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
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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 at-
tracted 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 ten-
layered 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 mar-
tensite phase here, nonmagnetic phase means the phase in
which it has no spontaneous magnetization to a ferromag-
netic 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 magne-
tocaloric 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 mar-
tensite 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 antiferromag-
netic with the Nel temperature at about 1100 K.13 This sug-
a
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 antiferromag-
netic, at least in the low concentration region of Sn. In the
present study, Mssbauer spectroscopy was applied to under-
stand 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 evacu-
ated 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 mea-
surement and thermal analysis were carried out. The thermo-
magnetization 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 dif-
ferential 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 dur-
ing heating after the specimen was cooled down to a low
temperature in a zero applied magnetic field and during cool-
ing in the applied magnetic field, respectively. The tempera-

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 042509-2 Umetsu et al. Appl. Phys. Lett. 93, 042509 2008

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 tem-
peratures 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 de-
fined using the intersection of the baseline and the tangent
FIG. 2. Color online Mssbauer spectra obtained at several measured tem-
line with the largest slope of the DSC peak as demonstrated peratures for Ni50Mn36.557Fe0.5Sn13 alloy.
in Fig. 1. These magnetic and martensitic transformation be-
haviors are in good agreement with the phase diagram for the
Ni50Mn37xFexSn13 alloys reported by Fukushima et al.14 in the temperature region from 235 to 295 K, but not antifer-
The 57Fe Mssbauer spectra taken at several selected romagnetic.
temperatures are shown in Figs. 2a2e and the hyperfine The spectrum at 80 K shows a broad sextet arising from
field distributions derived from the spectra at 293, 199, and the wide distribution of hyperfine fields and that at 199 K
80 K are exhibited in Fig. 3. The measurement was per- exhibits a considerably wide line intensity distribution
formed at fixed temperatures in the heating process from around maximum absorption due to the presence of the in-
80 to 312 K. The spectra of 312 and 264 K in Figs. 2a and ternal magnetic fields. Actually, the hyperfine field distribu-
2c are composed of a singlet with a narrow line width, tions at 199 and 80 K are much broader than that at 293 K as
while that at 293 K includes a very weak and broad subspec- exhibited in Figs. 3, indicating the occurrence of magnetic
trum around the base of the sharp singlet, indicating the co- components. It should be noted that the ZFC M-T curve
existence of magnetically ordered and disordered phases. Al- shows a clear increase with increasing temperature up to
though the specimen at 293 K should be in a martensite around 200 K, while the FC data indicate relatively plateau-
single-phase condition below As, both the paramagnetic and like behavior with a slight decrease of magnetization. On the
ferromagnetic components were detected, as shown in Fig. other hand, the average hyperfine field apparently decreases
3a. This is explained as being due to the presence of a with increasing temperature from 80 to 199 K. These results
small amount of the ferromagnetic parent phase. On the suggest that the net value of bulk magnetization would be
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 paramag-
netic parent+ martensite two-phase state at 312 K, and
strongly suggests that the martensite phase is paramagnetic

TABLE I. Determined magnetic and martensitic transformation tempera-

tures 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

235 309 307 278 295 321 FIG. 3. Color online Hyperfine field contributions obtained from Mss-
bauer spectra of Ni50Mn36.557Fe0.5Sn13IP:
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 042509-3 Umetsu et al. Appl. Phys. Lett. 93, 042509 2008

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 80 199 264 293 312

Phase Martensite Martensite Martensite Martensite PM Martensite PM

condition FM, Ferri, or SG FM, Ferri, or SG PM +parentPM +parentFM

different from the local internal field. Therefore, there are formed at the Center for Low Temperature Science, Institute
three possibilities with regard to the magnetism for the mar- for Materials Research, Tohoku University.
tensite phase in the temperature region below Ti = 235 K, i.e.,
1
a ferromagnetic, ferrimagnetic, or spin-glass-like state. The
magnetic nature of this phase, however, could not be clarified 2
by the present study. Further investigations and analyses are
3
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. 4
In conclusion, the magnetic and martensitic transforma-
tion temperatures in the parent and martensite phases were
5
determined by the DSC and magnetic measurements for the
Ni50Mn36.557Fe0.5Sn13 alloy. The Mssbauer spectra taken 6
from the parent+ martensite two-phase state at 312 K and
from the martensite single-phase state at 264 K are both sin-
7
glets, showing a typical paramagnetic feature. This strongly
suggests that the martensite phase at temperatures ranging
8
from 235 to 295 K is paramagnetic, not antiferromagnetic.
On the other hand, the spectra taken from the martensite 9
phase at 199 and 80 K are complicated, including some mag-
10
netic components.
11
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 12
for the Promotion of Science JSPS, by CREST, Japan Sci- K. Oikawa, K. Ishida, K.-U. Neumann, and K. R. A. Ziebeck, J. Magn.
ence and Technology Agency and by a grant based on the
13
High-Tech Research Center Program for private universities
from the Japan Ministry of Education, Culture, Sports, Sci- 14
ence and Technology MEXT. Parts of this work were per- Oikawa, and K. Ishida unpublished.
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