Microstructure, martensitic transitions, magnetocaloric, and exchange bias properties

in Fe-doped Ni-Mn-Sn melt-spun ribbons

X. G. Zhao, M. Tong, C. W. Shih, B. Li, W. C. Chang, W. Liu, and Z. D. Zhang

Citation: Journal of Applied Physics 113, 17A913 (2013); doi: 10.1063/1.4794881

View online: http://dx.doi.org/10.1063/1.4794881
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 JOURNAL OF APPLIED PHYSICS 113, 17A913 (2013)

Microstructure, martensitic transitions, magnetocaloric, and exchange

bias properties in Fe-doped Ni-Mn-Sn melt-spun ribbons
X. G. Zhao,1,2,a) M. Tong,2 C. W. Shih,1 B. Li,2 W. C. Chang,1,a) W. Liu,2 and Z. D. Zhang2
1
Department of Physics, National Chung Cheng University, Chia-Yi 62102, Taiwan
2
Shenyang National Laboratory for Materials Science, Institute of Metal Research, and International Centre
for Materials Physics, Chinese Academy of Sciences, Shenyang 110016, China
(Presented 18 January 2013; received 26 October 2012; accepted 29 November 2012; published
online 14 March 2013)
The effects of Fe substitution for Ni on microstructure, phase transformations, magnetocaloric effect,
and exchange-bias behavior of the Ni46xFexMn43Sn11 (x 03) alloy ribbons have been investigated.
The free surface of as-spun Fe-doped ribbons shows the granular microstructure containing multiple
shapes (the tree leaf-like, small columnar grain, etc.), while the ordered columnar grains are observed in
fracture cross-section. The martensitic structural transition temperature (TM) of as-annealed ribbons
decreases from 240 K for x 0 to 185 K for x 3 due to the decrease in valence electron concentration,
while the Curie temperature of the austenitic phase remains almost unchanged (TC 275 K). The
positive values of magnetic entropy changes (DSM), around TM, are 21.0, 29.1, 24.1, and 14.8 J/kg K
for x 03, respectively, while the negative DSM values vary in 3.03.5 J/kg K range around TC,
under a field change of 05 T. The values of exchange-bias field (HE) at 10 K change in the range of 469
to 534 Oe and the coercivity (HC) slightly decreases from 245 to 186 Oe, respectively, as x is increased.
C 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4794881]
V

Ni-Mn-X (X In, Sn, and Sb) ferromagnetic shape
memory alloys (FSMAs) have attracted much attention since
the discovery of magnetic-field-induced reverse martensitic
transformation (MT) by Sutou et al. in 2004.1 In these alloy
systems, the MT coincides with the magnetic transformation
from a cubic L21 structure ferromagnetic (FM) austenite to
an orthorhombic weak-magnetic martensite. It is reported
that the martensitic transformation temperature (TM) of
FSMAs can be tuned by altering the composition of the alloys
or substituting elements, and is very sensitive to the values of
the valence electron concentration e/a (electrons per atom).2
In 2006, Kainuma et al. achieved shape recovery accompany-
ing the martensitic transformation in Ni-Co-Mn-Sn polycrys-
talline alloys,3 demonstrating the potential of the alloys for
actuation applications in smart systems. Furthermore, these
alloy systems also exhibit other interesting properties, such as
large magnetoresistance (MR),4 giant magnetocaloric effects
(MCE),5 and exchange-bias (EB) behavior.6
On the other hand, rapid solidification by melt-spinning
process offers a metallurgically interesting route to synthesizing
ribbons with highly textured microstructure. The melt-spinning
technique has been employed to synthesize Ni-Mn-Sn (Ref. 7)
materials with improved magnetocaloric properties. In this
work, Ni46xFexMn43Sn11 (x 03) alloy ribbons were also
obtained using melt-spinning technique. The effects of Fe sub-
stitution for Ni on structure, phase transformations, MCE and
EB behaviors of these ribbons have been investigated.
The Ni46xFexMn43Sn11 (x 03) ribbon samples were
melt-spun using as-cast alloys in argon environment at a linear
speed of 30 m/s. Some of the as-spun ribbons were annealed
at 1123 K for 20 min and finally quenched in ice water.
a)
Author to whom correspondence should be addressed. Electronic mail:
xgzhao@imr.ac.cn, phywcc@ccu.edu.tw.
Microstructures of ribbons were examined using a scanning
electron microscope (SEM). The dependence of the magnet-
ization on temperature and field was studied using a SQUID
magnetometer in the temperature range of 10350 K, and in
external magnetic fields up to 50 kOe. Magnetic phase transi-
tion temperature was inferred from the maximum or minimum
in the dM/dT versus T curve.
Typical SEM micrographs of the fracture cross-section
and free surface of as-spun Ni45Fe1Mn43Sn11 ribbons are
shown in Fig. 1. As shown in Fig. 1(a), the small equiaxed
grains crystallize at the thin top layer of the wheel side and
change abruptly into an ordered columnar microstructure. The
longer axis of the columnar grains tends to align perpendicu-
larly to the plane surface of the ribbon, suggesting that heat
removal during rapid-solidification process induces directional
growth of the crystalline phase. While the free surface of
as-spun Fe-doped ribbons shows the granular microstructure
containing multiple shapes (the tree leaf-like, small columnar
grains, small size grains between columnar grains), in which
the grain sizes of about 210 lm are observed, as demon-
strated in Figs. 1(b)1(d). This may be due to the high cooling
rate and different growth dynamics during rapid-solidification
process.
Figure 2 shows the temperature dependence of magnet-
ization of the annealed Ni46xFexMn43Sn11 (x 03) rib-
bons in the zero-field cooled (ZFC) and field-cooled (FC)
modes, measured in a field of 200 Oe. From Fig. 2(a), with
increasing temperature, a magnetic transition was observed
at around 95 K in the ZFC curves. Since the EB phenomena
vanish around this temperature, we refer it as conventional
EB blocking temperature, TB. With further increase in tem-
perature, magnetization first decreases and an inflexion point
appears, which corresponds to Curie temperature of mag-
netic transition of the martensitic phase, TCM 178 K. Then,

0021-8979/2013/113(17)/17A913/3/$30.00 113, 17A913-1 C 2013 American Institute of Physics

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 17A913-2 Zhao et al. J. Appl. Phys. 113, 17A913 (2013)

FIG. 1. Typical SEM micrographs of Ni45Fe1Mn43Sn11 as-spun ribbons: (a)

fractured cross-section, (b)(d) free surface of different regions.
a sudden jump in magnetization is observed, which indicates
the occurrence of the first-order reverse martensitic transfor-
mation (TM 240 K). Finally, with further increasing tem-
perature, the magnetization decreases again, the Curie
temperature (TC) of the austenitic phase for a FM to para-
magnetic (PM) transition was determined to be 275 K. A
thermal hysteresis of about 10 K, which is a signature of the
first-order transformation nature, is observed around the MT
temperature. The values of phase transformation tempera-
ture, estimated from M-T curves, are listed in Table I. As
shown in Fig. 2 and Table I, the martensitic structural transi-
tion temperature (TM) of annealed ribbons decreases from
240 K for x 0 to 185 K for x 3, whereas TCM and TB
slightly decrease, the disappearance of TCM for x 3 samples
hereon may be due to the facts that TCM is higher than TM
from intersection method of tangent line. It was reported that
the characteristic temperatures in FSMAs are related to the
valence electron concentration e/a (electrons per atom).2 The
data of e/a for all of the samples are also shown in Table I.
From this table, we can observe that characteristic tempera-
tures decrease with decreasing values of e/a. This relation-
ship is helpful for us to tune the phase transition temperature
in FSMAs, which is essential for the application in magnetic
refrigeration. However, the Curie temperature of the austen-
itic phase remains almost unchanged (TC  275 K).
Figure 3(a) shows typical M (H) curves for
Ni45Fe1Mn43Sn11 in the vicinity of TM and TC at fields up to
50 kOe (other curves are not shown here). The typical
FIG. 2. Temperature dependence of ZFC and FC magnetization curves M
(T) for the annealed Ni46xFexMn43Sn11 (x 03) ribbons, measured at a
field of 200 Oe.
metamagnetic behaviors of M (H) due to the field-induced
reverse MT can be observed around 236 K. However, no
trace of metamagnetism can be observed from the M-H
curves around TC. The magnetic entropy changes (DSM) as a
function of temperature and magnetic field was calculated
from magnetization isotherms using the Maxwell relation.8
The temperature dependence of calculated DSM in the
vicinity of TM and TC is shown in Fig. 3(b). In Fig. 3(b), a
positive peak of magnetic entropy changes (DSM) can be
observed around MT temperature. The maximum values of
DSM are 21.0, 29.1, 24.1, and 14.8 J/kg K for x 03,
respectively, with a sharp and high peak over a narrow tem-
perature interval around TM, under a field change of 050
kOe. The large DSM in Ni46xFexMn43Sn11 (x 03) around
the MT temperature can be ascribed to the abrupt change of
magnetization between the low-temperature and high-
temperature phases. Compared to Ni46Mn43Sn11, larger
magnetization jumps can be obtained in Fe-doped
Ni46xFexMn43Sn11 ribbons for x 12, consequently
resulting in large DSM. On the other hand, the negative
DSM values vary in 3.03.5 J/kg K range with a wider peak
over a broader temperature range around TC, which is close
to room temperature. These values are larger than those in
amorphous Fe68.5Mo5Si13.5B9Cu1Nb3 ribbons.9
Another important aspect of evaluating a magnetic re-
frigerant is the refrigerant capacity (RC),8 which is con-
nected to the entropy absorbed by the refrigerant at the cold

TABLE I. The martensitic transformation temperature (TM), Curie temperature of the austenitic phase (TC), Curie temperature of the martensitic phase (TCM),
blocking temperature (TB), the valence electron concentration e/a, magnetic entropy change (DSM), the refrigerant capacity (RC-1 of the DSM, RC-2 of
DSM), EB field (HE), and coercivity HC for Ni46xFex Mn43Sn11 (x 03) ribbons.

x TM (K) TC (K) TCM (K) TB (K) e/a DSM (J/kg K) DSM (J/kg K) RC-1 (J/kg) RC-2 (J/kg) HE (Oe) HC (Oe)

0 240 275 178 95 8.05 21.0 3.35 184 212 469 245
1 238 275 176 95 8.03 29.1 3.50 169 221 524 200
2 225 275 174 90 8.01 24.1 3.34 202 273 534 194
3 185 276 80 7.99 14.8 3.02 163 314 492 186

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 17A913-3 Zhao et al.
FIG. 3. (a) Isothermal magnetization curves for annealed Ni45Fe1Mn43Sn11
ribbons obtained at a field of 50 kOe around TM and TC, (b) Magnetic en-
tropy changes (DSM) of Ni46xFexMn43Sn11 (x 03) annealed ribbons with
temperature at a field of 50 kOe around TM and TC.
end of the cycle and its temperature spun, which is of
practical significance. In this work, we use equation
(RC DSMmax  dTFWHM, dTFWHM is full width at half
maximum DSM) to calculate RC-1 of the DSM, and RC-2 of
DSM. The results are also listed in Table I. It can be seen that,
although the peak values of DSM are much larger, the RC-1 s of
DSM are less than RC-2 s of DSM due to narrow temperature
interval around TM. Zhang et al. have reported a specialized mag-
netic refrigerator,10 in which both magnetizing and demagnetizing
processes are utilized for cooling, which will certainly increase
the efficiency of the magnetic refrigerator. The materials that ex-
hibit both positive and negative DSM may be employed in such a
refrigeration cycle. In this work, the total RCs (RC-1s plus RC-2s)
on complete refrigeration cycle vary in 390477 J/kg range over
the entire temperature range. Such values of RC are comparable
to that of Gd (about 400 J/kg).8 Furthermore, considering the cost
of magnetic refrigerant materials, one would prefer relatively
cheaper magnetic alloys. The elements in our samples, Ni, Fe,
Mn, and Sn, are comparatively cheap.
Fig. 4 shows magnetic hysteresis loops at 10 K of the
annealed Ni46xFexMn43Sn11 (x 03) ribbons after FC at 20
kOe from 300 K. For clear visualization of the variation of the
loop shift, the magnified hysteresis loop from 2.5 to 2.5 kOe
is shown here. As an example, the variation of the EB field HE
and coercivity HC as a function of temperature from 10 K to
100 K for the annealed Ni45Fe1Mn43Sn11 ribbons is displayed
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J. Appl. Phys. 113, 17A913 (2013)
FIG. 4. Magnetic hysteresis loops in small field region measured at 10 K af-
ter FC at 20 kOe of the annealed Ni46xFexMn43Sn11 (x 03) ribbons,
inset shows the variation of the HE and HC as a function of temperature from
10 K to 100 K for the annealed Ni45Fe1Mn43Sn11 ribbons.
in the inset of Fig. 4. As it is evident from the figure, the values
of HE vary in 469 and 534 Oe range and the coercivity (HC)
decreases slightly from 245 to 186 Oe, as x is increased from 0
to 3. The value of HE decreases almost monotonously with
increase in temperature and becomes zero above 80 K, mean-
time, HC initially increases with temperature and then
decreases after reaching a maximum in the inset of Fig. 4, the
similar trends were also obtained for the other samples (not
shown here). Such temperature dependencies of HE and HC are
typical for EB systems. The EB phenomena above should be
attributed to the change of exchange interactions at antiferro-
magnetic (AFM)/FM interfaces in the Fe-substituted Ni-Mn-
Sn ribbons due to the slight change of distance between Mn
atoms by appreciable difference in atomic radius of Fe and Ni.
In the Ni46xFexMn43Sn11 (x 03) ribbons, the free
surface of as-spun Fe doped ribbons shows the granular
microstructure containing multiple shapes, while the ordered
columnar grains were observed in fracture cross-section.
With the addition of Fe, the MT temperature decreases,
while TC remains almost unchanged. Large DSM can be
obtained under DH 50 kOe for x 12 samples compared
to Ni-Mn-Sn ribbon. The large DSM, total RC values, adjust-
able MT temperatures, EB properties, and low costs suggest
that Ni-Fe-Mn-Sn ribbons would be promising candidates
for magnetic refrigeration and magnetic memory application.
This work has been supported by the National Science
Council, Taiwan under Grant No. NSC-101-2112-M-194-
005-MY3 and the National Natural Science Foundation of
China under Grant Nos. 51271179 and 50831006.
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