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6 AUTHORS, INCLUDING:
Katsunari Oikawa
Wataru Ito
Tohoku University
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APPLICATION
a
Institute of Multidisciplinary Research for Advanced Materials
(IMRAM), Tohoku University, Sendai, 980-8577, Japan. E-mail:
kainuma@tagen.tohoku.ac.jp
b
Department of Materials Science, Graduate School of Engineering,
Tohoku University, Sendai, 980-8579, Japan
c
Faculty of Engineering, Tohoku Gakuin University, Tagajo, 980-8579,
Japan
Introduction
Based on diffusionless phase transformation, which is termed
martensitic transformation, the shape memory effect (SME) in
alloys is known to be unique behavior by which an alloy
deformed in the low-temperature phase recovers its original
shape by reverse transformation upon heating to the reverse
transformation temperature. This effect was first observed in
AuCd alloys in 1951 and became well known with its discovery
in TiNi alloys in 1963.1 TiNi alloys are the most familiar shape
memory alloys (SMA) with applications in various fields such as
medical guidewires, cellar-phone antennae, and smart actuators.
Because the strain and stress generated by the SME are
extremely large as compared to those generated in piezoelectric
and magnetostrictive materials, SMAs are potential candidates
for actuators such as motors and supersonic oscillators.
However, since the output actuation in SMAs occurs through
Ryosuke Kainuma
Katsunari Oikawa
Fig. 1 Crystal structure of Ni2MnZ Heusler phase (a) and thermomagnetization curve21 of Ni50Mn34In16 in a magnetic field of H 0.05 (b).
Magnetic moments of Mn atoms in each state are schematically indicated
with arrows in insets of (b), where M(AF?), P(FM) and P(PM) are the
martensite phase with antiferromagnetic-like magnetism and the parent
phases with ferromagnetism and paramagnetism, respectively.
known to exhibit ferromagnetism,19,20 martensitic transformation in these alloys has not yet been reported. The authors
observed that martensitic transformation from the Heusler-type
P phase to the monoclinic or orthorhombic M phase occurs in
the NiMnNi2MnX sections.18 Fig. 1(b) shows the thermomagnetization curve of the Ni50Mn34In16 alloy (at%) for a magnetic
field of 0.05 T.21 The Curie temperature Tc of the P phase is
detected at around 280 K, and the martensitic transformation
starting temperature TMs appears at around 230 K. It is observed
that the magnetization drastically decreases with temperature
from the TMs to the martensitic transformation finishing
temperature TMf and that the thermal hysteresis is approximately
20 K. Such thermomagnetization behavior in a weak magnetic
field is sometimes observed in the M phase of conventional
FSMAs with large crystalline magnetic anisotropy energy.10
However, in the present case, the magnetization of the M phase
is very small, even in the presence of strong magnetic fields.
Fig. 222 shows the thermomagnetization curves for magnetic
fields of 0.05 T and 7 T and the magnetization curves at various
temperatures for a Ni46Mn41In13 alloy whose composition is
slightly different from that of the previous alloy. In Fig. 2(a), it
is observed that the difference in the saturated magnetization
between the P and M phases is approximately 100 emu g1 and
that the TMs and TMf temperatures and the temperatures TAs
and TAf at which the reverse transformation starts and ends,
respectively, decrease by 4050 K due to the increase in the
magnetic field from 0.05 T to 7 T. This result suggests that at
temperatures between 180 and 220 K, the M phase transforms
to the P phase due to application of the magnetic field of
7 T. This behavior, i.e., the magnetic field-induced reverse
200, 270, 290, and 320 K in the Ni45Co5Mn36.7In13.3 alloy, respectively.25 The characteristic features of the quaternary alloy are
basically similar to those of the NiMnIn ternary alloy;
however, the decrease in the value of TMs, which is only approximately 25 K in a magnetic field of 7 T, is smaller than that in the
Ni46Mn41In13 alloy. This issue is discussed in the next section. It
is also observed that the addition of Co results in a decrease in the
saturation magnetization in the M phase region. The origin of
this phenomenon is not yet clear, but it appears that the doped
Co has a strong magnetic interaction with Mn, which should
be dominant in the magnetic properties in this alloy. It should
be emphasized here that an apparent metamagnetic phase transition is detected at 290 K, as shown in Fig. 4(b). This indicates that
this quaternary alloy possibly has a magnetic field-induced SME
due to this metamagnetic phase transition at room temperature.
dT
DI
(1)
DI
DH
DTz
DS
J. Mater. Chem., 2008, 18, 18371842 | 1839
dsc
DS
dT 3,Vm
(2)
DS
DI
,DTz
,DH
3,Vm
3,Vm
(3)
Conclusion
The phase transformation from the ferromagnetic to the antiferromagnetic phase has already been reported for several alloy
compounds and ceramics. In the NiMn-based alloys discussed
in this study, the magnetic transition occurs with the thermoelastic martensite transformation accompanying the shape memory
effect and pseudoelasticity, which is different from that in the
previous materials. This combination of magnetic and structural
transitions has high potential for the development of many types
of multiferroic devices such as sensors, actuators, and thermomagnetic engines and can by controlled by three factors, namely,
temperature, stress, and magnetic field.
Since the reports on MMSMAs, many investigations have been
performed and some unique physical properties such as giant
magnetoresistance,32,33 giant magnetothermal conductivity,34
and inverse magnetocaloric effect35,36,37 have been reported. These
properties are also very interesting.
Acknowledgements
The authors are grateful to Mr Y. Imano, Dr H. Morito and
Prof. S. Okamoto, O. Kitakami and A. Fujita, Tohoku
University, for their assistance with the experiments. This study
was supported by a Grant-in-Aid from CREST, Japan Science
and Technology Agency (JST), Grants-in-Aid for Scientific
Research from the Japan Society for the Promotion of Science
(JSPS), Japan, and Global COE Project.
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