Mssbauer study on martensite phase in Ni 50 Mn 36.5 Fe 0.

5 57 Sn 13 metamagnetic
shape memory alloy
R. Y. Umetsu, R. Kainuma, Y. Amako, Y. Taniguchi, T. Kanomata, K. Fukushima, A. Fujita, K. Oikawa, and
K. Ishida
Citation: Applied Physics Letters 93, 042509 (2008); doi: 10.1063/1.2960551
View online: http://dx.doi.org/10.1063/1.2960551
View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/93/4?ver=pdfcov
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APPLIED PHYSICS LETTERS 93, 042509 2008

Mssbauer study on martensite phase in Ni50Mn36.557Fe0.5Sn13 metamagnetic

shape memory alloy
R. Y. Umetsu,1,a R. Kainuma,1 Y. Amako,2 Y. Taniguchi,2 T. Kanomata,3 K. Fukushima,3
A. Fujita,4 K. Oikawa,4 and K. Ishida4
1

Institute for Multidisciplinary Research for Advanced Materials, Tohoku University,

Sendai 980-8577, Japan
2
Faculty of Science, Shinshu University, Matsumoto 390-8621, Japan
3
Faculty of Engineering, Tohoku Gakuin University, Tagajo 985-8537, Japan
4
Department of Materials Science, Graduate School of Engineering, Tohoku University,
Sendai 980-8579, Japan

Received 30 May 2008; accepted 30 June 2008; published online 29 July 2008
Magnetic and differential scanning calorimetric measurements and Mssbauer examination were
carried out to clarify the magnetic features of Ni50Mn36.557Fe0.5Sn13. The magnetic field cooling
effects were observed in the thermomagnetization curves below 235 K and the Curie temperature of
the parent phase was near the martensitic transformation temperature. The Mssbauer spectra taken
from the parent+ martensite two-phase state at 312 K and from the martensite single-phase state
at 264 K were both singlets, showing a typical paramagnetic feature. On the other hand, the
Mssbauer spectra taken from the martensite phase at 199 and 80 K were complicated, including
some magnetic components. 2008 American Institute of Physics. DOI: 10.1063/1.2960551
Ferromagnetic shape memory alloys FSMAs have attracted much attention due to their potential application as
smart materials since 1996 when magnetic-field-induced
strain was found in the Ni2MnGa alloy.1 Recently, it was
found that the Heusler alloys Ni50Mn50xZx Z = In, Sn, and
Sb show martensitic transformation from the L21 structure
to some kinds of modulated structures, such as 10M tenlayered monoclinic structure, 14M 14-layered monoclinic
structure and 4O four-layered orthorhombic structure,
where the magnetization in the martensite phase for
Ni50Mn50xZx Z = In, Sn, and Sb is much smaller compared
with that in the parent phase.2 Especially in the NiMnIn
and the NiMnSn based systems, a magnetic-field-induced
martensitic reverse transformation from a nonmagnetic martensite phase here, nonmagnetic phase means the phase in
which it has no spontaneous magnetization to a ferromagnetic parent one was obtained and a magnetic-field-induced
shape memory effect, namely, the metamagnetic shape
memory effect, was confirmed.3,4 These FSMAs in the
Ni Mn Z Z = In and Sn based systems have attracted
much attention from the point of view of high performance
materials being controlled by a magnetic field.5,6
In the NiMnSn system, the crystal structures7,8 and the
physical properties, including the magnetism,8,9 the magnetocaloric properties,10 the electrical conductivity,11 and the
pressure effect on the transformation temperatures,12 have
been investigated. In spite of these investigations, the basic
nature of the nonmagnetic martensite phase is still under
discussion. It has been reported that the ferromagnetic martensite phase exists in the phase diagram of all the
Ni Mn Z Z = In, Sn, and Sb based systems.2 On the other
hand, it should be noted that the martensite phase with the
L10 structure in the Ni50Mn50 binary alloy is antiferromagnetic with the Nel temperature at about 1100 K.13 This suga

Author to whom correspondence should be addressed. Electronic mail:

rie@tagen.tohoku.ac.jp.

gests that the nonmagnetic phase appearing in the martensite

phase of the NiMnSn alloys could also be antiferromagnetic, at least in the low concentration region of Sn. In the
present study, Mssbauer spectroscopy was applied to understand the magnetic properties of the martensite phase in a
57
Fe-doped NiMnSn alloy.
Polycrystalline Ni50Mn36.557Fe0.5Sn13 was prepared by
repeated melting of appropriate quantities of the constituent
elements, namely, 99.99 % pure Ni, 99.99% pure Mn,
99.999% pure Sn, and pure Fe57 of the enrichment 99.5%, in
an argon arc furnace. Since the weight loss after melting was
negligible, the nominal composition was accepted as being
accurate. Samples cut out of the ingots were sealed in evacuated double silica tubes, heated at 1123 K for 3 days and
then quenched in water. In order to determine the magnetic
and martensitic transformation temperatures, magnetic measurement and thermal analysis were carried out. The thermomagnetization M-T curve was obtained in a magnetic field
of 500 Oe by a superconducting quantum interference device
magnetometer, where the heating and cooling temperature
rate was 2 K / min. Thermal analysis was performed by differential scanning calorimetric DSC measurement, where
the heating and cooling temperature rate was 10 K / min. 57Fe
Mssbauer spectroscopy measurements were carried out in
the 80 to 312 K temperature range in transmission geometry
using a conventional spectrometer with a 57Co Rh source.
Fittings with the obtained spectra were performed with
MOSSWINN 3.0 program.
The obtained DSC and M-T curves are shown in Fig. 1.
From the M-T curves, it is seen that the magnetic transition
in the parent phase occurs at almost the same time as the
martensitic transformation and that a magnetic cooling effect
starts to appear below 235 K. Here, the zero field-cooled
ZFC and field-cooled FC M-T curves were measured during heating after the specimen was cooled down to a low
temperature in a zero applied magnetic field and during cooling in the applied magnetic field, respectively. The tempera-

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2008
American Institute
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Appl. Phys. Lett. 93, 042509 2008

Umetsu et al.

FIG. 1. DSC and thermomagnetization curves for the Ni50Mn36.557Fe0.5Sn13

alloy. ZFC and FC M-T curves were measured during heating after the
specimen was cooled down to a low temperature in zero magnetic field, and
during cooling in the applied magnetic field, respectively.

ture showing the inflection point around 235 K is indicated

as Ti in the figure. The Curie temperature TC for the parent
phase, defined as the temperature with the largest negative
slope in the cooling M-T curve, was determined to be 309 K.
The martensitic transformation starting and finishing temperatures M s and M f , and the reverse transformation starting
and finishing temperatures As and A f , were determined as
listed in Table I. Those transformation temperatures are defined using the intersection of the baseline and the tangent
line with the largest slope of the DSC peak as demonstrated
in Fig. 1. These magnetic and martensitic transformation behaviors are in good agreement with the phase diagram for the
Ni50Mn37xFexSn13 alloys reported by Fukushima et al.14
The 57Fe Mssbauer spectra taken at several selected
temperatures are shown in Figs. 2a2e and the hyperfine
field distributions derived from the spectra at 293, 199, and
80 K are exhibited in Fig. 3. The measurement was performed at fixed temperatures in the heating process from
80 to 312 K. The spectra of 312 and 264 K in Figs. 2a and
2c are composed of a singlet with a narrow line width,
while that at 293 K includes a very weak and broad subspectrum around the base of the sharp singlet, indicating the coexistence of magnetically ordered and disordered phases. Although the specimen at 293 K should be in a martensite
single-phase condition below As, both the paramagnetic and
ferromagnetic components were detected, as shown in Fig.
3a. This is explained as being due to the presence of a
small amount of the ferromagnetic parent phase. On the
other hand, it should be noted that both full widths at half
maximum of the singlet spectra at 312 and 264 K are almost
equal. This result means that the hyperfine field distribution
of the spectrum taken from the nonmagnetic martensite
phase at 264 K is almost the same as that from the paramagnetic parent+ martensite two-phase state at 312 K, and
strongly suggests that the martensite phase is paramagnetic

FIG. 2. Color online Mssbauer spectra obtained at several measured temperatures for Ni50Mn36.557Fe0.5Sn13 alloy.

in the temperature region from 235 to 295 K, but not antiferromagnetic.

The spectrum at 80 K shows a broad sextet arising from
the wide distribution of hyperfine fields and that at 199 K
exhibits a considerably wide line intensity distribution
around maximum absorption due to the presence of the internal magnetic fields. Actually, the hyperfine field distributions at 199 and 80 K are much broader than that at 293 K as
exhibited in Figs. 3, indicating the occurrence of magnetic
components. It should be noted that the ZFC M-T curve
shows a clear increase with increasing temperature up to
around 200 K, while the FC data indicate relatively plateaulike behavior with a slight decrease of magnetization. On the
other hand, the average hyperfine field apparently decreases
with increasing temperature from 80 to 199 K. These results
suggest that the net value of bulk magnetization would be

TABLE I. Determined magnetic and martensitic transformation temperatures for the Ni50Mn36.557Fe0.5Sn13 alloy. Ti is the temperature showing the
inflection point in the martensite state of M-T curve.
Ti K

TC K

M s K

M f K

As K

A f K

FIG. 3. Color online Hyperfine field contributions obtained from Mss235

309
307
278
295
321
alloy.
bauer spectra of Ni50Mn36.557Fe0.5Sn13IP:
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042509-3

Appl. Phys. Lett. 93, 042509 2008

Umetsu et al.

TABLE II. Phase condition of the Ni50Mn36.557Fe0.5Sn13 alloy at the temperatures at which Mssbauer examination was performed. FM denotes ferromagnetic,
Ferri denotes ferrimagnetic, PM denotes paramagnetic, and SG denotes spin-glass-like.
Temperature
K
Phase
condition

80

199

264

293

312

Martensite
FM, Ferri, or SG

Martensite
FM, Ferri, or SG

Martensite
PM

Martensite PM
+parentPM

Martensite PM
+parentFM

different from the local internal field. Therefore, there are

three possibilities with regard to the magnetism for the martensite phase in the temperature region below Ti = 235 K, i.e.,
a ferromagnetic, ferrimagnetic, or spin-glass-like state. The
magnetic nature of this phase, however, could not be clarified
by the present study. Further investigations and analyses are
required to make clear the magnetic structure below Ti of the
martensite phase. The magnetic phase conditions as all the
measured temperatures are listed in Table II.
In conclusion, the magnetic and martensitic transformation temperatures in the parent and martensite phases were
determined by the DSC and magnetic measurements for the
Ni50Mn36.557Fe0.5Sn13 alloy. The Mssbauer spectra taken
from the parent+ martensite two-phase state at 312 K and
from the martensite single-phase state at 264 K are both singlets, showing a typical paramagnetic feature. This strongly
suggests that the martensite phase at temperatures ranging
from 235 to 295 K is paramagnetic, not antiferromagnetic.
On the other hand, the spectra taken from the martensite
phase at 199 and 80 K are complicated, including some magnetic components.
The authors would like to thank Professor H. Onodera
for helpful discussion. This work was partly supported by a
Grant-in-Aid for Scientific Research from the Japan Society
for the Promotion of Science JSPS, by CREST, Japan Science and Technology Agency and by a grant based on the
High-Tech Research Center Program for private universities
from the Japan Ministry of Education, Culture, Sports, Science and Technology MEXT. Parts of this work were per-

formed at the Center for Low Temperature Science, Institute

for Materials Research, Tohoku University.
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