The tunable magnetostructural transition in

MnNiSi-FeNiGe system
Cite as: Appl. Phys. Lett. 103, 132411 (2013); https://doi.org/10.1063/1.4823510
Submitted: 26 August 2013 • Accepted: 11 September 2013 • Published Online: 26 September 2013

C. L. Zhang, D. H. Wang, Z. D. Han, et al.

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© 2013 AIP Publishing LLC.

 APPLIED PHYSICS LETTERS 103, 132411 (2013)

The tunable magnetostructural transition in MnNiSi-FeNiGe system

C. L. Zhang,1,a) D. H. Wang,2 Z. D. Han,3 B. Qian,3 H. F. Shi,1 C. Zhu,1 J. Chen,1
and T. Z. Wang1
1
School of Science, Jiangnan University, WuXi 214122, China
2
National Laboratory of Solid State Microstructures, Department of Physics, Nanjing University,
Nanjing 210093, China
3
Jiangsu Laboratory of Advanced Functional Materials, Department of Physics,
Changshu Institute of Technology, Changshu 215500, China
(Received 26 August 2013; accepted 11 September 2013; published online 26 September 2013)
The tuning of magnetostructural transition was demonstrated for MnNiSi-FeNiGe system. The MnNiSi
alloy undergoes a structural transition around 1200 K in the paramagnetic region. By chemically
alloying MnNiSi with FeNiGe, the structural transition temperature was remarkably decreased by
nearly 1000 K. Magnetostructural transformation from the paramagnetic hexagonal phase to the
ferromagnetic orthorhombic phases, which can be induced by applying magnetic field, were realized
near room temperature, enabling the MnNiSi-FeNiGe system to become a promising candidate for the
C 2013 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4823510]
magnetoresponsive applications. V

Magnetostructural transformation (MST), a coinciding
magnetic and crystalline structural transition, is receiving
increasing attention from both the magnetism and the material
science community due to the associated magnetoresponsive
properties, such as magnetocaloric effect, magnetoresistance,
and magnetic-field-induced shape memory/strain.1–21 In order
to maximize these magnetic effects in a MST system, a large
magnetization difference between two structural phases is
necessary. Therefore, the MSTs which convert the magnetic
states from the paramagnetic (PM) or antiferromagnetic
(AFM) state to the ferromagnetic (FM) state are desired. In
addition, materials which undergo the MST around room tem-
perature (RT) with low driving field are appreciated from the
application point of view. Accordingly, the tuning of the MST
is very important for acquiring the excellent magnetorespon-
sive properties. Up to now, several effective methods, such as
stoichiometric tuning, foreign-atoms-substituting, stress-relax-
ation-annealing, interstitial-atoms-doping, and isostructural
alloying, have been introduced to manipulate the MST in a
large family of materials.6–21
Recently, the MST in a group of MnTGe-based (T ¼ Ni or
Co) intermetallic compounds have attracted much interests.7–21
The MnTGe alloys crystallize in the Ni2In-type hexagonal
structure (P63/mmc, 194) and transform to the TiNiSi-type
orthorhombic structure (Pnma, 62) on cooling.22–25 From the
crystallographic point of view, the TiNiSi-type structure can be
regarded as an orthorhombic distortion of the Ni2In-type hexag-
onal structure.22 The martensitic-like Ni2In-to-TiNiSi structural
transition often associates with remarkable jumps of lattice con-
stants and unit-cell volume, which is beneficial for the strain-
related applications.7–10 However, obvious magnetization
changes, which play a crucial role in the magnetoresponsive
properties, cannot be observed in stoichiometric MnTGe alloys
during the structural transition because it occurs between the
PM states.22–24 By substituting Cr for Mn and introducing inter-
stitial atoms B, Trung et al. obtained the MST from the PM
a)
Author to whom correspondence should be addressed. Electronic mail:
clzhang1982@gmail.com
Ni2In-type hexagonal phase to the FM orthorhombic phase
(PM-FM-type) in the MnCoGe-based alloys.11,12 In the case of
MnNiGe system, the MSTs from the FM Ni2In-type hexagonal
phases to the AFM orthorhombic phases were observed in the
transition-metal-vacant, the Sn-doped or Al-doped alloys.13–15
Recently, Liu et al. demonstrated the tuning of MST by chemi-
cally alloying MnNiGe with the compounds of FeNiGe,
MnFeGe, and CoNiGe which possess the stable Ni2In-type hex-
agonal structure.9,16 They observed the PM-FM-type MSTs in a
temperature window between the Curie temperature of hexago-
nal phase (TChexa ) and orthorhombic phase (TCorth ).9,16 The obser-
vations of large magnetocaloric effects in these MnTGe-based
systems suggest that materials which undergo the Ni2In-to-
TiNiSi structural transitions are promising candidates for the
magnetoresponsive applications.8–21
Besides the MnTGe alloys, MnNiSi ferromagnet experi-
ences the Ni2In-to-TiNiSi structural transition as well.26
Considering the relatively low cost of raw material in
MnNiSi alloy, it would be attractive if the PM-FM-type
MST can be realized in this system. Compared with the
structural transition temperature (Tt) of MnNiGe (470 K)
and MnCoGe (420 K) alloys, Tt of the MnNiSi alloy is
quite high (1200 K).26 It is a great challenge to decrease Tt
to RT in MnNiSi-based alloys, which has not been reported
up to now. In this work, we chemically alloy MnNiSi with
the stable hexagonal compound of FeNiGe and remarkably
decline Tt of MnNiSi for about 1000 K. A giant change of
cell volume is observed at the structural transition in the
MnNiSi-FeNiGe system. The magnetic-field-induced PM-
FM-type MST with sharp jumps of magnetization were
obtained around RT, which is responsible for the large mag-
netocaloric effects in these alloys.
Polycrystalline samples of (MnNiSi)1x(FeNiGe)x
(x ¼ 0.36, 0.38, 0.40, 0.42, 0.44, 0.46, 0.48, 0.50, and 0.52)
were prepared by arc-melting pure metals with the nominal
proportions in high-purity argon atmosphere. The as cast
ingots were sealed in vacuumed quartz tubes and annealed at
1073 K for four days followed by quenched in cool water.
The crystal structures of the specimens were identified by

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V
132411-2 Zhang et al. Appl. Phys. Lett. 103, 132411 (2013)

X-ray diffraction (XRD) analysis with Cu-Ka radiation. The

temperature-dependent magnetizations (M-T) and the low-
field isothermal magnetization (M-H) curves were measured
using a vibrating sample magnetometer (LakeShore, VSM
7407). The high-field magnetic measurements were carried
out in a superconducting quantum interference device
(Quantum design, MPMS-XL-7).
Figure 1 shows the XRD patterns measured at RT for
the (MnNiSi)1–x(FeNiGe)x system. As mentioned above, the
MnNiSi alloy exhibits the orthorhombic structure at RT,
while the FeNiGe alloy possesses the table hexagonal struc-
ture. The orthorhombic phase dominates for samples with
x ¼ 0.36 and 0.38 at RT, suggesting that their Tt are higher
than RT. The orthorhombic and hexagonal phases coexist in
samples with x ¼ 0.40, 0.42, and 0.44. Samples with higher
content of FeNiGe exhibit high-purity of hexagonal phase at
RT, indicating that their Tt are lower than RT. It is worth not-
ing that the isostructural alloying method has been used to
tune the MST in the MnNiGe-MnFeGe, MnNiGe-FeNiGe, FIG. 2. Temperature-dependent XRD (a), lattice constants (b), and cell
and MnNiGe-CoNiGe systems.9,16 There is only one differ- volumes (c) from 300 to 600 K for (NiMnSi)0.62(FeNiGe)0.38.
ent element between the two isostructural compounds in
these systems. However, in the present case, there are two point of view, the axes of the orthorhombic and hexagonal pffiffiffi
different elements between MnNiSi and FeNiGe. The structures are related as aortho ¼ chex, bortho ¼ ahex, cortho ¼ 3
co-substitution of Fe for Mn and Ge for Si has enhanced the ahex.22 As shown in Fig. 2(b), aortho (or chex) and bortho
relative stability of hexagonal phase and decreased Tt largely (or ahex) jumps abruptly during the structural transition. A
from about 1200 K to lower than RT. Apparently, the iso- giant decrease of 4.3% in unit-cell volume is found at the tran-
structural alloying method works well in tuning MST of the sition on heating, which is larger than the MnNiGe (2.68%)
MnNiSi-FeNiGe system. and MnCoGe (4.0%) alloys,9,10 indicating a remarkable
In order to further investigate the structural transition in the atomic displacement during the structural reconstruction.
MnNiSi-FeNiGe system, we performed the XRD analysis at Since the magnetic interactions in the Mn-based com-
several different temperatures which were arranged in a heating pounds are sensitive to the Mn-Mn distances,27 the consider-
sequence. As shown in Fig. 2(a), the (MnNiSi)0.62(FeNiGe)0.38 able changes of the lattice parameters and atomic surrounding
system exhibits the orthorhombic structure below 390 K. At could transform the magnetic states, resulting in the changes
420 K, the hexagonal phase appears, and the amount of of magnetization during the structural transition. Figure 3
orthorhombic phase decreases. High-purity of hexagonal shows the M-T curves measured under a field of 2 kOe for
phase is observed at higher temperatures, indicating that the samples with x ¼ 0.44, 0.46, and 0.48. Abrupt jumps of mag-
structural transition is almost complete. Figures 2(b) and 2(c) netization were observed during the MST between the low-
show the temperature-dependent of lattice parameters for temperature FM phase and the high-temperature PM phase.
(NiMnSi)0.62(FeNiGe)0.38 system. From the crystallographic The values of Tt are 292, 238, and 194 K for samples with
x ¼ 0.44, 0.46, and 0.48, respectively. Obviously, Tt decrease
with the increase of FeNiGe-content. Here, Tt is defined as the

FIG. 1. Room temperature XRD for (MnNiSi)1x(FeNiGe)x (x ¼ 0.36, 0.38, FIG. 3. M-T curves measured on heating and cooling under the field of
0.40, 0.42, 0.44, 0.46, 0.48, 0.50, and 0.52) system. 2 kOe for (MnNiSi)1x(FeNiGe)x (x ¼ 0.44, 0.46, and 0.48).
132411-3 Zhang et al.
temperature where the jdM=dTj is the maximum on heating.
Thermal hystereses of about 12 K are observed between heat-
ing and cooling processes, indicating the first-order nature of
the MST.
As we know, the realization of PM-FM-type MST
would meet the condition that Tt can be moved into the tem-
perature window between TChexa and TCorth .9,10,16 For the
MnTGe-based alloys, TCorth and TChexa are higher and lower
than RT, respectively. So the PM-FM-type MST can be
tuned around RT in the relatively wide temperature win-
dow.9,10,16 However, the temperature window which is given
by TChexa of FeNiGe (770 K) and TCorth of MnNiSi (662 K) is
much higher than RT.25 The obtaining of PM-FM-type MST
around RT implies that this temperature window is actually
expanded towards low-temperature in the MnNiSi-FeNiGe
system. In other words, not only Tt but also TChexa were
largely decreased by isostructural alloying. This result is
very different with those in the MnTGe-based alloys, which
exhibit a relative stable temperature window with the chang-
ing composition.9,10,16 Because the PM hexagonal phase
undergoes the MST before it orders ferromagnetically on
cooling, we cannot determine TChexa from Fig. 3. Instead, we
estimated the PM Curie temperatures of hexagonal phases
(hhexa
p ) from the temperature-dependent of reciprocal mag-
netic susceptibility. They are 187, 192, and 174 K for sam-
ples with x ¼ 0.44, 0.46, and 0.48, respectively, which are
far below RT. This result suggests that the FM interactions
in the hexagonal phase are weakened remarkably with the
doping of Mn and Si in the FeNiGe alloy. Because TChexa
(or hhexa
p ) is shifted below RT and TC
orth
remains higher than
RT, the temperature window which covers RT is established
for MnNiSi-FeNiGe system. By tuning the content ratio of
MnNiSi to FeNiGe appropriately, Tt can be adjusted in the
range from TChexa to TCorth , showing the PM-FM-type MSTs
with sharp jumps of magnetization.
Figure 4 shows the isothermal magnetization (M-H)
curves for (NiMnSi)0.56(FeNiGe)0.44 system around Tt under
a magnetic field up to 50 kOe. The M-H curves exhibit FM
and PM features at 284 and 268 K for the orthorhombic and
hexagonal phases, respectively. The magnetization differ-
ence between the orthorhombic and hexagonal phase reaches
up to 62 emu/g at 50 kOe. The metamagnetic behaviors were
FIG. 4. Isothermal M-H curves for (NiMnSi)0.66(FeNiGe)0.44 around Tt.
Appl. Phys. Lett. 103, 132411 (2013)
observed in the isothermal M-H curves between 278 and
272 K, corresponding to the stabilizing of the FM orthorhom-
bic phase by applying magnetic field. As mentioned above,
the MnNiSi-FeNiGe system experiences significant changes
of lattice parameters and cell volume during the structural
transition. The observation of the magnetic-field-induced
MST suggests the potential strain-based applications of the
MnNiSi-FeNiGe system under an applied field.
Magnetic refrigeration, which is based on the magneto-
caloric effect of magnetic materials, is considered to be a
promising refrigeration technology for its high energy-
efficiency and environmental friendliness. The magnetocaloric
effect manifests as an isothermal magnetic entropy change
(DSM) or an adiabatic temperature change in a varying mag-
netic field. Large values of DSM are usually observed in mate-
rials with sharp MST.1–3,9 Figure 5 shows the temperature-
dependence of DSM for the field change of 10 kOe, which are
estimated from the isothermal
ÐH M-H curves using the Maxwell
relation: DSM ðT; HÞ ¼ 0 ð@M=@TÞH dH. Negative values of
DSM were obtained at the PM-FM-type MSTs. Samples with
x ¼ 0.44, 0.46, and 0.48 exhibit the peak values of 11.5,
10.8, and 8.4 J/kg K, respectively, for the low-field change
of 10 kOe. These values are comparable with those of many
well-known magnetocaloric materials with MST.1–3,9 The
large values of DSM in MnNiSi-FeNiGe alloys are attributed
to the abrupt jumps of magnetization from the PM state with
highly disordered spins to the FM state with highly ordered
spins.16 Here, it should be stated that although the Maxwell
relation has been widely used for evaluating DSM even for the
systems with first-order phase transition (FOT), it usually
overestimates DSM due to the discontinuous change of mag-
netization in the mixed-phase regime which associates with
the irreversibility of the FOT.28–30 Alternatively, DSM can be
determined from the integrated specific heat as a function of
temperature, i.e., from the entropy curves, under different
magnetic field. Further studies on the magnetocaloric effect
using the specific heat method are needed for the MnNiSi-
FeNiGe isostructural system.
In conclusion, we have demonstrated the tuning of MST
in the MnNiSi-FeNiGe isostructural system. The MnNiSi
alloy undergoes a structural transition between the orthorhom-
bic and hexagonal phases in the PM region, while the FeNiGe
alloy exhibits stable hexagonal structure. Both MnNiSi and
FeNiGe alloys are ferromagnet with quite high Curie tempera-
tures. By chemically alloying MnNiSi with FeNiGe, Tt can be
adjusted in a wide range of nearly 1000 K. The MSTs from
FIG. 5. Temperature-dependent DSM for (MnNiSi)1x(FeNiGe)x (x ¼ 0.44,
0.46, and 0.48) under the field change of 10 kOe.
132411-4 Zhang et al.
12
PM hexagonal to FM orthorhombic phases, which can be
induced by applying magnetic field, were realized around RT
13
in the temperature window between TChexa and TCorth . Abrupt
jumps of magnetization around MST lead to large magneto- 14
caloric effects in MnNiSi-FeNiGe alloys, suggesting that this
15
system can work as promising magnetoresponsive materials.
16
This work was supported by the National Natural
Science Foundation of China (51101074, 51001019, and
17
21203077).
18
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