Effect of annealing on the martensitic transformation and magnetocaloric effect in Ni

44.1 Mn 44.2 Sn 11.7 ribbons

H. C. Xuan, K. X. Xie, D. H. Wang, Z. D. Han, C. L. Zhang, B. X. Gu, and Y. W. Du

Citation: Applied Physics Letters 92, 242506 (2008); doi: 10.1063/1.2948904

View online: http://dx.doi.org/10.1063/1.2948904
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 APPLIED PHYSICS LETTERS 92, 242506 共2008兲

Effect of annealing on the martensitic transformation and magnetocaloric

effect in Ni44.1Mn44.2Sn11.7 ribbons
H. C. Xuan, K. X. Xie, D. H. Wang,a兲 Z. D. Han, C. L. Zhang, B. X. Gu, and Y. W. Du
National Laboratory of Solid State Microstructures and Department of Physics, Nanjing University,
Nanjing 210093, People’s Republic of China
共Received 22 April 2008; accepted 31 May 2008; published online 18 June 2008兲
The Ni44.1Mn44.2Sn11.7 ribbons were prepared by melt spinning. A single-phase austenite with L21
structure was confirmed in the melt-spun ribbons at room temperature. After the heat treatment, the
martensitic transformation temperature increases obviously in the annealed ribbons. This method
may be an effective way to tune the characteristic temperatures in the ferromagnetic shape memory
alloys. Giant magnetic entropy changes are observed in the annealed ribbons. The peak values at
10 kOe are 32.1 and 20.1 J / kg K, for the ribbons annealed at 1123 and 1173 K, respectively.
© 2008 American Institute of Physics. 关DOI: 10.1063/1.2948904兴

Ferromagnetic shape memory alloys 共FSMAs兲 exhibit nealed for 10 min at 1123 and 1173 K, which are denoted A
ferromagnetic and shape memory effect simultaneously, in and B ribbons, respectively. The structure of these ribbons is
which the shape memory effects can be controlled by tem- identified by x-ray diffraction 共XRD兲 at room temperature.
perature and stress, as well as by magnetic field. Recently, Microstructure and elemental compositions were examined
the Ni– Mn– X 共X = Sn, In, and Sb兲 alloys are the mostly by using a scanning electron microscope 共SEM兲 equipped
investigated FSMAs.1 They undergo the martensitic transfor- with an x-ray energy dispersive spectroscopy 共EDS兲 system.
mation 共MT兲 from the parent austenitic phase to the marten- The magnetization measurements were carried out using a
sitic phase on cooling. Since the austenite and martensite vibration sample magnetometer 共7300, Lakeshore兲 under a
have different crystal structures and magnetizations, large magnetic field up to 10 kOe. The applied magnetic field was
magnetocaloric effects 共MCE兲 and magnetoresistance 共MR兲 parallel to the ribbon’s surface 共along the ribbon axis兲.
can be observed in Ni– Mn– X FSMAs.2–6 On heating, the Typical SEM images of fracture cross section and free
magnetic phase transitions in these FSMAs are presented in surface of these ribbons are presented in Fig. 1. As shown in
the following sequence:6 共i兲 ferromagnetic-paramagnetic Fig. 1共a兲 ordered columnar microstructure is observed in the
phase transition in the martensite, 共ii兲 the MT from cross section, indicating that the rapid solidification process
ferromagnetic/paramagnetic martensite to ferromagnetic aus- induces the formation of textured polycrystalline ribbons.7–9
tenite, and 共iii兲 ferromagnetic-paramagnetic transition in the
austenite. When the MT occurs between a ferromagnetic aus-
tenite and a paramagnetic martensite, a large magnetization
change 共⌬M兲 can be obtained. It is well known that large
⌬M around the MT is the key parameter for obtaining large
magnetic entropy changes 共⌬SM 兲 in FSMAs, so tuning the
MT to a certain temperature is of great importance for the
MCES.
Very recently, rapid quenching by melt spinning is re-
ported as an effective method to achieve homogeneous
Ni– Mn– X FSMAs,7–10 which can avoid or reduce the time
of annealing, and is easy to obtain highly textured polycrys-
talline ribbons.7–9 Up to now, the most used methods to ad-
just the MT temperature in Ni– Mn– X FSMAs are tuning the
composition or doping elements with a small atomic
radius.11,12 In this letter, we report on the microstructure and
magnetic properties of melt-spun Ni–Mn–Sn ribbons, and
find that with different annealing temperatures, the MT tem-
peratures of the annealed ribbons increase obviously. Since
the MT occurs between a ferromagnetic austenite and a para-
magnetic martensite, giant values of ⌬S M are observed in
these ribbons.
Ni–Mn–Sn ribbons were prepared by melting the as-cast
Ni–Mn–Sn alloys in a quartz crucible and ejected onto a
rotating copper wheel with a surface velocity of 10 m / s. The
melt-spun ribbons were vacuumed in quartz tubes and an-
FIG. 1. Typical SEM micrograph of the different regions of
a兲
Electronic mail: wangdh@nju.edu.cn. Ni44.1Mn44.2Sn11.7 ribbons: 共a兲 fractured cross section; 共b兲 free surface.

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 242506-2 Xuan et al. Appl. Phys. Lett. 92, 242506 共2008兲

FIG. 4. 共Color online兲 共a兲 The isothermal magnetization curves for A rib-
bons around the MT temperature. 共b兲 The temperature dependence of ⌬SM
for the melt-spun, A, and B ribbons in the magnetic field of 5 and 10 kOe,
respectively.
FIG. 2. 共Color online兲 The XRD patterns for the melt-spun, A, and B rib-
bons at room temperature.
that the MT temperatures and TCA increase after annealing. As
we know, the heat treatment, involving stress relaxation, may
From Fig. 1共b兲, the equiaxed crystallized grains at the free
decrease the strain energy. Recent report about the FePd
surface are observed. The grain sizes increase with the in-
FSMAs showed that the size dependence of MT temperature
creasing annealing temperature, and the average sizes are
should be ascribed to the change of strain energy.13 In the
0.9, 4.0, and 8.0 ␮m, for the melt-spun, A, and B ribbons,
sample with small grain sizes, the strain energy becomes
respectively. The average elemental chemical composition of
large, and thus the large driving force is required for the
the ribbons is determined as Ni44.1Mn44.2Sn11.7, which is es-
transformation, which results in the decrease in the MT
timated by the EDS microanalysis.
temperature.13 On the other hand, the atom site in melt-spun
The XRD patterns of all the ribbons are shown in Fig. 2.
ribbons may be not too stable, since they are prepared by the
The melt-spun and annealed ribbons all have the cubic L21
quick transition from the liquid to the solid state, and do not
type structure 共austenitic phase兲 at room temperature. It is
take up an equilibrium position, in which they would have
obvious that the diffraction peaks become narrower in A and
lower energy. After annealing, the melt-spun ribbons undergo
B ribbons, indicating that the grain sizes of annealed ribbons
structural relaxation,14 which may modify the atom site
increase, which is consistent with the SEM results. From Fig.
slightly, resulting in the change of Mn–Mn distance. It is
2, we can observe that, after annealing, the diffraction peaks
reported that, for the Ni–Mn based Heusler alloys, including
shift towards high angles, suggesting the decrease in cell
nonstoichiometric ones, the exchange interactions and, con-
volumes. The lattice constants are 5.950, 5.948, and 5.942 Å,
sequently, magnetic ordering temperatures are sensitive to
for melt-spun, A, and B ribbons, respectively.
the Mn–Mn distance.12,15–17 So the effect of annealing on the
Figure 3 shows the temperature dependence of magneti-
MT temperatures and TCA in Ni44.1Mn44.2Sn11.7 ribbons should
zation for these ribbons under the field of 100 Oe from
be ascribed to the stress and structural relaxations.
200 to 320 K. For each sample on heating, a weak magnetic
Isothermal magnetization curves M-H for the
behavior is first observed, indicating that the Curie tempera-
Ni44.1Mn44.2Sn11.7 ribbons were measured around the MT
tures of the martensite 共TC 兲 for these ribbons are below
M
temperatures with a field up to 10 kOe. The typical M-H
200 K. Further increasing the temperature causes a sudden
curves for A ribbons are shown in Fig. 4共a兲. An obvious
jump of magnetization, corresponding to the reverse MT. Fi-
metamagnetic behavior, due to the field-induced MT, can be
nally, the magnetization decreases with the increasing tem-
observed at 236 K. As shown in Fig. 3, the MT of all ribbons
perature, until a ferromagnetic-paramagnetic transition oc-
occurs between a ferromagnetic austenite and a paramagnetic
curs at the Curie temperature of austenite 共TC兲. It is obvious
A
martensite, so large values of ⌬M = 48 emu/ g can be ob-
tained in the A ribbons. From Fig. 4共a兲, it is clear that in the
austenitic state, the magnetization approaches the saturation
quickly even at the low fields. This soft magnetic behavior is
due to the low anisotropy of the cubic symmetry for austen-
ite and the easy magnetization direction paralleling to the
ribbon’s surface.8
The ⌬S M as a function of temperature and magnetic field
for these ribbons were calculated from isothermal magneti-
zation curves. As shown in Fig. 4共b兲, giant ⌬S M were ob-
served in A and B ribbons, even at the relatively low mag-
netic field. The values of ⌬S M at 5 kOe for A and B ribbons
are larger than those of Ni50−xMn39+xSn11 alloys, which were
measured at 10 kOe.3 The giant ⌬SM in those ribbons are
attributed to the abrupt change in the magnetization around
the MT temperatures. It is well known that in Ni– Mn– X
FIG. 3. 共Color online兲 The temperature dependence of magnetization under FSMAs, the martensite and the austenite have different struc-
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a magnetic field of 100 Oe for the melt-spun, A, and B ribbons on heating. tures, and the magnetization of martensite is often less than
131.156.59.191 On: Thu, 11 Sep 2014 09:03:46
 242506-3 Xuan et al. Appl. Phys. Lett. 92, 242506 共2008兲

that of austenite.1 As for Ni44.1Mn44.2Sn11.7 ribbons, owing to

the abrupt change of magnetization and large values of ⌬M,
giant ⌬S M can be obtained around the MT temperatures. Due
to the inhomogeneity of concentration in the melt-spun rib-
bons, the magnetization changes relatively gradually around
the MT temperature,13 which can be observed in Fig. 3. So
compared with the annealed ribbons, the values of ⌬S M for
melt-spun ribbons are lower, while the peaks of ⌬S M are
broader.
In conclusion, the effects of annealing on the MT and
⌬S M in Ni44.1Mn44.2Sn11.7 ribbons have been investigated.
After annealing, the MT temperatures and TCA increase re-
markably, owing to the stress and structural relaxations. Gi-
ant ⌬S M at low magnetic field, are observed in the annealed
ribbons. The convenient preparing method, adjustable MT
temperatures, giant ⌬SM at low magnetic field, and low cost
make Ni44.1Mn44.2Sn11.7 ribbons have promising potential in
the application of magnetic refrigeration.
This work was supported by the National Key Project
for Basic Research 共2005CB623605兲 and the National Natu-
ral Science Foundation of China 共50701022兲, respectively.
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