Investigation of the intermediate phase and

magnetocaloric properties in high-pressure

annealing Ni–Mn–Co–Sn alloy
Cite as: Appl. Phys. Lett. 97, 052506 (2010); https://doi.org/10.1063/1.3476351
Submitted: 27 June 2010 . Accepted: 18 July 2010 . Published Online: 05 August 2010

S. C. Ma, H. C. Xuan, C. L. Zhang, L. Y. Wang, Q. Q. Cao, D. H. Wang, and Y. W. Du

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Appl. Phys. Lett. 97, 052506 (2010); https://doi.org/10.1063/1.3476351 97, 052506

© 2010 American Institute of Physics.

 APPLIED PHYSICS LETTERS 97, 052506 共2010兲

Investigation of the intermediate phase and magnetocaloric properties

in high-pressure annealing Ni–Mn–Co–Sn alloy
S. C. Ma, H. C. Xuan, C. L. Zhang, L. Y. Wang, Q. Q. Cao, D. H. Wang,a兲 and Y. W. Du
National Laboratory of Solid State Microstructures and Key Laboratory of Nanomaterials for Jiang
Su Province, Nanjing University, Nanjing 210093, People’s Republic of China
共Received 27 June 2010; accepted 18 July 2010; published online 5 August 2010兲
The Ni–Mn–Co–Sn alloy is prepared by high-pressure annealing method. Besides the enhanced
martensitic transformation temperature and the Curie temperature of austenite, an intermediate
phase above the martensitic transformation is observed in this alloy. As a result, two successive
magnetic entropy changes with the same sign are obtained around room-temperature, corresponding
to the martensitic transformation and intermediate phase transition, respectively. The origin of the
intermediate phase for high-pressure annealing Ni–Mn–Co–Sn alloy is discussed. © 2010 American
Institute of Physics. 关doi:10.1063/1.3476351兴

Ni–Mn–Ga Heusler alloys, which are the prototypical The Ni–Mn–Co–Sn ribbons were first prepared by melt-
ferromagnetic shape memory alloys 共FSMAs兲, have drawn spinning the as-cast alloy with the nominal composition
much attention during the recent years due to the giant Ni43Mn41Co5Sn11 with a surface velocity of 10 m s−1. And
magnetic-field-induced strain and other functional then, the melt-spun ribbons were wrapped in tantalum foils
properties.1–3 More interestingly, some of these alloys with and pressed into a graphite pipe heater with the shape of
composition close to the stoichiometric Ni2MnGa exhibit cylinder. The heater was pressed to 4 GPa by a Halltype
a weak first-order phase transition from the austenitic hexahedral anvil press and heated to 1123 K for 10 min. The
phase to the intermediate phase at a temperature prior to the magnetic measurement was carried out using a vibration
martensitic transformation 共MT兲.3–20 This intermediate sample magnetometer 共7300, Lakeshore兲 with a magnetic
phase transition is often characterized by anomaly in the field up to 10 kOe. The electrical resistance measurement
elastic,4–7 thermal,6–10 resistivity,3,5,8,9,11–15 and magnetic was performed by a physical property measurement system
properties.3,5–10,13–16,18 It is widely believed that the interme- 共PPMS, Quantum Design兲 from 200 to 370 K. Thermal be-
diate phase transition originates mainly from the magneto- havior was investigated using a differential scanning calo-
elastic coupling between the magnetic and the structural de- rimeter 共DSC兲 with the heating and cooling rates of 10
grees of freedom in Ni–Mn–Ga alloy system.4–7,10,14,16,19 K/min.
Recently, some Ga-free FSMAs have been found in Figure 1 presents the temperature dependence of magne-
Ni– Mn– X 共X = Sn, In, and Sb兲 alloys.21–33 Among these al- tization M 共T兲 for the melt-spun ribbons and high-pressure
loys, an MT from the ferromagnetic parent phase to a weak- annealing 共HPA兲 Ni–Mn–Co–Sn alloy in the field of 100 Oe
magnetic martensite phase, which is often accompanied by on heating. Both samples show similar thermomagnetic be-
the sharp change in the magnetization and resistivity, has havior. With increasing temperature, an MT between the
been observed in some particular composition ranges. As a weak-magnetic martensitic phase and ferromagnetic austen-
consequence, a variety of interesting properties such as giant itic phase is first observed. Further heating leads to a ferro-
magnetic-field-induced shape recovery,22 large magnetoca- magnetic transition occurring at the Curie temperature of
loric effect 共MCE兲,23–30 and magnetoresistance30–32 have austenite TCA. It is obvious that T M and TCA increase after HPA
been observed around the MT temperature T M . Therefore, process. This enhancement can be understood from the effect
tuning T M and enlarging the working-temperature interval for
these FSMAs are of great importance. Considering the strong
dependence of T M on the valence electron concentration per
atom e / a and Mn–Mn interatomic distances, up to now, the
mostly used methods to tune T M in Ni–Mn based FSMAs
are as follows: 共i兲 adjusting the elemental chemical
composition,21,23,24,30 共ii兲 partial substitution for X with the
same main group isoelectronic elements,29 共iii兲 doping the
interstitial atoms,25 共iv兲 applying hydrostatic pressure,28,33
and 共v兲 changing the annealing condition.26,27 In this paper,
we prepared the Ni–Mn–Co–Sn alloy by annealing the melt-
spun ribbons under high pressure, in which T M were adjusted
to room temperature. Interestingly, an intermediate phase
transition prior to the MT, which was rarely reported in Ga-
free Ni–Mn based FSMAs, was observed.
FIG. 1. 共Color online兲 Temperature dependence of the magnetization for
Ni–Mn–Co–Sn melt-spun ribbon and HPA alloy in the field of 100 Oe on
a兲
Electronic mail: wangdh@nju.edu.cn. heating. The inset presents the enlarged view for the HPA alloy.

0003-6951/2010/97共5兲/052506/3/$30.00 97, 052506-1 © 2010 American Institute of Physics

052506-2 Ma et al. Appl. Phys. Lett. 97, 052506 共2010兲

FIG. 3. 共Color online兲 Intermediate phase transition temperature as a func-

tion of magnetic field in HPA alloy with the solid line as a fit. The inset is a
plot of intermediate phase transition temperature vs M 2 with a linear fit to
the data.

tioned experimental results would suggest the existence of an

intermediate phase in HPA Ni–Mn–Co–Sn alloy.
As we know, the intermediate phase in Ni–Mn–Ga alloys
is a consequence of the magnetoelastic coupling.4–7,10,14,16,19
According to a Landau expansion model,6,14 the free energy
of this intermediate phase transition system can be expressed
as follows:
FIG. 2. 共Color online兲 共a兲 Variation in the resistivity for HPA alloy versus F = Fe + Fm + Fem , 共1兲
temperature and 共b兲 DSC curves upon cooling and heating at a rate of 10
K/min for HPA alloy. where Fe is the elastic energy term, Fm is the magnetic en-
ergy term and Fem is the magnetoelastic energy term, respec-
tively. Some related theoretical and experimental results in-
of annealing and pressure on the phase transition in dicate that Fem contribution plays a crucial role in the free
FSMAs.26,28,33 First, the stress and structural relaxations re- energy of intermediate phase in Ni–Mn–Ga alloys.5–7,14,19
sulting from annealing would be responsible for the increase As a result, the intermediate phase transition temperature
in T M and TCA.26 On the other hand, the stabilization of the TI would decrease with increasing magnetic field.5,16,17 To
martensite and the enhancement of the antiferromagnetic in- investigate the magnetic field dependence of TI in HPA
teraction in the martensitic phase induced by pressure may Ni–Mn–Co–Sn alloy, we measured the M共T兲 curves of our
be another expected reason for the increment.28,33 It is worth sample in different applied fields. Figure 3 shows TI depen-
noting that an anomaly of the thermomagnetic behavior is dence of applied magnetic field for HPA Ni–Mn–Co–Sn al-
observed in HPA alloy, occurring between MT and the ferro- loy. It is obvious that TI is almost inversely proportional
magnetic transition of austenite. As shown in the inset of Fig. to the applied magnetic field and tends to saturation with
1, magnetization above MT displays a bump at a temperature the increasing field, which is consistent with the results of
around 334 K. The rise in magnetization between austenitic Ni–Mn–Ga alloys.5,16,17 As stated in the Landau expansion
finish temperature A f and 334 K is somewhat similar to the model,6,14,16 Fem is quasilinear with the squared magnetic
jump of magnetization observed around T M , suggesting that moment of intermediate phase 共M 2兲. The inset of Fig. 3
the martensitic phase transition should be a two-step process shows TI versus M 2 curve for HPA Ni–Mn–Co–Sn alloy.
and an intermediate phase may exist in HPA Ni–Mn–Co–Sn Similar to Ni–Mn–Ga alloys, TI of our sample decreases al-
alloy.18 most linearly with increasing M 2.14,16 Based on the afore-
To further investigate the intermediate phase of HPA Ni– mentioned experimental results, we argue that a large mag-
Mn–Co–Sn alloy, the electrical resistance and calorimetric netoelastic interaction may exist in HPA Ni–Mn–Co–Sn
measurements were carried out. Figure 2共a兲 shows the resis- alloy.5,14,16 As we know, our sample is obtained by high-
tivity of HPA alloy as a function of temperature ␳共T兲 on pressure method. Applying external stress may induce a ro-
heating. As presented in some earlier reports of the ␳共T兲 tation of magnetic domains, leading to a change in the mag-
behavior in Ni– Mn– X 共X = In, Sn, Sb兲 FSMAs,30–32 the re- netization. On the other hand, the applied stress would
sistivity increases near linearly above A f , showing a metallic deform the unit cells and then modify the values of elastic
behavior. But in the case of our HPA alloy, a change in the constants.4,20 Therefore, the application of pressure can en-
slope of ␳共T兲 curve is observed at a higher temperature hance the magnetoelastic coupling in HPA Ni–Mn–Co–Sn
above A f . As shown in the DSC curves of HPA alloy 关Fig. alloy, which would be responsible for the appearance of in-
2共b兲兴, small peaks between the MT and ferromagnetic tran- termediate phase
sition of austenite can be observed on heating and cooling Another point that deserves attention is the expected ef-
process, indicating the occurrence of a phase transition. Ac- fect of two-step phase transition process on MCE for HPA
cording to the resistivity and thermal behaviors of the inter- Ni–Mn–Co–Sn alloy. Here we calculated the magnetic en-
mediate phase in Ni–Mn–Ga alloys,3,5,6,9–15 the aforemen- tropy changes ⌬S M of this alloy around T M and TI in the field
052506-3 Ma et al. Appl. Phys. Lett. 97, 052506 共2010兲

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