Beruflich Dokumente
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Physics Letters A ()
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Physics Letters A
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Kun Xu
a,
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Department of Physics and Electronic Engineering, Key Laboratory for Advanced Functional and Low Dimensional Materials of Yunnan Higher Education
Institute, Qujing Normal University, Qujing 655011, China
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Department of Physics, Shanghai University, Shanghai 200444, China
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a r t i c l e
i n f o
Article history:
Received 14 September 2015
Received in revised form 15 October 2015
Accepted 15 October 2015
Available online xxxx
Communicated by L. Ghivelder
Keywords:
Heusler alloy
Magnetocaloric effect
ClausiusClapeyron equation
Maxwell relation
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a b s t r a c t
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Taking into account the phase fraction during the structural transition for the rst-order magnetocaloric
materials, an improved isothermal entropy change ( S T ) determination has been put forward based
on the ClausiusClapeyron (CC) equation. It was found that the S T value evaluated by this method
is in excellent agreement with those determined from the Maxwell relation (MR) using magnetic
measurements for some Heusler alloys with a weak eld-induced phase transforming behavior, such
as NiMnSn Heusler alloys. In comparison with the MR based on isoeld magnetization measurements
(MRIF), this method is very convenient to obtain the S T derived from only few thermomagnetic curves.
More importantly, it is quite superior to the MR-based method in eliminating the overestimation of
S T due to the appearance of the spurious spike derived from MR employing isothermal magnetization
measurements (MRIT).
2015 Published by Elsevier B.V.
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1. Introduction
The magnetocaloric effect (MCE), which reects the magnetoresponsive ability of refrigerating when a magnetic material is submitted to the external magnetic eld variations, has emerged as an
attractive option in the new generation of energy-ecient cooling
technologies. Since the discovery of pseudo-binary Gd5 Si2 Ge2 compound by Pecharsky and Gschneidner in 1997 [1], the MCE became
a promising contender to the conventional vapor-compressive refrigerating methods under ambient conditions due to its environmental friendliness, higher cooling eciency and compactness. Since then, the giant MCE has also been extensively studied in other intermetallic compounds, such as MnAs1x Sbx [2],
MnFeP1x Asx [3], (Mn,Fe)2 P1x Six [4], La(Fe1x ,Six )13 /its hydrides
[5,6], and the family of Heusler alloys like NiMnGa [7] and Ni
MnZ (Z = In, Sn, Sb) [8]. Among these materials, the outstanding MCE is due to the involvement of latent heat produced by
structural transition in combination with magnetic ordering and
changes in the electronic band structure. In general, for the materials with direct MCE, both the lattice entropy change ( S L ) and
magnetic entropy change ( S mag ) contribute positively to the total measured MCE [9]. Whereas for the materials with inverse MCE,
the magnetocaloric response comes from the S L , and the S mag
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Corresponding author.
E-mail address: xukun0830@hotmail.com (K. Xu).
http://dx.doi.org/10.1016/j.physleta.2015.10.029
0375-9601/ 2015 Published by Elsevier B.V.
H 2
ST =
H1
M i +1 M i
M
H .
dH
T
T i +1 T i
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effect. Meanwhile, Sun et al. [14] also pointed out that CC equation is just a special case of integrated Maxwell relation and is
inadequate to evaluate the S T value for an incomplete transformation. Particularly, recent progress on the inverse MCE research for NiMnSn alloys aroused a new round of argument once
again. Zou et al. [15,16] claimed that the S T value is seriously
overestimated by MRIT in Ni43 Mn46 Sn11 due to the occurrence
of a magnetically inhomogeneous martensitic state. On the contrary, Maosa et al. [17] proved that the S T values respectively
obtained from MRIT and calorimetric measurements are in well
agreement for Ni50 Mn35 Sn15 . Despite the validity and generality of
MRIT being still under debate, it is undeniable that the direct application of MRIT would lead to some unphysical results. In most
cases, a spike is always observed on the S T ( T ) curve, especially in some materials with a pronounced eld-induced transition
[2,1822]. A spike value for Mn0.997 Fe0.003 As unexpectedly attains
up to 320 J/kg K for a eld change of 5 T under the ambient pressure [23]. This value is far above those reported for all
known magnetocaloric materials as well as the theoretical prediction. Such a colossal MCE can be attributed to the incorrect
application of MRIT, which gives rise to a spurious artifact. In fact,
some practical methods to modify the S T values obtained from
MRIT have been proposed by Liu et al. [24] and Cui et al. [25].
Nevertheless, the former one was found to be inadequate for an
extreme case of Mn0.99 Cu0.01 As [26], while the latter one is very
complex for the practical use. In addition to MRIT, the S T can
be also determined accurately by using Maxwell relation based on
isoeld magnetization measurements (referred to as MRIF here)
[27], but this method needs a large number of thermomagnetic
curves with great measuring cost. In the present work, a proper
method based on the CC equation using isoeld magnetization
measurements (CCIF) has been proposed to estimate the realistic
MCE for the magnetocaloric materials with FOMT. The feasibility
of this method was tested on the Ni43 Mn46 Sn11 , Ni50 Mn35 Sn15 and
Ni45 Co5 Mn36.6 In13.4 Heusler alloys with their inverse MCE, as well
as MnAs and Gd5 Si2 Ge2 compounds with direct MCE. All these experimental results demonstrate that such a new method using to
evaluate the S T is superior to the MR-based method.
2. Experimental
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Nominal stoichiometry Ni43 Mn46 Sn11 and Ni50 Mn35 Sn15 ingots
were prepared by arc melting high-purity Ni, Mn, Sn metals under
an argon atmosphere. After melting, the samples were sealed in
evacuated quartz tubes in order to homogenize at 1173 K for 24 h,
and then subsequently quenched in ice-water. Their crystal structures and phases were veried by the X-ray diffraction (Rigaku,
Ultima IV) using Cu K radiation. The results show that both the
Ni43 Mn46 Sn11 and Ni50 Mn35 Sn15 samples are single phase with a
L21 cubic structure (austenite phase) at room temperature. The
magnetic characterizations were carried out by a Quantum Design VersaLab magnetometer (VersaLab, 3 Tesla). When dealing
with the Ni45 Co5 Mn36.6 In13.4 , MnAs and Gd5 Si2 Ge2 samples, the
correlatively experimental data were directly extracted from previous literatures [2,22,28].
The isoeld magnetization measurements were carried out as:
cooling the sample down to T (a full martensitic state) in the
absence of magnetic elds, and then the measurement was made
on increasing temperature from the T to T + (a full austenitic
state) with a scan rate of 1.0 K/min in the presence of magnetic
eld (H , T T + ). In this way, the isoeld M ( T ) heating curve
was obtained. Subsequently, the measurement was taken on the
decreasing temperature from the T + to the T without removing
the magnetic eld (H , T + T ), and the isoeld M ( T ) cooling
curve was acquired as well.
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Fig. 1. The M ( T ) curve under a static magnetic eld of 1 T for Ni43 Mn46 Sn11 sample
(full circles). The red and blue dot lines represent M A ( T ) and M M ( T ) obtained by
extrapolating the linear part of magnetization. The corresponding austenite fraction
f ( T ) is represented using a green solid line. (For interpretation of the references to
color in this gure legend, the reader is referred to the web version of this article.)
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f (T ) =
M (T ) M M (T )
M A (T ) M M (T )
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(2)
Following Eq. (2), the resultant f ( T ) curve at H = 1 T was obtained, as indicated by the green solid line in Fig. 1.
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Fig. 2. The schematic illustration of calculated f ( T ) (the black dashed line for H =
50 mT, and the green one for H = 3 T) and the corresponding f ( T ) (red solid
line) curves in the heating run for Ni43 Mn46 Sn11 sample. Inset: The M ( T ) heating
curve under elds of 50 mT and 3 T. (For interpretation of the references to color
in this gure legend, the reader is referred to the web version of this article.)
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S tr = M (dT t /dH )1 .
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Fig. 3. (a) The M ( T ) isoeld curves upon heating and cooling in magnetic elds
of 50 mT, 1 T, 2 T and 3 T. (b) T t versus H phase diagram deduced from isoeld
curves. (c) Field dependence of M for Ni43 Mn46 Sn11 .
S T f S tr = f M
dT t
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(3)
dH
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Fig. 4. The calculated S T values for Ni43 Mn46 Sn11 : (a)(b) by CCIF; (c)(d) by
MRIT; (e)(f) by MRIF. The left panel shows those upon cooling, and the right panel
shows those for heating.
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Fig. 5. (a) The M ( T ) isoeld curves upon heating and cooling in magnetic elds of
50 mT, 0.5 T, 1 T, 2 T and 3 T. (b) T t versus H phase diagram deduced from isoeld
curves. (c) Field dependence of M for Ni50 Mn35 Sn15 . (For interpretation of the
references to color in this gure, the reader is referred to the web version of this
article.)
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Fig. 6. The calculated S T values for Ni50 Mn35 Sn15 : (a)(b) by CCIF; (c)(d) by
MRIT; (e)(f) by MRIF. The left panel shows those upon cooling, and the right panel
shows those for heating.
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Ni50 Mn35 Sn15 alloy, more importantly, the S T ( T ) curves calculated by every method (CCIF, MRIF and MRIT) are all coincident
(see Fig. 6), and are also in well agreement with that obtained
by quasi-direct calorimetric measurements [17]. These experimental results further prove that the CCIF method proposed by us to
determine MCE in NiMnSn alloys is faithworthy. According to
previous works [10,35], we can nd that an inverse MCE in Mnrich NiMn based Heusler alloys should primarily rely on three parameters including the M, the dT t /dH and the transition width.
Considering the fact that the magnetic contribution works against
the structural contribution in the NiMnSn system, it is necessary
to decrease the M suitably, and simultaneously maintain a strong
coupling to the magnetic eld for obtaining an optimized MCE.
Under this condition, in terms of Eq. (3), a larger S tr requires
a smaller dT t /dH . In this case, the only a partial phase transition
(corresponding to a small f ) would be arrested by magnetic eld
in the presence of wide transition width. For example, the dT t /dH
with a value of 2 K/T in Ni43 Mn46 Sn11 alloy, applying a magnetic
eld change of 3 T can only shift its f ( T ) curve by 6 K, which is
signicantly lower than that of transition width (25 K). As a consequence, only 50% of the transition can be induced by the eld
(see in Fig. 2) and resultant S T will thus be decreased dramatically in comparison to its S tr (see in Fig. 4). Therefore, we can
conclude that a relatively low dT t /dH is accompanied with a broad
transition width for these two NiMnSn samples, which leads to
the fact that f can only maintain in a narrow temperature interval, thus giving rise to a peak-shape S T ( T ) curves (see in Figs. 4
and 6). In reality, such a phenomenon actually reects the intrinsic nature of inverse MCE for NiMnSn system with martensitic
transformation.
A great deal of experimental studies indicated that the introduction of suitable transition-metal (Co, Fe, etc.) can improve
the inverse MCE of ternary NiMnZ alloys [22,3840]. For instance, Chen et al. have obtained an enhanced MCE in quaternary
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Fig. 7. The S T curves for a eld change H = 5 T of Ni45 Co5 Mn36.6 In13.4 by CCIF
(red open circles) and MRIT (black solid rectangles). The spike (shadow area) corresponding to MRIT was removed by the authors of Ref. [22]. (For interpretation
of the references to color in this gure legend, the reader is referred to the web
version of this article.)
Fig. 8. The S T curves of MnAs by both CCIF (solid lines) and MRIT (dot lines). The
original M ( T ) data and S T results derived from MRIT are extracted from Ref. [2].
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f (T ) =
M ( T ) M LT ( T )
M HT ( T ) M LT ( T )
(5)
Here, the M LT ( T ) and M HT ( T ) denote the magnetizations of lowand high-temperature phases, respectively. Adopting the M and
the dT t /dH with the values of 95.5 emu/g and 3.4 K/T, the S T of
MnAs in various magnetic elds were recalculated by using CCIF,
as displayed in Fig. 8. From this gure, it can be remarkably distinguished that the maximum S T for this sample is 28.09 J/kg K,
rather than the spike value (40.8 J/kg K) calculated by the authors. The appearance of spurious spike has also been observed
in other giant magnetocaloric compounds [28,41], which means
that the MRIT is incapable used in the case of mixed phase near
transition point. Consequently, from the results calculated by us,
the S T quickly reaches a saturated value at a low magnetic eld,
while the further increasing magnetic eld only plays a pivotal
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Fig. 9. (a) The S T curves of Gd5 Si2 Ge2 by MRIT, CCIF and another M ( T )-based
method in Ref. [28]. (b) The background removed S T curves from these three
methods. (c) The S T curve by CCIF with consideration of the variation of M.
Insets: The eld dependences of T t and M.
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ST
n
S Ti
n
i
f i M i
dH
dT t
(6)
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[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[25]
[26]
4. Conclusions
[28]
In summary, the method based on CC-equation while accounting for the phase fraction change was developed to determine
the S T for some representative materials, such as NiMnSn,
NiCoMnIn, MnAs and Gd5 Si2 Ge2 . Our experimental results unambiguously demonstrated that this method is a quite simple and
effective way to obtain a realistic value of S T in the particularly interesting class of magnetocaloric materials. In comparison
to MRIF, moreover, this method only requires a few M ( T ) curves
and reduces the cost of measuring signicantly. Such a method
should be helpful to equitably deal with the MCE for many magnetic materials during FOMT.
[29]
[24]
[27]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
Acknowledgements
[37]
This work was supported by the National Natural Science Foundation of China (Grant Nos. 11364035, 11404186, and 51371111),
the Key Basic Research Program of Science and Technology Commission of Shanghai Municipality (Grant No. 13JC1402400), Project
for Innovative Research Team of Qujing Normal University (Grant
No. TD201301), and Project for Applied Basic Research Programs of
Yunnan Province (Grant Nos. 2013FZ110 and 2012FD051).
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[3]
[4]
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