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Scripta Materialia 104 (2015) 4144
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Enhanced large magnetic entropy change and adiabatic temperature change

of Ni43Mn46Sn11 alloys by a rapid solidication method

Yu Zhang,a Qiang Zheng,b, Weixing Xia,a Jian Zhang,a Juan Dua, and Aru Yana
a

Key Laboratory of Magnetic Materials and Devices, Ningbo Institute of Material Technology & Engineering, Chinese Academy of
Sciences, Ningbo 315201, PR China
b
School of Materials Science and Engineering, Ningbo University of Technology, Ningbo 315016, PR China
Received 10 February 2015; revised 3 April 2015; accepted 5 April 2015
Available online 11 April 2015

The eect of arc melting and melt-spinning on magnetocaloric eect related magnetic properties of Ni43Mn46Sn11 alloys has been contrastively
studied. Dierent measurements based on isothermal magnetization and heat capacity were carried out. For ribbon sample, extremely high magnetic
entropy change DSM of 41.4 J kg1 K1 and adiabatic temperature change DTad of 3.5 K (05 T) were achieved, which increases by 40.3% and 16.7%
compared with that of bulk sample respectively. The martensitic transition related magnetic properties have been systematically discussed.
2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: NiMnSn alloy; Martensitic transformation; Magnetocaloric eect; Adiabatic temperature change; Rapid solidication

Magnetic refrigeration based on the magnetocaloric

eect (MCE) is a potentially high ecient, low cost, gas-free
and no green-house eect refrigeration technology, which is
drawing more attention as an alternative to the existing
vapor compression refrigeration. Recently, magnetic refrigerants, such as GdSiGe [1], LaFeSi [2,3], MnFePAs
[4] and NiMn-based Heusler alloys [5] came into research
focus due to their giant MCE caused by rst-order
phase transition. Among them, rare-earth-free NiMnX
(X = Sn, In, Sb) Heusler alloy systems have aroused peoples
great interest due to their large inverse MCE in the vicinity of
martensitic transition temperature TM, low cost raw materials, and easy preparation method [68]. But from the point of
application, it is important for a magnetic refrigeration
material to have not only a large magnetic entropy change
(DSM) or adiabatic temperature change (DTad) but also a
large refrigeration capacity (RC) [911]. Amorphous structure is in favor of a large RC, while in a compensation for
a relative low DSM [1214]. Therefore, how to increase RC
and keep a large DSM or DTad at the same time is a key issue
for a magnetic refrigeration material.
There are two methods to fabricate NiMnSn alloys, one
is arc-melting followed by annealing, which is the conventional method and bulk samples can be obtained. Later on,
melt-spinning method is developed to shorten annealing time
and getting ribbon samples, which can also be adopted to
prepare LaFeSi alloys [15]. As is well-known, both ribbon

Corresponding

authors; e-mail addresses: qiangzheng616@hotmail.

com; dujuan@nimte.ac.cn

and bulk samples need to be annealed for a period of time to

obtain a uniform phase due to dierent atom diusion distances [16,17]. Dierent preparation methods have dierent
eects on microstructure, microcomposition et al., which
may strongly inuence magnetic properties, such as TM,
DSM, DTad and RC. How these parameters evolve for
NiMnSn alloy using these two preparation methods and
which method is better to get magnetocaloric eect optimized are of importance to be investigated. In this paper, a
series of related work have been done to nd out these issues.
It was found that optimized melt-spun ribbons have extremely higher DSM of 41.4 J kg1 K1 and eective RC of
100.8 J kg1 by measuring isothermal magnetization, which
is increased by 40.3% and 21.6% respectively compared with
optimized arc-melting bulk samples. In order to rule out
magnetic measurement errors for this rst order magnetic
martensitic transition, heat capacity Cp was carried out in 0
and 5 T eld to get a more reliable parameter like adiabatic
temperature change of DTad. A DTad of 3.5 K was achieved
for ribbon sample, which is 0.5 K higher than that of bulk
one. The results show that the melt spinning method is better
to get enhanced magnetic refrigeration properties for
NiMnSn system.
The as-cast ingot of Ni43Mn46Sn11 was prepared by arcmelting under high purity argon atmosphere. The purities
of all raw elements are better than 99.9%. An additional
1 wt.% Mn was added to compensate for its evaporation.
The arc-melted ingot was cut into small pieces, and some
of them were annealed directly to get bulk sample and some
of them will be followed by melt-spun experiment. For
melt-spun ribbon samples, small as cast alloy pieces were

http://dx.doi.org/10.1016/j.scriptamat.2015.04.004
1359-6462/ 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

42

Y. Zhang et al. / Scripta Materialia 104 (2015) 4144

induction melted in a quartz tube with a rectangular nozzle

(6 mm * 0.5 mm) and then ejected onto a copper wheel
rotating at a surface velocity of 15 m/s. The bulk and ribbon samples were homogenized by annealing at 1173 K in
a sealed quartz tube and annealed for 24 h and 60 min
respectively. After annealing, the quartz tube was quenched
in water. The magnetic measurements were carried out
using a super conducting quantum interference device
(SQUID). Heat capacity measurements were carried out
using physical property measuring system (PPMS).
Previous results [11] showed that the maximum magnetic
entropy change for NiMnSn bulk alloy is found to
increase with increasing annealing time from 0 to 24 h
and it approaches saturation when annealing time is close
to 24 h. Arup Ghosh et al. have also studied the inuence
of annealing time on the magnetocaloric eect of NiMn
Sn bulk sample at 1173 K [18]. Generally, many researchers
found annealing at 1173 K for 24 h is optimized to
homogenize bulk sample and a maximum MCE can be
obtained. Our related research on annealing temperature
and time obtained similar results, therefore, in this study,
annealing at 1173 K for 24 h is selected for bulk sample.
Our recent work found that the optimal annealing condition for ribbons is 1173 K for 60 min. In this situation, it
has not only a large magnetic entropy change, but also a
large eective cooling capacity [19]. So annealing at
1173 K for 60 min is selected for ribbon sample in this
paper.
The temperature dependence of magnetization during
heating and cooling for Ni43Mn46Sn11 ribbons and bulk
samples in a low magnetic eld of 100 Oe is shown in

Figure 1. Temperature dependence of the magnetization of bulk

sample annealed at 1173 K for 24 h (a) and ribbon annealed at 1173 K
for 60 min (b) of Ni43Mn46Sn11 measured at the magnetic eld of
100 Oe.

Figure 1. Both samples have a martensitic transformation

temperature (TM) at around 200 K. The slight increase of
TM for ribbons compared with that of bulk sample may
be ascribed to the evaporation of Mn melting once more
during ribbon fabrication process, which would lead to
an increase in e/a value [20].
While TM during cooling and heating does not coincide
for bulk and ribbon samples, which indicates that thermal
hysteresis exists in both samples. The rst order transformation in ribbon sample is sharper than that of bulk
samples which can be conrmed by the temperature range
of martensitic transformation (DTM), which can be calculated using the following formula DTM = [(Af  As) +
(Ms  Mf)]/2, where As and Af, Ms and Mf are the starting
and nishing temperature of the austenite phase and
martensitic phase, respectively. The values of DTM for bulk
and ribbon samples are 8 K and 3 K, respectively. The
martensitic transition related magnetic properties have been
listed in Table 1. So the martensitic transformation nishes
in a narrower temperature change for ribbon sample.
Thereby, the rst order transformation in ribbon is sharper
than that of bulk sample and thermal hysteresis would also
be larger while, in fact, the thermal hysteresis DThys in bulk
sample is about 10 K and that of ribbon sample is about
7 K. Thermal hysteresis is an important characteristic
parameter for magnetocaloric eect material associated
with a rst order magnetic transition. Generally, the sharper
the rst order transformation, the larger the thermal
hysteresis. However, ribbon can be looked as a kind of
two-dimensional material and bulk sample has threedimensions. The stress produced from phase transformation
can be easily released in ribbon sample; on the other hand,
atom diusion length is shorter than that of bulk sample;
therefore thermal hysteresis would be smaller in ribbon sample. These two factors aect the thermal hysteresis in an
opposite way, thus leading to the smaller thermal hysteresis
in ribbon nally. The smaller thermal hysteresis in ribbon is
facilitating for their applications, and the sharper TM also
indicates a higher magnetic entropy change.
Figure 2(a and b) shows the isothermal magnetization
(MH) curves up to 5 T near TM for these two samples.
From the MH curves, it is obvious that both samples show
a typical ferromagnetic behavior. And an obvious metamagnetic behavior between 208 and 217 K was due to the
eld-induced martensitic transition, which would lead to
a large magnetocaloric eect. The dashed area in
Figure 2(a and b) represents the largest magnetic hysteresis
loss obtained at 211 K, and the larger the dashed area, the
larger the magnetic hysteresis loss. The values of the maximum magnetic hysteresis loss DMhys are 138.4 J kg1 and
168.6 J kg1 for bulk and ribbon samples, respectively.
For ribbon sample, the grain size is much smaller than that
of bulk, therefore the movement of magnetic domains will
encounter large resistance due to more grain boundaries,
which resulted in a large DMhys.

Table 1. The starting temperature of the austenitic phase (As), the temperature range for transformation (DTM), dierence of saturation
magnetization between austenite and martensite (DMAM), the magnetic hysteresis loss (DMhys), thermal hysteresis (DThys), magnetic entropy change
(DSM), the refrigerant capacity (RC), eective cooling capacity (RCe) of bulk sample and ribbon samples.

Bulk
Ribbon

As
(K)

DTM
(K)

DMAM
(emu/g)

DMhys
(J kg1)

DThys
(K)

DSM
(J kg1 K1)

RC
(J kg1)

RCe
(J kg1)

214
220

8
3

46
55

138.4
168.6

10
7

29.5
41.4

221.3
269.4

82.9
100.8

Y. Zhang et al. / Scripta Materialia 104 (2015) 4144

43

Figure 3. Temperature dependence of the isothermal magnetic entropy

change DSm with a magnetic eld change of 5 T for bulk sample (a)
and ribbon sample (b).

Figure 2. Isothermal magnetization (MH) curves of bulk sample and

ribbon samples up to 5 T near TM (a and b). The dashed area indicates
magnetic hysteresis loss. Arrott plots of bulk and ribbon samples at
211 K (c).

Figure 2(c) shows Arrott plots comparing with that of

bulk sample just at 211 K. The obvious appearance of
negative slopes conrms the occurrence of a rst order
transition [21], which usually results in a giant magnetic
entropy change DSM and high adiabatic temperature
change DTad. But, the degree of negative slope in ribbon
is larger than that in bulk sample, indicating that martensitic transition in ribbon is faster and sharper than that in
bulk sample, which is in good agreement with the results
obtained from the isothermal magnetization curves, herein
a larger DSM and higher DTad would be expected in ribbons
than in bulk.
DSM for Ni43Mn46Sn11 ribbon and bulk samples were
calculated in a magnetic eld change of 05 T according
to isothermal magnetization curves around TM by using
Maxwell relations, which is shown in Figure 3. The
maximum values of DSM are 41.4 J kg1 K1 and
29.5 J kg1 K1 for ribbon and bulk samples, respectively.
Compared to bulk sample, DSM increases by 40.3% for ribbon sample. This matches well with the description of rst
order transformation in ribbons aforementioned.
Apparently, the increasing manner of magnetization vs eld
around (cyan diamond curve in Figure 2(a and b)) 211 K
for ribbon is much sharper than bulk sample. This means
the rst order transition is faster, which in turn has a good
match with Arrott plots in Figure 2(c). On the other hand,
the magnetization dierence between austenitic and
martensitic phase (DMAM) for ribbon is 55 emu/g, which
is much larger than that of 46 emu/g for bulk (from the

data in Figure 2(a and b)). Such dierences in magnetization DMAM (listed in Table 1) during the progress of
martensitic transition nally results in the following larger
magnetic entropy change of DSM for ribbon sample.
Above, only a rough estimation by Maxwell calculation
had been done by measuring MH curve on each temperature around TM. It is well known that rst-order magnetic
phase transitions are often accompanied by volume deformation. It is an indication that strong couplings exist, such
as the magnetoelastic coupling, so the results calculated
from Maxwell relation give the total entropy change of
the system, which is much higher than real one [22]. And,
for a rst order transition like Martensitic transition, a
spike phenomenon may occur using this calculation
[23]. Caron et.al have proposed a Loop Process [23] to
get a more reliable DSM. In this work, heat capacity has
been measured to obtain more convincing DSM and adiabatic temperature change DTad, which is a true parameter
for a magnetic refrigeration material.
The specic heat Cp vs T in 0 eld and 5 T eld have
been measured as shown in Figure 4(a and b). A small step
of 1 K around TM has been chosen in order to rule out the
spike phenomenon. According to thermodynamics, DSM
can be calculated by Eq. (1), and DTad can be calculated by
Eq. (2).
Z T
C H T  C 0 T
DST
dT
1
T
0
DT ad T DH T SH  T S0 S

Both DSM and DTad calculated by heat capacity for bulk

and ribbon samples are shown in the inset of Figure 4(a and
b). A DTad of 3.5 K and DSM of 6.8 J kg1 K1 are
achieved for the ribbon sample, which is much higher than
that of bulk samples 3.0 K and 6.0 J kg1 K1 respectively.
In this work, the DTad of 3.5 K for ribbon sample is much
higher than previous reports in NiMnSn [22,24], which is
generally much lower than 2.5 K in the same eld change.

44

Y. Zhang et al. / Scripta Materialia 104 (2015) 4144

eld change of 5 T were obtained by Maxwell relation

through measuring isothermal magnetization, which are
much higher than those (DSM of 29.5 J kg1 K1 and
RCe of 82.9 J kg1) in bulk sample. Heat capacity has been
measured and used to calculate DSM (6.8 J kg1 K1 and
6.0 J kg1 K1 for ribbon and bulk respectively) and DTad
(3.5 K and 3.0 K for ribbon and bulk, respectively), which
have come to the same conclusion. The Melt-spinning
method is better to obtain excellent magnetocaloric eect
for Ni43Mn46Sn11 alloys.
This work was supported by Natural Science
Foundation of Zhejiang Province (Grant No. LR12E01001),
National Natural Science Foundation of China (Grant No.
51422106), Natural Science Foundation of Ningbo City (Grant
No. 2012A610102), the Key Research Program of the Chinese
Academy of Sciences (Grant No. KGCX-EW-215-3), Ningbo
City Scientic and Technological Project (Grant No.
2012B81001), Scientic and Technology Project of Zhejiang
Province (Grant No. 2013TD08).

Figure 4. Temperature dependence of heat capacity of bulk sample (a)

and ribbon sample (b) in 0 and 5 T eld, the insets are DSm and DTad
calculated by heat capacity.

For NiMnSn alloy, DSM calculated only by heat capacity

is generally much lower than 5 J kg1 K1 in literatures
[22,24]. For our ribbon sample, DSM calculated by the same
method is 6.8 J kg1 K1. Comparing Figures 3 and 4(a
and b), for both bulk and ribbon, the DSM calculated by
Maxwell relation is somewhat overestimated, but still consistent with that calculated by heat capacity. However, the
specic heat option for PPMS tends to make underestimation of heat jump caused by the latent heat of the rst-order
transition. In this work, no matter which method was
applied, the conclusions can be made that melt-spinning
method is better than arc-melting from DSM and DTad.
Refrigerant capacity (RC) is another important parameter to evaluate magnetic refrigeration materials, which can
be calculated by the product of DSM and the full width of
the temperature at half maxima of the DSM peak. The values of RC for the ribbon and bulk samples are 269.4 J kg1
and 221.3 J kg1, respectively. Hysteresis loss must be considered for evaluating the usefulness of a magnetic refrigerant during a thermodynamic cycle. Eective cooling
capacity RCe can be obtained by subtracting the hysteresis
loss at 211 K from RC value. So the values of RCe are estimated to be 100.8 J kg1 and 82.9 J kg1 for ribbon and
bulk samples, respectively. Compared to the bulk sample,
an increase of 21.7% and 21.6% was obtained for RC and
RCe in ribbon samples, respectively.
In conclusion, the preparation method of arc melting and
melt-spinning on martensitic transition temperature TM,
thermal/magnetic hysteresis DThys, magnetocaloric eect
DSM and refrigeration capacity RC of Ni43Mn46Sn11 alloys
has been systematically studied. The ribbon has a little
higher TM and narrower temperature change DTM of phase
transition than that of bulk sample. For ribbon sample, it
has lower thermal hysteresis DThys due to a shorter diusion
length, but higher magnetic hysteresis DMhys, which is due
to the ne grains. A high DSM of 41.4 J kg1 K1 and a high
RCe of 100.8 J kg1 in ribbon sample under a magnetic

[1] V.K. Pecharsky, K. Gschneidner Jr., Phys. Rev. Lett. 78

(1997) 4494.
[2] F.X. Hu, B.G. Shen, J.R. Sun, Z.H. Cheng, G.H. Rao, X.X.
Zhang, Appl. Phys. Lett. 78 (2001) 3675.
[3] A. Fujita, S. Fujieda, Y. Hasegawa, K. Fukamichi, Phys.
Rev. B 67 (2003) 104416.
[4] O. Tegus, E. Bruck, K. Buschow, F. De Boer, Nature 415
(2002) 150.
[5] T. Krenke, E. Duman, M. Acet, E.F. Wassermann, X.
Moya, L. Manosa, A. Planes, Nat. Mater. 4 (2005) 450.
[6] J. Du, Q. Zheng, W.J. Ren, W.J. Feng, X.G. Liu, Z.D.
Zhang, J. Phys. D Appl. Phys. 40 (2007) 5523.
[7] V.D. Buchelnikov, V.V. Sokolovskiy, Phys. Met. Metallogr.
112 (2012) 633.
[8] J. Liu, T. Gottschall, K.P. Skokov, J.D. Moore, O.
Guteisch, Nat. Mater. 11 (2012) 620.
[9] M.E. Wood, W.H. Potter, Cryogenics 25 (1985) 667.
[10] K.A. Gschneidner Jr., V.K. Pecharsky, A.O. Pecharsky, C.B.
Zimm, Mater. Sci. Forum 315 (1999) 69.
[11] V. Provenzano, A.J. Shapiro, R.D. Shull, Nature (London)
429 (2004) 853.
[12] J. Du, Q. Zheng, Y.B. Li, Q. Zhang, D. Li, Z.D. Zhang, J.
Appl. Phys. 103 (2008) 023918.
[13] Q. Luo, D.Q. Zhao, M.X. Pan, W.H. Wang, Appl. Phys.
Lett. 89 (2006) 081914.
[14] F. Yuan, J. Du, B.L. Shen, Appl. Phys. Lett. 101 (2012)
032405.
[15] J.J. Liu, Y. Zhang, J. Zhang, W.X. Xia, J. Du, A.R. Yan, J.
Magn. Magn. Mater. 350 (2014) 94.
[16] H.C. Xuan, K.X. Xie, D.H. Wang, Z.D. Han, C.L. Zhang,
B.X. Gu, Y.W. Du, Appl. Phys. Lett. 92 (2008) 242506.
[17] H.X. Zheng, D.Z. Wu, S.C. Xue, J. Frenzel, G. Eggeler, Q.J.
Zhai, Acta Mater. 59 (2011) 5692.
[18] A. Ghosh, K. Mandal, Appl. Phys. Lett. 104 (2014) 031905.
[19] Y. Zhang, Q. Zheng, J. Du, et al., Sci. Rep. (submitted).
[20] Z. Han, D. Wang, B. Qian, J.F. Feng, X.F. Jiang, Y.W. Du,
Jpn. J. Appl. Phys. 49 (2010) 010211.
[21] A. Arrott, Phys. Rev. 108 (1957) 1394.
[22] J.D. Zou, B.G. Shen, B. Gao, J. Shen, J.R. Sun, Adv. Mater.
21 (2009) 693.
[23] L. Caron, Z.Q. Ou, T.T. Nguyen, D.T. Cam Thanh, O.
Tegus, E. Bruck, J. Magn. Magn. Mater. 321 (2009) 3559.
[24] V.A. Chernenko, J.M. Barandiaran, J.R. Fernandez, D.P.
Rojas, J. Gutierrez, P. Lazpita, I. Orue, J. Magn. Magn.
Mater. 324 (2012) 3519.