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Phase diagram and composition optimization for magnetic shape memory

effect in Ni–Co–Mn–Sn alloys

Article in Applied Physics Letters · August 2010

DOI: 10.1063/1.3454239 · Source: IEEE Xplore

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 APPLIED PHYSICS LETTERS 97, 021908 共2010兲

Phase diagram and composition optimization for magnetic shape memory

effect in Ni–Co–Mn–Sn alloys
D. Y. Cong,a兲 S. Roth, M. Pötschke, C. Hürrich, and L. Schultz
Institute for Metallic Materials, IFW Dresden, P.O. Box 270116, D-01171 Dresden, Germany
共Received 6 April 2010; accepted 24 May 2010; published online 13 July 2010兲
The composition dependent phase transformation and magnetic properties of the Ni50−xCoxMn39Sn11
共0 ⱕ x ⱕ 10兲 alloys were systematically investigated. Based on the obtained results, the phase
diagram of this alloy system was established. Considering the combination of large magnetization
difference across phase transformation ⌬M and small transformation entropy change ⌬S, the
optimal composition range of 5 ⱕ x ⱕ 8 for magnetic-field-induced phase transformation 共MFIPT兲
and consequently magnetic shape memory effect was figured out. Furthermore, the decrease in
martensitic transformation temperatures by magnetic fields and almost fully reversible MFIPT from
martensite to austenite were confirmed in the alloys within this composition range. © 2010
American Institute of Physics. 关doi:10.1063/1.3454239兴

Magnetic shape memory alloys 共MSMAs兲 display a
shape memory effect 共SME兲 actuated by magnetic fields1–3
and have promising prospects for applications as actuators
and sensors. According to the actuation mechanism, the
MSMAs can be classified into two classes. The first class of
alloys 共e.g., Ni–Mn–Ga兲 show a magnetic SME 共MSME兲
originating from the rearrangement of martensitic
variants.1,2,4–8 This MSME can be up to ⬃10% 共Ref. 5兲 but
the blocking stress is quite low. Recently, the other class of
MSMAs 共e.g., Ni–Co–Mn–In and Ni–Co–Mn–Sn兲 which
display a MSME due to the magnetic-field-induced phase
transformation 共MFIPT兲 from martensite to austenite, was
developed.3,9–11 The high output stress level3,9 and relatively
large MSME 共Ref. 3兲 make this class of MSMAs extremely
attractive. Among these MSMAs, the Ni–Co–Mn–In alloys
are most extensively studied 共see e.g., Refs. 3 and 9兲; never-
theless, the Ni–Co–Mn–Sn alloys are also quite promising
for practical applications because they contain no expensive
elements and, particularly, considerable MSME can be ob-
tained even in polycrystals.10 A ⬃1.0% one-way MSME and
a ⬃0.3% two-way MSME have been observed in a polycrys-
talline Ni–Co–Mn–Sn alloy.10 However, in spite of some
scattered studies,12–14 there is no systematic investigation on
the composition dependent phase transformation and mag-
netic properties of Ni–Co–Mn–Sn alloys up to now. Conse-
quently, the phase diagram of the quaternary Ni–Co–Mn–Sn
system has not been established and the optimal composition
range for MSME remains unknown. In this paper, we
report on the establishment of the phase diagram of the
Ni50−xCoxMn39Sn11 alloy system and the composition optimi-
zation for MSME in this alloy system. Such an investigation
helps to understand the correlation between composition and
materials properties and thus is of great importance to the
design of high-performance Ni–Co–Mn–Sn MSMAs.
A series of polycrystalline Ni50−xCoxMn39Sn11 共at. %,
x = 0 , 1 , 2 , . . . , 10兲 rod ingots each of ⬃30 g were prepared
by induction melting under an Ar atmosphere. The ingots
were subsequently annealed at 1223 K for 6 h under an
Ar/5% H2 atmosphere for homogenization. The phase trans-
a兲
Author to whom correspondence should be addressed. Electronic mail:
d.cong@ifw-dresden.de.
formation temperatures and transformation entropy change
were determined by differential scanning calorimetry 共DSC兲
in the temperature range of 213–473 K, with a heating and
cooling rate of 10 K/min. The magnetic properties and
MFIPT were investigated using a vibrating sample magneto-
meter 共VSM兲 and a superconducting quantum interference
device 共SQUID兲; both the magnetization versus temperature
关i.e., M共T兲兴 curves and magnetization versus magnetic field
关i.e., M共H兲兴 curves were measured.
DSC measurements show that the martensitic transfor-
mation temperature TM 关defined as 共M s + M f + As + A f 兲 / 4,
where M s, M f , As, and A f are martensitic and reverse
transformation start and finish temperatures兴 of the
Ni50−xCoxMn39Sn11 alloys first decreases slowly when 0 ⱕ x
ⱕ 5 and then decreases rapidly when 5 ⬍ x ⱕ 8, with x in-
creasing, as shown in the phase diagram in Fig. 1 共DSC
results of the representative alloys are displayed in the insets
of Fig. 2兲. In the alloys with x = 9 and 10, no martensitic
transformation was observed in the DSC measurement 关see
the inset of Fig. 2共c兲兴; M共T兲 measurements under a magnetic
field of 0.01 T were performed during cooling from 300 to
10 K to further study the transformation behavior of these
alloys but no phase transformation was observed. Therefore,
it can be concluded that the austenite in these two alloys
FIG. 1. 共Color online兲 Phase diagram of the quaternary Ni50−xCoxMn39Sn11
共0 ⱕ x ⱕ 10兲 alloys. T M and TC denote the martensitic transformation tem-
perature and the Curie temperature of austenite, respectively.

0003-6951/2010/97共2兲/021908/3/$30.00 97, 021908-1 © 2010 American Institute of Physics

021908-2 Cong et al.
FIG. 2. 共Color online兲 M共T兲 curves under a constant magnetic field of 0.05 or 1.9 T for the Ni49Co1Mn39Sn11 共a兲, Ni44Co6Mn39Sn11 共b兲, and Ni41Co9Mn39Sn11
共c兲 alloys. Note the different scales of the magnetization axis in 共a兲, 共b兲, and 共c兲. The insets of 共a兲, 共b兲, and 共c兲 show the DSC curves of the respective alloys.
remains stable down to 10 K. Careful microstructure obser-
vation shows that precipitation embedded in the austenitic
matrix occurs in the alloys with x = 9 and 10 共but not in the
alloys with 0 ⱕ x ⱕ 8兲. This is the main reason for the disap-
pearance of martensitic transformation in these two alloys.
It was further revealed by DSC measurements that the
transformation entropy change ⌬S of the Ni50−xCoxMn39Sn11
alloys remains almost constant 关⬃42 J / 共kg K兲兴 when 0 ⱕ x
ⱕ 4 but decreases rapidly with x increasing when 4 ⬍ x ⱕ 8
and reaches ⬃16 J / 共kg K兲 when x = 8. According to the
Clausius–Clapeyron relation in the magnetic phase diagram,3
the decrease in T M 共⌬T M 兲 of the MSMAs induced by mag-
netic field change 共⌬H兲 can be expressed as
⌬T M ⬇ ␮0共⌬M/⌬S兲⌬H,
where ⌬M is the magnetization difference between austenite
and martensite. Therefore, the combination of a large ⌬M
and a small ⌬S will lead to a large ⌬T and thus benefit the
MFIPT at a constant temperature close to As.
According to the different characteristics of the M共T兲
curves 共see curves for the representative alloys in Fig. 2兲, the
Ni50−xCoxMn39Sn11 alloys can be classified into three groups.
The alloys in Group A 共with 0 ⱕ x ⱕ 4兲 have an austenite and
a martensite both with very low magnetization 关Fig. 2共a兲兴,
and thus a small ⌬M. In contrast, the alloys in Group B 共with
5 ⱕ x ⱕ 8兲 have an austenite with high magnetization and a
martensite with low magnetization across transformation
关Fig. 2共b兲兴, and consequently a large ⌬M. The alloys in
Group C 共with 9 ⱕ x ⱕ 10兲 have an austenite with high mag-
netization below Curie temperature 关Fig. 2共c兲兴, which re-
mains stable down to very low temperatures, as there is no
martensitic transformation in these alloys. The detailed mag-
netic properties of these three groups of alloys are analyzed
as follows. Once again the alloys whose M共T兲 curves are
shown in Fig. 2 are selected as representative alloys.
For the alloys in Group A, the M共H兲 curve for austenite
shows a linear dependence on magnetic field 关Fig. 3共a兲兴. The
magnetic susceptibility ␹ of austenite is quite low and, fur-
thermore, the 1 / ␹ versus temperature curve can be well fitted
linearly 关Fig. 3共b兲兴, indicating that the temperature depen-
dence of ␹ follows the Curie-Weiss law ␹ = C / 共T − ␪C兲 with
␪C ⬎ 0. All these results provide unambiguous evidence that
the austenite is paramagnetic. Similarly, the martensite of
this group of alloys is also determined to be paramagnetic
关Figs. 3共a兲 and 3共b兲兴. For the alloys in Group B, the M共H兲
curve in Fig. 3共c兲 clearly demonstrates that the austenite
shows a typical ferromagnetic behavior. In contrast, the
M共H兲 curve in the inset of Fig. 3共d兲 shows that the magne-
tization of martensite first increases rapidly and then in-
creases relatively slowly as magnetic field increases; it does
Appl. Phys. Lett. 97, 021908 共2010兲
not saturate even in the high magnetic field of 9 T 关Fig. 3共d兲兴.
The M共H兲 curve shows no magnetic hysteresis 关inset of Fig.
3共d兲兴 and the magnetization is low. This suggests that super-
paramagnetic behavior may exist in the martensite. Further
detailed analyses show that the M共H兲 curves at various tem-
peratures 关Fig. 3共d兲兴 can be well fitted according to the modi-
fied Langevin model that describes the magnetic behavior of
superparamagnetic clusters 共with a density N and an average
moment of ␮ ¯ 兲 embedded in a paramagnetic matrix of suscep-
tibility ␹0 : M共H兲 = N␮¯ L共s兲 + ␹0H, in which L共s兲 = coth共s兲
− 1 / s is the Langevin function and s = ␮¯ ␮0H / kBT 共kB being
Boltzmann constant兲. These good fittings 关Fig. 3共d兲兴 un-
equivocally corroborate that the martensite indeed shows su-
perparamagnetic behavior.15,16 For the alloys in Group C, the
共1兲 M共H兲 curve of austenite is similar to that shown in Fig. 3共c兲,
indicating that the austenite is ferromagnetic.
The Curie temperature of austenite 共TC兲 of the alloys in
Group B and Group C is determined from the low-field M共T兲
measurement 关Fig. 2共b兲兴. It should be noted that TC of the
alloys in Group A cannot be detected as it lies below T M of
these alloys 关Fig. 2共a兲兴. It is found that in the whole compo-
sition range 5 ⱕ x ⱕ 10, TC increases almost linearly as x in-
creases, with ⌬TC / ⌬x ⬇ 15 K, as shown in the phase dia-
FIG. 3. 共Color online兲 共a兲 M共H兲 curves at 423 K for austenite and at 296 K
for martensite, and 共b兲 temperature dependence of inverse magnetic suscep-
tibility of austenite and martensite, of the Ni49Co1Mn39Sn11 alloy. The open
symbols and solid lines in 共b兲 denote the experimental data and the Curie–
Weiss fittings, respectively. 共c兲 M共H兲 curve at 370 K for austenite of the
Ni44Co6Mn39Sn11 alloy. 共d兲 Experimentally recorded M共H兲 curves 共open
symbols兲 at 150, 200, 250, and 310 K for martensite of the Ni44Co6Mn39Sn11
alloy and the corresponding curves 共solid lines兲 fitted according to the modi-
fied Langevin model. The inset shows a full magnetic hysteresis loop ex-
perimentally recorded at 298 K, in the magnetic field range between ⫾1 T.
021908-3 Cong et al.
FIG. 4. 共Color online兲 ⌬M / ⌬S as a function of Co content x in the
Ni50−xCoxMn39Sn11 alloys.
gram in Fig. 1. The enhancement of TC by substitution of Co
for Ni could be attributed to the stronger Co–Mn exchange
interaction as compared to that between the Ni–Mn pair.17
Similar results were also found in Ni–Co–Mn–Ga alloys.17
Based on the above results on phase transformation and
magnetic properties, the phase diagram of the quaternary
Ni50−xCoxMn39Sn11 共0 ⱕ x ⱕ 10兲 alloys is established, as
shown in Fig. 1. In order to evaluate how effectively the T M
of the alloys can be lowered by applying a magnetic field
关see Eq. 共1兲兴 and to find out the optimal composition range
for MFIPT, ⌬M / ⌬S 关in Eq. 共1兲兴 as a function of x in the
Ni50−xCoxMn39Sn11 alloys is plotted in Fig. 4. Obviously, for
the alloys in Group A, ⌬M / ⌬S is very small, although it
increases slightly with x increasing. In contrast, for the alloys
in Group B, ⌬M / ⌬S has a large value and, what is more, it
increases rapidly as x increases. Therefore, it can be con-
cluded that the optimal composition range for MFIPT and
consequently MSME is 5 ⱕ x ⱕ 8.
From the M共T兲 measurements under different magnetic
fields we have confirmed that there is no magnetic-field-
induced decrease in T M in the alloys in Group A 关see Fig.
2共a兲兴. In contrast, the magnetic-field-induced decrease in TM
and MFIPT were indeed observed in the alloys in Group B.
Take the Ni42Co8Mn39Sn11 alloy as an example. From the
M共T兲 curves in Fig. 5共a兲, it can be clearly seen that the TM is
significantly lowered by the application of magnetic fields,
particularly with ⌬As / ␮0⌬H ⬇ 5.2 K / T. From the M共H兲
curves in Fig. 5共b兲, it is found that, while the M共H兲 curves at
150 and 300 K exhibit typical magnetic behaviors of marten-
site and austenite, the curves at 240, 250, and 260 K clearly
indicate a MFIPT from martensite to austenite. Furthermore,
the M共H兲 curves recorded during the first and second cycles
of increasing and decreasing magnetic field almost overlap
with each other, which, according to Ref. 18, indicates that
the MFIPT at these temperatures is almost fully reversible.
All these results unambiguously indicate that MSME could
be expected in this alloy.
In summary, we systematically investigated the compo-
sition dependent phase transformation and magnetic proper-
ties of the Ni50−xCoxMn39Sn11 共0 ⱕ x ⱕ 10兲 alloys and estab-
lished the phase diagram of this alloy system. Considering
the combination of a large ⌬M and a small ⌬S, the optimal
composition range for MFIPT and consequently MSME is
found to be 5 ⱕ x ⱕ 8. The decrease in T M induced by apply-
ing magnetic fields and the MFIPT from martensite to aus-
tenite were confirmed in the alloys within this composition
range. These results provide fundamental experimental data
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Appl. Phys. Lett. 97, 021908 共2010兲
FIG. 5. 共Color online兲 共a兲 M共T兲 curves under constant magnetic fields of
0.05, 5, and 9 T, and 共b兲 M共H兲 curves at 150, 240, 250, 260, and 330 K, for
the Ni42Co8Mn39Sn11 alloy. The solid and open symbols in 共b兲 denote, re-
spectively, the M共H兲 curves recorded during the first and second cycles of
increasing and decreasing magnetic field.
that are crucial to the development of promising MSMAs
with excellent properties.
This work is supported by DFG 共Grant No. SPP 1239兲
and the Alexander von Humboldt Foundation. Experimental
assistance from Dr. T. G. Woodcock and A. Pöhl is greatly
acknowledged.
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