40 phases.
DO3
The solid common-tangent lines were constructed in Fig. 1 to
B32
show the stability limits of the different phases. Among the struc-
-60 tures considered, the most energetically favourable intermetallic
B2
phases at absolute zero are the DO3 Mg3Li, B2 MgLi, DO22 and L12
MgLi3 and MgLi7 compounds. The DO3 structure is metastable at
-80
0 20 40 60 80 100 25 at.% Li, while the B32 and L10 structures are metastable at 50 at.%
Li Mg Li. Our equilibrium calculations predict DO3 to be the most stable
Mg at. %
structure at A3B (Mg-rich) composition, while at Li-rich side (AB3)
Fig. 1. Predicted heats of formation for MgeLi alloys. The common-tangent the face-centered structures (L12 and DO22) show more stability
construction for stability limits of the different phases is indicated by the dashed lines. over the body-centered phase.
2086 M.J. Phasha et al. / Intermetallics 18 (2010) 2083e2089

The Mg-rich compounds, the bcc supercell Mg15Li and the fcc 3.2. Mechanical stability
supercell Mg7Li, lie well above the tangent line connecting hcp Mg
(Hf ¼ 0 eV) with DO3 Mg3Li. This clearly indicates the instability of The calculated elastic constants for the cubic MgeLi alloys are
the bcc and fcc MgeLi compounds around this region. This insta- listed in Table 1. The elastic constants of the fcc Mg lattice are in
bility supports Hafner’s earlier work [3] that hcp MgeLi compounds good agreement with the available theoretical results [27] while
are dominant in the region with less than 18 at.% Li concentration. the bcc phase is found to be mechanically unstable, since the
The formation energy of Mg3Li in both the DO22 and L12 structures tetragonal shear modulus C0 is negative. Our results for pure Li in
lie above tangent line, which indicates the instability of the fcc both fcc and bcc lattices show mechanical stability with the elastic
lattice in this region. Most of MgeLi compounds at the Li-rich side constants being in good agreement with both experimental [28,29]
lie either exactly or very close to the tangent line connecting B2 and previous theoretical [30,31] results, except for the case of C11
MgeLi with elemental hcp Li. For example, fcc MgLi7 shows and C44 of the bcc lattice which are overestimated. The elastic
a strong sign of metastability as it was earlier pointed [3]. Thus, low constants in Ref. [32] are derived from calculated phonon disper-
temperature sequence of hcp / bcc / hcp alloy phases with the sions. Our predicted elastic constants were calculated at equilib-
existence of metastable fcc phase in Li-rich dual phase region is rium lattice constants rather than the experimental values, hence
predicted, resulting to possible hcp / fcc / bcc / hcp stability led to slight difference from experimentally determined elasticity.
trend. Structural formation energy differences, DHf, between cor- This may be ascribed to the elastic constants being sensitive to the
responding bcc and fcc MgeLi compounds, against the electron per lattice constant of the crystal [33].
atom ratio, as illustrated in Fig. 2(a) also suggest the same trend. Other elastic moduli such as shear modulus (G), Young’s
The above predicted stability profile is in full agreement with both modulus (E), and B/G ratio of MgeLi alloys are also listed in Table 1.
experimental as well as theoretical results [3]. Although Zhang et al. Most of the elastic constants of MgeLi structures listed in satisfy
[11] dealt with the enthalpies of formation for binary Mg the mechanical stability criteria of cubic systems as outlined else-
compounds other than MgeLi using a different plane wave pseu- where [18,30,34] as follows:
dopotential method (VASP code), we note that their findings in
enthalpies of formation have similar V-shaped trend as in our C44 > 0; C11 > jC12 j and C11 þ 2C12 > 0
current work; in particular the 50e50 composition is more ener-
getically favourable than the 3:1 ratio (Mg3X), except for the except for Mg bcc, Mg7Li, Mg3Li (L12) and MgLi7 structures which
MgeLa. are mechanically unstable. These elastic stability conditions also
lead to a restriction on the magnitude of B. Since B is a weighed
average of C11 and C12 and stability requires that C12 be smaller than
C11, we are then left with the result that B is required to be inter-
a -30 mediate in value between C11 and C12: C12 <B < C11.
B2-L10 There is a good agreement between the bulk moduli obtained
from elastic constants as well as from equation of states with
-20 available experimental [35] and other previous theoretical results
ΔHf (Hfbcc-Hffcc) (meV/atom)

DO3-L12
[10,22]. With increasing Li concentration, the bulk modulus
decreased monotonically. Pugh proposed the B/G ratio to predict
-10
the ductility (>1.75) or brittleness (<1.75) [36]. For cubic MgeLi
alloys in Table 1, the B/G increases from very brittle (50 at.% Li) to
ductile (>50 at.% Li) with increasing Li composition. The bcc phases
0
have maximum ductility at 75 at.% Li, while the same is achieved at
87.5 at.% Li for fcc MgeLi structures although accompanied by
DO3-L12
10 mechanically instability. The negative values of B/G also reflect
instability of the corresponding compounds. As expected from
thermodynamics, it is evident from Table 1 that the fcc phases at
20 low Li content (<50 at.%) are mechanically unstable. It is also
b B2-L10 DO3-L12 interesting to note that the bcc Mg15Li and DO3 (Mg3Li) structures
10
are the only mechanically stable phases (C11 > C12) in this Mg-rich
8 region supporting earlier theoretical work [37], although their B/G
ΔC' (C'bcc-C'fcc) (GPa)

values is lower than 1.75, indicating brittleness, and hence have the
6
highest Young’s modulus E. This stability is in agreement with
4 experiment, that in this composition range the bcc phase is
mechanically stable, and coexists with the hcp phase [2,3].
2 However, in agreement with predictions by Counts et al. [10], our
0 results reveal brittleness between 25 and 50 at.% Li. Furthermore, at
50:50 composition we predict B2 to be the most stable phase
-2 compared to B32, in agreement with experiment [38], but we note
the opposite with regard to ductility, where B2 is brittle. The
-4
DO3-L12 superiority of B32 in ductility is in agreement with results obtained
-6 in Ref. [10]. At MgLi3 composition, our elasticity results suggest the
1.0 1.2 1.4 1.6 1.8 2.0 fcc phase to be the most mechanically stable than bcc, in agreement
Li Mg
e/a ratio with Hafner’s work [3] and experiment at low temperature,
although bcc is still the most ductile than any other composition, in
Fig. 2. (a) Structural formation energy differences, DHf between corresponding bcc
and fcc MgeLi compounds, against the electron per atom ratio and (b) change in shear
agreement with recent reports [10].
modulus between bcc and fcc superstructures. Note that the plot (a) has negative axis Besides B/G, it was recently found that the C’ is also very
running vertically upwards to make comparison with (b) real. significant on the mechanical properties of materials [39]. The
 M.J. Phasha et al. / Intermetallics 18 (2010) 2083e2089 2087

mechanical stability can be quantified by calculation of the those in Ref. [9], we could not find any work done on fcc-based
tetragonal shear modulus, C0 . The C0 for the bcc and fcc ordered MgeLi alloys to compare our results with.
phases is also listed in Table 1 and shown as a function of compo-
sition in Fig. 3. The ordered fcc phases are mechanically unstable at 3.3. Electronic structure
50 at.% Mg and above (Mg-rich), while for concentrations less than
50 at% Mg, the ordered bcc structures are either unstable or The relation between structural stability and the behaviour of
metastable compared to fcc. The elastically unstable structures the electronic density of states (DOSs) in the vicinity of the Fermi
showed negative Young’s modulus. As observed in Li-rich compo- energy can be formalized by a Jones-type analysis [44]. Using
sitions, the smaller C’ the lower the Young’s modulus. This elastic a rigid-band model, the theory shows how structure in the density
behaviour in crystals has been reported to yield better plasticity of states translates into an energy difference for competing phases
[39,40]. as a function of the electron count. Within the rigid-band approx-
The corresponding structural shear modulus C0 differences, DC0 , imation we assume that the bands of hcp, fcc, and bcc lithium
between bcc and fcc ordered MgeLi compounds, against the elec- remain unchanged (or rigid) on alloying. A Jones-type analysis then
tron per atom ratio ranging from 1 (Li) to 2 (Mg), relative to hcp Mg states that the structural energy difference between any two
and Li lattices, are plotted in Fig. 2(b). We find an interesting lattices at the same atomic volume is given by
correlation between these quantities, that, in the region where bcc
is very stable compared to fcc, the shear modulus is positive for bcc 2 3
ZEF
but negative for fcc (i.e. the fcc lattice is mechanically unstable) and
DU ¼ DUband ¼ D4 EnðEÞdE5 (2)
vice versa. A similar behaviour had been pointed out earlier for
NieCr disordered bcc and fcc phases by Craievich and Sanchez [41]
and for B2 and L10 TiAl by Sob et al. [42]. This reflects the under- where nðEÞ is the electronic density of state (DOS) per atom and EF
lying change in hcp to fcc to bcc to hcp structural stability as the is the Fermi energy. The difference in the band energy DUband, is
electron per atom ratio changes from 1 (Li) to 2 (Mg). In terms of the calculated under the constraint that the potential within the
predicted phase stability trend, a common behaviour is found WignereSeitz (WS) spheres remain unchanged on going from one
between the change in tetragonal shear modulus (DC0 ) and structure-type to another. The band energy difference equation
formation energy differences of corresponding bcc and fcc ordered allows us to perform a Jones-type analysis that links the relative
compounds relative to hcp Mg and Li lattices, which seem to stability of the two structures to the relative behaviour of the cor-
correlate the two structural properties. However, since in the low responding DOS. This link results from the relationship between
concentration limit as well as for higher temperatures the effect of the Fermi energy, EF, and the number of valence electrons, N,
the chemical disorder on the elastic properties of MgeLi alloys according to
could be significant, some more work concerning the random fcc
and bcc phases would require attention. ZEF
Another crucial elastic moduli considered to have a significant N ¼ nðEÞdE (3)
implication in engineering science is the elastic anisotropy of
crystals, since it is reported to be highly correlated with the In order to understand the behaviour of the band energy
possibility to induce micro-cracks in the material [43]. For difference, DUband, we exploit the following expressions for the first
a completely isotropic material A ¼ 1, while values smaller or and second derivatives of DUband (Eq. (2)) with respect to the
greater than unity measure the degree of elastic anisotropy. As electron number, N, as follows:
observed in Table 1, cubic MgeLi alloys are generally anisotropic. In

general, the observed trends on mechanical properties (G, B, B/G) d dEF
ðDUband Þ ¼ D EF nðEF Þ ¼ DEF (4)
are similar those of Ganeshan et al. [12], who carried out calcula- dN dN
tions on elastic constants of 25 binary Mg compounds other than
MgeLi using the plane wave method. While our predicted

d2 1
mechanical properties for bcc-based structures compare well with ðD Uband Þ ¼ D (5)
dN2 nðEF Þ
where n(EF) is the DOS at the Fermi energy for the electron
10
number N ¼ e/a. Taking the difference of Eq. (4) for two different
fcc-based DO3 structures, we see that the derivative of the energy difference is
8 B2
bcc-based
zero at certain special band fillings for which the two Fermi
6 L12 energies are equal. At these values of N, the band energy differ-
4 ence DUband is extremal. To identify a maximum or a minimum, we
take the difference of the inverses of their DOS at EF, as given on
C' (GPa)

2 DO3
the right-hand side of Eq. (5). If one of the structures has a lower
DOS at this Fermi level, an extremum is present and this structure
0
has a lower energy.
-2 We employed the ab initio TB-LMTO-ASA (tight-binding-linear
L10 L12 muffin-tin orbitals within atomic sphere approximation) method
-4
[45e47] to calculate the DOS for the hcp, fcc and bcc Li structures.
-6 The unit cells were set up in the ideal configuration at their
respective equilibrium internal parameter and using the atomic
-8
0 20 40 60 80 100 volumes determined from fcc Li and Mg. We carried out self-
Li Mg consistent calculations for the fcc cases, transferred the self-
Mg at.%
consistent potential to the bcc and hcp structures, and carried out
Fig. 3. Calculated MgeLi elastic constants (tetragonal shear modulus) C’ ¼ (C11  C12)/2 a single iteration with all potential parameters frozen. The results
as a function of composition for ordered bcc and fcc phases. of the Jones-type analysis using both Li and Mg densities of states
2088 M.J. Phasha et al. / Intermetallics 18 (2010) 2083e2089

a 0.06
b 0.02

0.04
0.01
0.02
ΔUband (eV/atom)

ΔUband (eV/atom)
0.00
0.00
-0.02

-0.04 -0.01

-0.06
-0.02
-0.08
fcc-bcc
-0.10
-0.03 fcc-hcp
-0.12
0.8 0.15

fcc-bcc
0.6 0.10
fcc-hcp
0.4
0.05

ΔEF (eV)
ΔEF(eV)

0.2
0.00
0.0
-0.05
-0.2

-0.10
-0.4

1.0 0.6
bcc
bcc
fcc
0.8 0.5 fcc
n (EF) (states.eV-1atom-1)

hcp
n(EF) (states eV-1atom-1)

hcp
0.6 0.4

0.4 0.3

0.2
0.2

0.1
0.0

0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0

N N

Fig. 4. Analysis of fcc, bcc, and hcp relative structural stabilities within the rigid-band approximation for MgeLi alloys. The difference in band energy DUband with respect to
elemental (a) Li and (b) Mg rigid bands, Fermi energies DEF, and the density of states at the Fermi level EF for bcc, fcc, and hcp lattices, are plotted as a function of band filling, N.

are plotted in Fig. 4(a) and (b), respectively. The difference of the strong deviations from free-electron behaviour above the Fermi
band energy, the Fermi energy difference and DOS are presented as energy. This is a direct consequence of this first-row element
a function of electron number N ¼ e/a. In Fig. 4(b), the fccehcp having no p core electrons.
energy difference curve has a maximum around N ¼ 1.0 where the
hcp DOS is lowest, a minimum around N ¼ 1.6 where the fcc DOS is 4. Conclusions
lowest, and a maximum around N ¼ 2.15 where the hcp DOS is
lowest, whereas the fccebcc curve has a maximum around Our current DFT results are consistent with other works carried
N ¼ 1.75 where the bcc DOS is lowest. The hcp structure is most out by ab initio techniques to investigate the phase stability and
stable around N ¼ 1.0, where DEF z 0, and the fcc DOS is lowest. mechanical properties of Mg-based binary alloys. Using ab initio
We see that with increasing electron concentration (band filling), technique, the phase stability of cubic MgeLi alloys has been pre-
the structural trend from (Li) hcp / fcc / bcc / hcp (Mg) is dicted from heats of formation and elasticity, both complementing
driven by the van Hove singularities in the density of states, in each other. The observed stability trend (Li) hcp / fcc / bcc / hcp
agreement with previous theoretical predictions [3]. The occupied (Mg) has also been confirmed by the Jones-type analysis-based
part of the DOS for Mg in Fig. 4(b) shows approximate free-elec- density of states due to electron band filling, and the established
tron behaviour. This confirms that Mg is a good nearly-free elec- trends are in excellent agreement with other previous studies that
tron (NFE) metal since its occupied DOS are only a relatively small used either one of the above approaches. On the basis of established
perturbation of the free-electron density of states. Li displays very phase stability, the existence of cubic MgeLi alloys in chosen
 M.J. Phasha et al. / Intermetallics 18 (2010) 2083e2089 2089

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