Materials Science-Poland, 32(3), 2014, pp.

396-401
[Link]
DOI: 10.2478/s13536-014-0219-8

Electronic structure and possible martensitic transformation

in Ni2FeIn alloy
Y UNGAO G U 1 , FANG X UE 1 , G UOQING Z HAO 1 , G UODONG L IU 2 , YANG L IU 3 , S ONGTAO L I 3∗

1 Department of Physics and Electrical Engineering, Handan College,

Handan, 056005, [Link]
2 School of Material Science and Engineering, Hebei University of Technology,
Tianjin 300130, P.R. China
3 School of Mathematics and Physics, North China Electric Power University,
Baoding 071003, P.R. China

The electronic structure and magnetic properties of Heusler alloys (Ni2 FeIn) have been studied by first principle calcula-
tions. The possible tetragonal martensitic transformation has been predicted and the structure optimization was made on cubic
austenitic Ni2 FeIn in Cu2 MnAl type. The equilibrium lattice constant of austenitic Ni2 FeIn is 6.03 Å. In tetragonal phase,
the global energy minimum occurs at c/a = 1.29. The corresponding equilibrium lattice constants for martensite Ni2 FeIn are
a = b = 5.5393 Å and c = 7.1457 Å, respectively. In the austenitic phase, EF is located at the peak in the minority DOS for
c/a = 0.96 to 1.20, but in the martensitic phase, EF moves to the bottom of the valley in the minority DOS, reducing the value
of N(EF ) effectively. Both austenitic and martensitic phases are ferromagnetic and the Ni and Fe partial moments contribute
mainly to the total moments. Therefore, the martensitic transformation behavior in Ni2 FeIn is predicted.
Keywords: electrical structure; martensitic transformations; first principle calculations
© Wroclaw University of Technology.

1. Introduction have been predicted to be FSMAs by experimental

and theoretical studies. Moreover, Ni–Co–Mn–In
In 1996 K. Ullakko et al. [1] reported that the Heusler alloys exhibiting shape memory effect
large magnetic-field-induced strains were found in have been reported by R. Kainuma et al. [10].
Ni2 MnGa alloy. Since then, Ni-based Heusler al- Stresses of over 100 MPa are generated in the ma-
loys [2–4] have received considerable attention for terials under the application of a magnetic field
their potential application as ferromagnetic shape- of 70 kOe. Such stress levels are approximately
memory alloys (FSMAs) in many technical fields, 50 times larger than that generated in a previous
such as magnetic actuators or magnetocaloric ma- ferromagnetic shape-memory alloy [11]. In recent
terials. FSMAs are magnetic materials that exhibit years a large amount of Heusler alloys [12–14]
a martensitic transformation together with large have been predicted to be FSMAs.
magnetic-field-induced strains. The alloys have not
only large strain but also high response frequency In this paper we have studied the electronic
because the shape memory effect can be controlled structure and magnetic properties of Heusler al-
by applying magnetic field – in addition to conven- loys Ni2 FeIn by first principle calculations. The
tional controls – by temperature and stress. possible tetragonal martensitic transformation has
been predicted. We observed that Ni2 FeIn alloy has
Until now, the most common FSMAs among a ferromagnetic character in both austenitic and
the Heusler alloys are Ni–Mn based alloys. The martensitic phases, and – to a great extent – the Ni
Ni–Mn–Z (Z = Ga, In, Fe, Al, Sn) [5–9] alloys and Fe partial moments contribute to the total mo-
ments. Theoretical calculations show that Ni2 FeIn
∗ E-mail: songtaoli2001@[Link] is probably a ferromagnetic shape-memory alloy.

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 Electronic structure and possible martensitic transformation in Ni2 FeIn alloy 397

2. Computational methods 1/4 1/4) sites, and the Y atom enters the C (1/2
1/2 1/2) site, whereas Z atom occupies the D (3/4
The electronic structure of Ni2 FeIn alloy was
3/4 3/4) site in Wyckoff coordinates. In contrast, in
calculated by means of CASTEP (Cambridge Se-
Cu2 MnAl type structure the X atoms occupy the A
quential Total Energy Package) code based on
and the C sites, and Y atom enters the B site, leav-
pseudopotential method with a plane-wave basis
ing the D site to Z atom. As an example, Fig. 1
set [15, 16]. The interactions between the atomic
presents the general structure of the Heusler alloys.
core and the valence electrons were described by
According to the previous studies, for 3d transition
the ultrasoft pseudopotential [17]. The electronic
metal elements, the site preference is determined
exchange-correlation energy was treated with the
by the number of valence electrons of transition
generalized-gradient-approximation (GGA) [18].
metal elements; the elements with less electrons
For all cases, a plane-wave basis set cut-off of
prefer to occupy the B site, while others prefer to
500 eV was used. A mesh of 15 × 15 × 9 k-points
enter the (A, C) sites [19]. So, in Ni2 FeIn, the two
was employed for Brillouin zone integrations.
Ni atoms occupy the (A, C) sites and Mn enters the
These parameters ensured good convergences for
B site, forming the Cu2 MnAl type structure. The
total energy. The convergence tolerance for the cal-
same type of structure is also observed in Ni2 FeGa
culations was selected as a difference of the total
alloy [20].
energy within 1 × 10−6 eV/atom.

3. Results and discussion

3.1. Electronic structure in austenitic and
martensitic phase

Fig. 2. The calculated total energies as a function of

the lattice parameters for austenitic Ni2 FeIn in
Cu2 MnAl type structure.

Fig. 1. The austenite and martensite structures of First, we investigated the electronic structure
Ni2 FeIn alloy. of austenitic Ni2 FeIn and made structure optimiza-
tion on cubic austenitic Ni2 FeIn of Cu2 MnAl type
Heusler alloys crystallize in a highly-ordered by using first principle calculations. Both para-
cubic structure and have a stoichiometric compo- magnetic and ferromagnetic coupling between Ni
sition of X2 YZ, where X and Y atoms are transi- atoms at A and C sites have been considered in cal-
tion metal elements, and Z atom is a main group culations. Fig. 2 shows the calculated total energies
element, which is arranged in four interpenetrat- as a function of the lattice parameters for austenitic
ing face-centered-cubic (fcc) lattices. There are two Ni2 FeIn in Cu2 MnAl type structure. The equilib-
possible structures in austenitic phase: Hg2 CuTi rium lattice constant of austenitic Ni2 FeIn was de-
type and Cu2 MnAl type. In Hg2 CuTi type struc- rived by minimizing the total energy. The lattice
ture, the X atoms occupy the A (0 0 0) and B (1/4 constant is 6.03 Å, which is much larger than the

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398 Y UNGAO G U et al.

5.74 Å in Ni2 FeGa alloy [20] and a bit smaller than a = b = 5.5393 Å and c = 7.1457 Å, as listed in
the 6.07 Å in Ni2 MnIn alloy [21]. It follows from Table 1.
the fact that the radius of the main group element,
In atom, is much larger than that of Ga atom and
the radius of transition metal element, Fe atom, is a
bit smaller than that of Mn atom.

Fig. 4. Calculated spin-projected total and partial DOS

of Ni2 FeIn in austenitic and martensitic phases.

Fig. 3. The calculated total energy as a function of the 3.2. DOS and PDOS in austenitic and
c/a ratio for Ni2 FeIn alloy in the martensitic martensitic phases
phase.
The calculated spin-projected total and partial
density of states (DOS) for Ni2 FeIn in austenitic
The structural phase transition is nearly volume and martensitic phases are presented in Fig. 4. For
conserving [22], which is a characteristic feature both austenitic and martensitic phases it is found
of a shape memory alloy. In the optimization of that the majority spin DOS is mainly below EF , and
the martensitic phase, for convenience sake, it has the bonding peak at −3.5 eV comes from the cova-
been assumed that there is no volume difference lent hybridization between d electrons of Ni and
between the austenitic and martensitic phases. In Fe atoms. The anti-bonding peak in the minority
Fig. 3 the calculated total energy as a function of spin state around 0.5 eV is mainly contributed by
the c/a ratio for Ni2 FeIn alloy in the martensitic the Fe atom. It has been reported that the covalent
phase is shown, and the zero of total energy Etot is hybridization between the lower-energy d states of
the energy in austenitic phase. It is clear that there the higher-valence transition metal atom, like Ni,
are two local energy minima in the Etot = f(c/a) and the higher-energy d states of the lower-valence
curve: a shallow one at c/a = 1.00 (austenite), and transition metal atom, like Fe, can be strong and
a deep one at c/a = 1.29. Around c/a = 1.00 the lead to the formation of bonding and antibonding
energy of Ni2 FeIn changes a little, which means a bands [23].
very small tetragonal distortion. The energy from For austenite and martensite, the total DOS
c/a = 0.94 to 1.05 is nearly constant, and for from −3 eV to 0 eV, in both majority spin and mi-
c/a = 1.00 there is a metastable minimum. At nority spin states, mainly consists of Ni atoms at A
c/a = 1.29 there is the lowest energy in the and C sites. The covalent hybridization between d
whole curve indicating the most stable structure. electrons of Ni and Fe atoms forms the DOS around
So, in the possible martensitic transformation, the −3.5 eV in the majority spin state and 0.5 eV in
c-axis lattice will expand and a, b-axes in the the minority spin state. Below −5 eV the contri-
lattice will contract. The corresponding equilib- bution is mainly from In atom at D site. The differ-
rium lattice constants for martensite Ni2 FeIn are ence of total DOS between austenite and martensite

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 Electronic structure and possible martensitic transformation in Ni2 FeIn alloy 399

Table 1. The calculated lattice parameters a, b, c and magnetic moments for austenitic and martensitic Ni2 FeIn.

Ni2 FeIn a(Å) b(Å) c(Å) c/a Mtot (µB ) MNi (µB ) MFe (µB ) MIn (µB )
Austenite 6.03 6.03 6.03 1.00 3.52 0.32 2.86 0
Martensite 5.5393 5.5393 7.1457 1.29 3.56 0.40 2.76 −0.02

is small but tetragonal distortion impacts the DOS peak at EF in the austenitic phase is divided into
around EF in minority spin state. two peaks – below and above EF , with tetrago-
nal distortion – resulting in a dropping of the to-
tal energy and causing the martensitic transforma-
tion [24]. This indicates that the tetragonal phase
is more stable and that a martensitic transformation
may occur at lowering temperature.

3.3. Magnetic properties

The total DOSs in majority spin and minority
spin states are asymmetric in Fig. 4. It means that
the Ni2 FeIn alloy is magnetic. In the PDOS of Fe
at B site, the spin splitting of Fe atom is large,
resulting in a large local moment. The PDOS of
Ni atom has a better symmetry and the spin mo-
ment is smaller than that of Fe atom. For austenitic
phase and martensitic phase, In atom is nearly para-
magnetic and its moment is 0 and −0.02 µB , re-
Fig. 5. The calculated total DOS of Ni2 FeIn for spectively. The calculated magnetic moments for
c/a = 0.90 to 1.40. Ni2 FeIn of austenitic and martensitic phases are
listed in Table 1. Ni2 FeIn is a ferromagnetic ma-
In order to investigate the influence of tetrag- terial, which is mainly determined by the parallel
onal distortion, the total DOS of Ni2 FeIn for aligned Ni and Fe atom spin moments.
c/a = 0.90 to 1.40 have been calculated and shown The variation of the martensitic moment in
in Fig. 5. The insets in Fig. 5 show the enlarged Ni2 FeIn alloy is related to the partial moments of
area around the EF . The shape of the total DOS Ni(A, C) and Fe(B). In Fig. 6 the total and partial
remains substantially unchanged with c/a rising spin moments of Ni2 FeIn as a function of c/a ratio
from 0.90 to 1.40, and the majority spin DOS is are presented. The total moment around c/a = 1.00
mainly below EF . The bonding peak and the anti- changes a little corresponding to the metastable
bonding peak are located at −3.5 eV and 0.5 eV, structure of austenite. For the part of c/a > 1 the
respectively. It should be noted that EF is lo- total moment increases and drops with the increase
cated at the peak in the minority spin DOS from in c/a ratio. It is strongly related to the increas-
c/a = 0.96 to 1.20 because the energy around ing trend of Ni(A, C) atom spin moment and the
c/a = 1.00 changes a little. However, in the decreasing trend of Fe(B) atom spin moment. The
martensitic phase, EF moves to the bottom of the possible martensitic transformation appears at the
valley in the minority DOS reducing the value of point of c/a = 1.29. The total moment of marten-
N(EF ) effectively. The total DOS decreases with site at c/a = 1.29 is a little larger than that of the
c/a increasing due to the tetragonal distortion. It is austenite at c/a = 1.29. In Fig. 6, with c/a in-
known as the Jahn-Teller effect, in which the DOS creasing, the Ni2 FeIn alloy becomes ferromagnetic

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400 Y UNGAO G U et al.

Fig. 6. Total and partial spin moments as a function of the c/a ratio for Ni2 FeIn.

because the spin moments of Ni and Fe atoms bottom of the valley in the minority DOS reduc-
keep parallel aligned in the tetragonal distortional ing the value of N(EF ) effectively. This indicates
process. that the tetragonal phase is more stable and that a
martensitic transformation may occur at lowering
4. Conclusions temperature. The spin moments of Ni and Fe atoms
keep parallel aligned in the tetragonal distortional
The electronic structure and magnetic proper- process, so they contribute greatly to the total mo-
ties of Heusler alloys Ni2 FeIn have been studied ments. Both austenitic and martensitic phases are
theoretically. We investigated the electronic struc- ferromagnetic.
ture of austenitic Ni2 FeIn and made structure opti-
mization on cubic austenitic Ni2 FeIn of Cu2 MnAl Acknowledgements
type by using first principle calculations. The equi- This work has been supported by the National Science
librium lattice constant of austenitic Ni2 FeIn is Foundation of China (11004055, 50901028), the Fundamen-
6.03 Å. In the tetragonal phase, the global en- tal Research Funds for the Central Universities (11ML63,
ergy reaches minimum at the point of c/a = 1.29. 12MS142, 13ZD23), the Beijing-funded Joint Development
Program of the Central Universities in Beijing and the
The corresponding equilibrium lattice constants for Program for New Century Excellent Talents in University
martensite Ni2 FeIn are a = b = 5.5393 Å and c = (NCET-12-0844).
7.1457 Å, respectively. However, the energy differ-
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 Electronic structure and possible martensitic transformation in Ni2 FeIn alloy 401

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