CHIN. PHYS. LETT. Vol. 26, No.

11 (2009) 117102

Electronic Structure and Elastic Properties of Ti3 AlC from First-Principles

Calculations *
DU Yu-Lei(杜宇雷)**
Department of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094

(Received 11 May 2009)

We perform a first-principles study on the electronic structure and elastic properties of Ti3 AlC with an antiper-
ovskite structure. The absence of band gap at the Fermi level and the finite value of the density of states at the
Fermi energy reveal the metallic behavior of this compound. The elastic constants of Ti3 AlC are derived yielding
𝑐11 = 356 GPa, 𝑐12 = 55 GPa, 𝑐44 = 157 GPa. The bulk modulus 𝐵, shear modulus 𝐺 and Young’s modulus 𝐸
are determined to be 156, 151 and 342 GPa, respectively. These properties are compared with those of Ti3 AlC2
and Ti2 AlC with a layered structure in the Ti-Al-C system and Fe3 AlC with the same antiperovskite structure.

PACS: 71. 20. Ps, 62. 20. D−, 81. 05. Je

It is known that there are three ternary carbides
in the Ti-Al-C system, i.e. Ti3 AlC2 , Ti2 AlC and
Ti3 AlC.[1] Among them, both Ti3 AlC2 and Ti2 AlC
crystallize in the hexagonal layered structure and be-
long to the so-called MAX phases (M𝑛+1 AX𝑛 , where
𝑛 = 1, 2, 3, 𝑀 is an early transition metal, 𝐴 is an
A-group element, and 𝑋 is either 𝐶 or 𝑁 ),[2] while
Ti3 AlC has a perovskite-like cubic structure.[3] Re-
cently, single-phase Ti3 AlC2 and Ti2 AlC have been
successfully prepared by hot pressing sintering[4,5] and
pulse discharge sintering.[6,7] Their unique proper-
ties, such as high thermal and electrical conductiv-
ity, high strength and modulus, damage tolerance
and thermal shock resistance, and more importantly
being machinable, were revealed. Like other MAX
phases, Ti3 AlC2 and Ti2 AlC are promising materi-
als for high temperature applications. Ti3 AlC were
usually observed as precipitates in carbon containing
C have been chosen to be 1.9, 2.5 and 1.7 a.u., respec-
tively. The convergence parameter 𝑅𝑚𝑡 𝐾max , which
controls the size of the basis set for the wave function,
was set to 7.0, where 𝑅𝑚𝑡 is the minimum spheres
radii and 𝐾max is the maximal value of the reciprocal
lattice vector used in the plane wave expansion. In-
tegrations in the reciprocal space were performed by
using the tetrahedron method with a 𝑘-mesh of 56 𝑘-
points in the irreducible wedge of Brillouin zone (BZ).
The total energy is converged to within 0.1 m 𝑅𝑦/unit
cell during the self-consistency cycle.
C
Ti

Ti-Al intermetallics.[8,9] The improvement of the high

temperature performance of the intermetallic matrix
was attributed to the precipitation strengthening ef-
fect of Ti3 AlC. However, up to now it is still difficult
to prepare single-phase Ti3 AlC.[10] As a result, the
physical and mechanical properties of Ti3 AlC are not
very clear yet. In this Letter, in order to clarify the
nature of Ti3 AlC, we perform first-principles calcula-
tions to investigate the electronic structure and elastic
properties of this compound.
The first-principles calculations performed in the
present work are based on the density functional
theory (DFT). The total energies are calculated us-
ing the full-potential linearized augmented plane-wave
method (FLAPW) plus the local orbital as imple-
mented in WIEN2K code.[11] The effects of the ap-
proximation to the exchange-correlation energy are
treated by the generalized gradient approximation
(GGA). The muffin-tin sphere radii 𝑅𝑖 of Ti, Al and
Al
Fig. 1. Crystal structure of Ti3 AlC.
Figure 1 illustrates the crystal structure of Ti3 AlC.
The perovskite-like structure of Ti3 AlC is called the
antiperovskite structure because the metal element Ti
is located at the corner of the octahedron cage and
the non-metal element 𝐶 is located at the bulk cen-
ter position in Ti3 AlC in contrast to the ordinary per-
ovskite structure. The experimental lattice constant 𝑎
of Ti3 AlC is 4.144 Å.[12] In our calculations, the value
of 𝑎 was firstly optimized to ensure that the calcula-
tions were based on the equilibrium crystal structure.
Fitting of the Murnaghan equation of states to the
total energies versus lattice volume yields the equilib-
rium lattice constant of 𝑎𝑒𝑞 = 4.181 Å. Compared with

* Supportedby the Qinglan Project of Jiangsu Province.

** Towhom correspondence should be addressed. Email: yldu njust@mail.njust.edu.cn
○
c 2009 Chinese Physical Society and IOP Publishing Ltd

117102-1
 CHIN. PHYS. LETT. Vol. 26, No. 11 (2009) 117102
the experimental value, we find a 0.9% overestimation.
Fig. 2. The calculated electronic band structure of
Ti3 AlC.
Fig. 3. (a) Total and partial densities of states for
Ti3 AlC; (b) total densities of states for Ti3 AlC2 and
Ti2 AlC.
Figure 2 exhibits the calculated energy band struc-
ture of Ti3 AlC at equilibrium lattice parameters along
selected high-symmetry directions within the first
Brillouin zone. It is seen that valence and conduc-
tion bands overlap considerably at the Fermi level
and as a result there is no energy gap at 𝐸𝐹 . This
suggests that Ti3 AlC would exhibit metallic conduc-
tivity just like Ti3 AlC2 and Ti2 AlC. The total and
partial density of states (DOS) of Ti3 AlC are plot-
117102-2
ted in Fig. 3(a). The lowest-lying states from about
−12 eV to −9 eV are from C 2𝑠 states. The states
from about −7 eV to −5 eV and from −5 eV to −3 eV
are mainly from Al 3𝑠 and C 2𝑝 states respectively. A
strong hybridization between Ti 3𝑑 and Al 3𝑝 states
was observed at about −1.8 eV. The hybridization be-
tween Ti 3𝑑 and C 2𝑝 was observed in the range of
−5 to −2 eV. The states in the vicinity of the Fermi
level are mainly occupied by Ti 3𝑑 states. Obviously,
Ti 3𝑑 states give rise to the electrical conductivity in
Ti3 AlC. The DOS at the Fermi level for Ti3 AlC is
2.95 states/(eV·unit cell). As shown in Fig. 3(b), the
DOS for Ti3 AlC2 and Ti2 AlC also remains finite at
the Fermi level. This phenomenon reveals the metallic
behavior of these three ternary carbides in the Ti-Al-
C system. Above the Fermi level, the anti-bonding Ti
3𝑑 states dominate with less contribution from 3𝑠 and
3𝑝 states of Al atoms and 2𝑝 states of C atoms.
Elastic properties are of fundamental interest in
materials science. Nowadays first-principles calcula-
tions have been successfully used to study the elastic
properties of solids.[13−15] In the present work, the
elastic constants are calculated by the strain-energy
method. An appropriate set of strains is applied to
the undeformed unit cell lattice with the relaxed struc-
ture. Then, the elastic constants are determined from
the resulting change in total energy on the deforma-
tion. For the cubic crystals, there are three indepen-
dent elastic constants, which are usually referred to as
𝑐11 , 𝑐12 and 𝑐44 . Three distortions involving bulk mod-
ulus 𝐵, 𝑐11 −𝑐12 and 𝑐44 are employed to determine all
the elastic constants. The detailed procedures can be
found in the literature.[16−18] Table 1 lists the values
of the calculated elastic constants. The bulk modulus
𝐵, the shear modulus 𝐺, and Young’s modulus 𝐸 are
calculated according to the following relations:
𝐵 = (𝑐11 + 2𝑐12 )/3, (1)
𝐺 = (𝑐11 − 𝑐12 )/2, (2)
𝐸 = 9𝐵/(1 + 3𝐵/𝐺), (3)
where 𝐵, 𝐺 and 𝐸 of Ti3 AlC are calculated to be
156, 151 and 342 GPa, respectively. As reported pre-
viously, the calculated 𝐵, 𝐺 and 𝐸 was 137, 117 and
273 GPa for Ti2 AlC and 161, 132 and 310 GPa for
Ti3 AlC2 .[19] It is seen that Ti3 AlC with antiperovskite
structure exhibits a higher shear and Young’s modu-
lus than Ti3 AlC2 and Ti2 AlC with layered structure.
The decrease in elastic modulus of these two MAX
phases, i.e. Ti3 AlC2 and Ti2 AlC, can be attributed to
their special layered crystal structure. As is known,
the relatively weak 𝑀 − 𝐴 bonds are introduced by
the insertion of 𝐴-element layers into the MX skele-
ton in MAX phases,[2] which results in the reduction
of elastic modulus. The calculated elastic constants
𝐵, 𝐺 and 𝐸 of another antiperovskite ternary carbide
 CHIN. PHYS. LETT. Vol. 26, No. 11 (2009) 117102
Fe3 AlC are also listed in Table 1.[18] It can be seen
that 𝐵, 𝐺 and 𝐸 of Fe3 AlC are much higher than
those of Ti3 AlC, which can be understood in terms of
the fact that the unit cell volume of Fe3 AlC is about
29% smaller than that of Ti3 AlC. As is known, the de-
crease of unit cell volume means that the atom pack-
ing densities increase, which will lead to the enhance-
ment in the bulk modulus,[20] Young’s modulus and
shear modulus. Similar results have been observed
in antiperovskite-type materials RRh3 B and RRh3 C
(R=Sc, Y and La).[16] From the point of view of elec-
tronic structure, the high elastic modulus of Ti3 AlC
and Fe3 AlC can be attributed to the stronger cova-
lent type bonding between Ti-C and Fe-C atoms. As
reported previously, the C 𝑝 and Fe 𝑑 states strongly
hybridize around −7 to −4 eV.[18] Obviously, the Fe-
C bonds are stronger than the Ti-C bonds, since the
former appear at a lower energy. As a result, 𝐵, 𝐺
and 𝐸 of Fe3 AlC are higher than those of Ti3 AlC.
Table 1. Calculated elastic constants (𝑐𝑖𝑗 in GPa), bulk modu-
lus (𝐵 in GPa), shear modulus (𝐺 in GPa), and Young’s modu-
lus (𝐸 in GPa) for Ti3 AlC. For comparison, the corresponding
values for Fe3 AlC, Ti3 AlC2 and Ti2 AlC are also listed.
Compound 𝑐11 𝑐12 𝑐44 𝐵 𝐺 𝐸 [12] Jeitschko W, Nowotny H and Benesovky F 1964 Monotsch
Ti3 AlC 356 55 157 156 151 342
Fe3 AlC[18] 549 53 140 218 248 539
Ti3 AlC2 [19] 161 132 310
Ti2 AlC[19] 137 117 273
In conclusion, we have studied the electronic
structure and elastic properties of Ti3 AlC by first-
principles calculations. The electronic structure of
Ti3 AlC shows a metallic-like character like Ti3 AlC2
and Ti2 AlC. The strong hybridization between Ti 3𝑑
and Al 3𝑝 states and between Ti 3𝑑 and C 2𝑝 states
stabilizes the structure of Ti3 AlC. The elastic con-
stants, bulk modulus, shear modulus and Young’s
117102-3
modulus of Ti3 AlC are calculated. The elastic prop-
erties of Ti3 AlC are compared with two other ternary
carbides Ti3 AlC2 and Ti2 AlC in the Ti-Al-C system,
and another antiperovksite ternary carbide Fe3 AlC.
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