Large magnetic field-induced work output in a NiMnGa seven-layered modulated

martensite
,
E. Pagounis , M. J. Szczerba, R. Chulist, and M. Laufenberg

Citation: Appl. Phys. Lett. 107, 152407 (2015); doi: 10.1063/1.4933303

View online: http://dx.doi.org/10.1063/1.4933303
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Published by the American Institute of Physics
 APPLIED PHYSICS LETTERS 107, 152407 (2015)

Large magnetic field-induced work output in a NiMnGa seven-layered

modulated martensite
E. Pagounis,1,a) M. J. Szczerba,2 R. Chulist,2 and M. Laufenberg1
1
ETO MAGNETIC GmbH, Hardtring 8, 78333 Stockach, Germany
2
Institute of Metallurgy and Materials Science, Polish Academy of Sciences, 30-059 Krakow, Poland
(Received 16 July 2015; accepted 5 October 2015; published online 14 October 2015)
We report the performance of a Ni-Mn-Ga single crystal with a seven-layered lattice modulation
(14M martensite), demonstrating large actuation work output driven by an external magnetic field.
A magnetic field-induced strain of 11.2%, a twinning stress of 0.64 MPa, and a magneto-crystalline
anisotropy energy of 195 kJ/m3 are measured at room temperature, which exceed the best results
reported in Ni-Mn-Ga 14M martensites. The produced magnetically induced work output of about
70 kJ/m3 makes the material attractive for actuator applications. Detailed XRD investigation
reveals that the studied 14M martensite is stress-induced. With increasing compression stress, the
stress-induced intermartensitic transformation sequence 10M ! 14M ! NM was demonstrated.
C 2015 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4933303]
V

Magnetic shape memory (MSM) materials based on Ni-
Mn-Ga single crystals have been the subject of intensive
investigation due to their large potential in actuator, sensor,
and energy harvesting applications.13 Magneto-mechanical
properties in these materials are significantly affected by the
martensitic structure in which the MSM effect takes place.
Among the three martensites obtained in Ni-Mn-Ga alloys,
namely, the five-layered (10M), the seven-layered (14M), and
the non-modulated (NM) one, materials with the 14M modu-
lation have received the least attention. This is because such
structures are obtained in a relatively narrow temperature
interval, they are unstable, and very much dependent on the
chemical composition and prior thermo-mechanical treatment.
The seven-layered martensite in Ni-Mn-Ga alloys was
first discovered by Martynov and Kokorin,4 and its structure
has been studied in detail by Chernenko, Pons, and co-work-
ers.5,6 Righi et al.7 determined the modulated crystal struc-
ture of 14M martensite by refining the X-ray powder
diffraction pattern using the Rietveld method. They found
that the basic structure belongs to monoclinic symmetry.
While most of those studies were carried out using polycrys-
talline samples, little progress has been reported on the
magneto-mechanical properties of 14M single crystalline
alloys. This is because appropriate Ni-Mn-Ga single crystals
that possess a pure 14M lattice modulation suitable for such
measurements have been difficult to produce repeatedly, as
this martensitic structure usually coexists with the thermody-
namically more stable NM one.
Because of the larger magnetic field-induced strain
(MFIS) obtained in 14M structures, as compared to the widely
used 10M martensites, these materials are attractive for engi-
neering applications. To date, the largest MFIS in 14M mar-
tensites measured around 9.5%.8,9 This is close to the
maximum theoretical strain due to lattice distortion, which in
these alloys measured 10.66%.8 Straka10 reported that the
large lattice distortion of around 10% is the reason that MFIS
a)
Author to whom correspondence should be addressed. Electronic mail:
e.pagounis@etogroup.com
is difficult to obtain in 14M martensites. This is because a
larger driving force is necessary to achieve MSM effect in an
alloy with large distortion of the lattice. Magnetic anisotropy
measurements have been carried out by Sozinov, Straka, and
co-workers,11,12 and a room temperature anisotropy of nearly
170 kJ/m3 was deduced. In order, however, for such materials
to be usable for actuator applications a reversible MFIS is
needed, as well as a large magnetic field-induced work out-
put.13,14 To date, no fully reversible MFIS or positive work
output has been obtained in 14M martensites. In the present
work, we repeatedly produced Ni-Mn-Ga actuator elements
with 14M martensitic structure, demonstrating a large actua-
tion work output. Magneto-mechanical properties such as
MFIS, magneto-stress and magneto-crystalline anisotropy are
studied in detail, and are correlated with the obtained crystal
structure.
The Ni-Mn-Ga single crystal has been grown using a
modified Bridgman technique at ETO MAGNETIC GmbH.
Details of the process are described elsewhere.15 After pro-
duction the crystal was heat treated and oriented using mar-
tensitic crystal structure data and electron backscattered
diffraction (EBSD). Subsequently, the crystal was cut in such
a way that the sample faces were nearly parallel to the {100}
planes of the parent cubic phase. Chemical composition was
measured by EDX to be Ni50.5-Mn28.9-Ga20.6 at. % (accu-
racy 6 0.6%). Transformation temperatures were determined
using differential scanning calorimetry (DSC) with a Netzsch
analyser (Model DSC 204). The austenite, martensite, and
Curie point temperatures measured TA 351 K, TM 343 K,
and TC 369 K, respectively.
X-ray diffraction (XRD) measurements, using a Bruker
D8 diffractometer with a Co radiation and a linear detector
with an angular range of 2.5 were performed to analyze the
martensitic structures. The lattice parameters were obtained
by texture type measurements consisting of h/2h scans per-
formed at different v and u values (differently oriented sin-
gle crystal). This procedure enables to scan an appropriate
orientation region in order to detect diffraction peaks of the
{400} planes. In each of the scans, a large range of 2h angles

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V
152407-2 Pagounis et al. Appl. Phys. Lett. 107, 152407 (2015)

(from 65 to 83 ) was analyzed. Further measurements of

possible modulations of the structure were analyzed by a se-
ries of detector scans.16
Samples for magnetic and magneto-mechanical measure-
ments had the dimensions of 2  3  15 mm. In a fully com-
pressed single variant state, the [001] crystallographic
direction was along the 15 mm edge, the [010] direction along
the 3 mm edge, and the [100] direction along the 2 mm
edge. Magnetization measurements were carried out in a
R
PERMAGRAPHV-electromagnet (Magnet-Physik EP2). A set
of pick-up coils placed around the sample was used to measure
the field strength and the magnetization. The MSM samples
were constrained by a compression fixture to avoid MFIS dur-
ing the magnetization measurements. Demagnetization effects
due to the sample shape were taken into account in the results.
Magneto-mechanical measurements were carried out by
subjecting the Ni-Mn-Ga sample to a true actuation cycle.
The detailed procedure is described elsewhere.17 Here, the
material elongates in the presence of the magnetic field and
returns back to its original shape by mechanical compression
at zero field. The resulting stress-strain curves are useful
because they provide direct measurements of the magnetic
stress output rM , the MFIS, the twinning stress rtw , as well
as the work output and efficiency of the material. The strain
vs. field curve was also derived according to the experimen-
FIG. 1. XRD measurements of the Ni-Mn-Ga single crystal obtained after
tal procedure described in Ref. 17.
mechanical training. (a) Combined h/2h scans at different orientations of the
Prior to the magneto-mechanical measurements the Ni- crystal showing the {004} reflections from which the lattice parameters of
Mn-Ga samples were trained to achieve the single variant the Ni-Mn-Ga martensitic structure can be calculated. The S14M is a satellite
state. Various training techniques have been reported in Ni- reflection due to lattice modulation. (b) Scattering intensity distribution in
the reciprocal space revealing six extra satellite reflections coming from the
Mn-Ga martensites, depending on their structure. In 10M mar- lattice modulations.
tensites, a simple magnetic or mechanical compression
(<3 MPa) has proven sufficient to achieve the single variant lattice distortion of e0 1  c=a 11:4%, which also sets
state with the [001] axis along the field or stress.17 In 14M the maximum theoretical MFIS.
martensites, the training has been more complicated so far. It Magnetization curves measured along the [100], [010],
includes repeated compression along the three main crystallo- and [001] directions of the fully compressed nearly single var-
graphic directions,8 cooling from the austenite parent phase iant sample are shown in Fig. 2. Accordingly, the [001] is the
under high compressive stress,12 training within a rotating easy magnetization c-axis (short), [100] is the hard a-axis
magnetic field,9 or a combination of mechanical and magnetic (long) and [010] the intermediate b-axis. The two anisotropy
treatments.10,18 In the present study, a simple compression constants, typical for 14M martensites, can be deduced as
along the 15 mm edge with a stress of 710 MPa was suffi- Ka 195 kJ/m3 and Kb 84 kJ/m3. The small amount of hys-
cient to obtain the (nearly) single variant state, with the [001] teresis in all curves indicates that reversible rotation processes
direction along the stress. Correct selection of the compressive are occurring.19 The magneto-crystalline anisotropy energy
stress is important because larger stress caused the loss of the Ka in the present alloy is larger than the 160170 kJ/m3
desired structure, as will be discussed later.
From the XRD measurements in Fig. 1(a), the lattice pa-
rameters of the martensitic structure after compression (train-
ing) are: a14M 6.23 A, b14M 5.73 A, and c14M 5.52 A.
These correspond well to those of a 14M martensite. The addi-
tional satellite reflections associated with modulations were
observed between the (400) and (620) main reflections in the
reciprocal space dividing this distance into seven equal parts
(Fig. 1(b)). As the a14M and b14M lattice parameters differ sig-
nificantly in this martensitic structure, additional measure-
ments of modulations were performed between the (040) and
(260) main reflections. In each case, no sequence of modula-
tions indicating 10M martensite was observed. These results
unambiguously prove the existence of the seven-layered modu-
lated (14M) structure within the single crystal. The difference FIG. 2. Magnetization curves measured along different crystallographic
between the lattice parameters of a14M and c14M yields a huge directions of the fully compressed Ni-Mn-Ga single crystal.
152407-3 Pagounis et al.
reported earlier in 14M martensites.8,12 A reasonable explana-
tion for this is the faster approach to saturation measured
along the [001] direction, compared to that reported in the
previous studies.12 It suggests that during the measurement
only few remaining variants with hard axes in the magnetiza-
tion direction exist. Accordingly, when fully compressed, the
present sample is believed to have a structure which is very
close to the single variant state.
In Fig. 3, the magneto-mechanical stress-strain curve of
the Ni-Mn-Ga single crystal is shown. The experimental pro-
cedure to obtain this curve is identical to that described in
Ref. 17 for a Ni-Mn-Ga sample with a 10M structure. The
measurement demonstrates a huge MFIS of 11.2%, which is
the largest reported to date in Ni-Mn-Ga 14M martensites. It
is also very close to the maximum theoretical MFIS of
11.4%. It confirms the observation, derived above from the
magnetization curve, that in the present alloy the single vari-
ant structure is easier to obtain. Furthermore, the large MFIS
is combined with a reduced twinning stress of 0.64 MPa, and
a magnetically-induced work output of WM 70 kJ/m3.
Because of the low twinning stress and the resulting low me-
chanical work needed to reset the sample a positive effective
work output of 20 kJ/m3 was produced.
The widely used MSM model proposed by Likhachev
and Ullakko combines the magneto-crystalline anisotropy
energy Ka with lattice parameters and the magneto-stress of
an MSM material as follows:20
Ka rmax
M  e0 ; (1)
where rmax
M is the maximum magneto-stress and e0 is the lat-
tice distortion. Using the experimentally measured anisotropy
Ka 195 kJ/m3 and the lattice distortion of 11.4%, a maxi-
mum magnetic stress of rmax
M 1:71 MPa is calculated. This
is slightly lower than the experimentally measured magneto-
stress of 1.78 MPa (Fig. 3), but larger than that previously
reported in the literature.11 It should be, however, mentioned
that an experimental error of around 65% for the maximum
magnetic stress derived from the measurement presented in
Fig. 3 is typically introduced due to the influence of external
FIG. 3. Stress vs. strain curve during a complete actuation cycle, demon-
strating a MFIS of 11.2%. The Ni-Mn-Ga sample elongates in the presence
of the magnetic field (H 1 T), and returns to its original shape by mechani-
cal compression at zero field. The maximum magnetic stress rmax M , the twin-
ning stress rtw at half the maximum strain, and the effective work output
Weff 20 kJ/m3 are indicated, too. In the inset, the strain vs. field curve at
zero pre-stress further demonstrates the giant MFIS of 11.2%.
Appl. Phys. Lett. 107, 152407 (2015)
stresses associated with sample fixation, friction effects, etc.
This error has been confirmed in several hundred measure-
ments carried out internally at ETO MAGNETIC, and has
also been reported in the literature.10,21
It is interesting to observe in Fig. 3 that a fully reversible
MFIS is obtained in the present alloy. It means that the
magneto-stress the sample produces is larger than the me-
chanical force needed to return the sample to its initial shape
over the complete elongation cycle of 11.2%. The condition
for achieving a reversible MFIS is:10
Ka =e0 > 2rtw : (2)
In Ni-Mn-Ga alloys with a 10M martensitic structure, it
is well established that the Equation (2) is fulfilled when
rtw < 1:5 MPa.10 To date, no fully reversible MFIS has been
reported in Ni-Mn-Ga alloys with a 14M martensitic struc-
ture, because the twinning stresses exceeded 1 MPa (typi-
cally 1.5 MPa) and the ratio measured Ka =e0  1.6 MPa. In
the present alloy, however, a considerably lower twinning
stress of rtw 0.64 MPa is measured and, thus, Equation (2)
is fulfilled.
Until recently, the largest MFIS in Ni-Mn-Ga 14M mar-
tensites has been around 9.5%, with the theoretical limit being
10.66%.8,9 In Ref. 8 a twinning stress of rtw  1.5 MPa was
measured in the 14M martensite, while the magnetic stress
can be calculated as rmax
M  1.5 MPa. Taking into account the
widely accepted condition for the MSM effect (rtw < rmax M ),
the reported MFIS of over 9% cannot be actually justified. In
fact, based on Fig. 3 measured in that study, a smaller MFIS
of about 5%6% should have been obtained. Nevertheless,
the magneto-mechanical properties rmax M and rtw were very
close to each other, and, by assuming experimental errors, the
large MFIS reported in Ref. 8 is plausible.
The larger lattice distortion measured in the present
alloy may be attributed to its higher martensite transforma-
tion temperature TM, which in fact is linked to the chemical
composition. Previous work with 10M martensites has
shown that lattice distortion at room temperature is propor-
tional to the TM.16,22 The same applies also for the 14M
structure, however, the increase in lattice distortion with TM
is only moderate here.22 This can also be concluded from the
experimental results in Ref. 11.
In a further investigation, the structure of the self-
accommodated (i.e., non-trained) martensite was found to have
a five-layered modulation (10M), as can be deduced from Fig.
4(a). The measured lattice parameters were a10M 5.98 A,
b10M 5.94 A, and c10M 5.56 A, which are typical for a 10M
structure. This observation indicates that the uni-axial com-
pression (training) at room temperature initiated a stress-
induced 10M ! 14M intermartensitic transformation, which in
turn increased the effective MFIS of the Ni-Mn-Ga sample. No
reverse transformation has been observed when the compres-
sion stress was removed. Similar stress-assisted transformation
in a Ni-Mn-Ga single crystal was observed by Martynov.23
However, in that study, a substantially larger compression
stress had to be applied to initiate the process, and no MFIS
was measured.
The increased lattice distortion in the present alloy may,
accordingly, also be attributed to the stress-induced nature of
152407-4 Pagounis et al. Appl. Phys. Lett. 107, 152407 (2015)

detwinning process of 14M nanotwins. A more detailed

investigation of the stress-induced intermartensitic transfor-
mation sequence 10M ! 14M ! NM, with accurate determi-
nation of the transformation stresses, and of the obtained
structures, is planned by the authors in a next work.
In conclusion, we report a huge MFIS of 11.2% in a Ni-
Mn-Ga single crystal with a 14M lattice modulation. The ma-
terial has a low twinning stress of 0.64 MPa, a fully reversible
MFIS, and a large magnetically induced work output. The re-
sultant positive effective work output has not been previously
produced in 14M martensites. These properties make the pres-
ent crystal suitable for applications in actuators, sensors, and
energy harvesters. The studied martensite is confirmed to be
stress-induced at room temperature, with a larger lattice dis-
tortion than that previously reported in similar structures.
With increasing compressive stress the intermartensitic trans-
formation sequence 10M ! 14M ! NM was demonstrated at
room temperature.

The authors would like to thank M. Maier and S. Roos of

ETO MAGNETIC for assistance during the measurements.
M.S. and R.C. acknowledge financial support from the Polish
National Center of Science, Project No. DEC-2011/03/D/ST8/
04017, and the Ministry of Science and Higher Education of
Poland, Project No. 0063/IP2/2015/73.
1
O. Soderberg, I. Aaltio, Y. Ge, O. Heczko, and S. P. Hannula, Mater. Sci.
FIG. 4. Combined h/2h scans at different orientations of the crystal showing
Eng. A 481482, 80 (2008).
the {004} reflections from which the lattice parameters of the Ni-Mn-Ga 2
D. C. Dunand and P. M ullner, Adv. Mater. 23, 216 (2011).
martensitic structure can be calculated. (a) Measurements performed in the 3
J. Stephan, E. Pagounis, M. Laufenberg, O. Paul, and P. Ruther, IEEE
self-accommodated (non-trained) state indicating the 10M structure. The
Sens. J. 11, 2683 (2011).
inset shows a scan in the reciprocal space revealing four extra satellite 4
V. V. Martynov and V. V. Kokorin, J. Phys. III 2, 739 (1992).
reflections resulting from the lattice modulations. (b) Measurement after fur- 5
V. A. Chernenko, C. Segu, E. Cesari, J. Pons, and V. V. Kokorin, Phys.
ther compressing the trained 14M structure with a stress of over 15 MPa,
Rev. B 57, 2659 (1998).
revealing a mixture of 14M and NM martensites. 6
J. Pons, V. A. Chernenko, R. Santamarta, and E. Cesari, Acta Mater. 48,
3027 (2000).
7
L. Righi, F. Albertini, E. Villa, A. Paoluzi, G. Calestani, V. Chernenko, S.
the 14M martensite. The structure and magneto-mechanical Besseghini, C. Ritter, and F. Passaretti, Acta Mater. 56, 4529 (2008).
8
properties of a stress-induced martensite as compared to A. Sozinov, A. A. Likhachev, N. Lanska, and K. Ullakko, Appl. Phys.
Lett. 80, 1746 (2002).
those of a thermally induced one have not been thoroughly 9
P. Mullner, V. A. Chernenko, and G. Kostorz, J. Appl. Phys. 95, 1531 (2004).
investigated so far in Ni-Mn-Ga crystals. A stress-induced 10
L. Straka, Ph.D. thesis, Helsinki University of Technology, Finland, 2004.
11
14M martensite may possess a larger lattice distortion than a A. Sozinov, A. A. Likhachev, N. Lanska, O. S oderberg, K. Ullakko, and
thermally induced one. In a direct comparison of thermally- V. K. Lindroos, Mater. Sci. Eng., A 378, 399 (2004).
12
L. Straka, O. Heczko, and K. Ullakko, J. Magn. Magn. Mater. 272276,
and stress-induced 10M martensites using XRD techniques 2049 (2004).
Martynov23 found that crystal structure and lattice parame- 13
B. Kiefer, H. E. Karaca, D. C. Lagoudas, and I. Karaman, J. Magn. Magn.
ters are almost identical for both of them. Mater. 312, 164 (2007).
14
When the 14M martensite sample was further com- Y. Ganor, D. Shilo, T. W. Shield, and R. D. James, Appl. Phys. Lett. 93,
122509 (2008).
pressed with a stress larger than 15 MPa, an intermartensitic 15
E. Pagounis and M. Laufenberg, in Proceedings of Actuator 2010
transformation to the NM structure took place (Fig. 4(b)). A (Bremen, 2010), p. 731.
16
mixture of 14M and NM martensites was observed within E. Pagounis, R. Chulist, M. J. Szczerba, and M. Laufenberg, Appl. Phys.
the whole sample, which effectively blocked the MFIS. The Lett. 105, 052405 (2014).
17
E. Pagounis, A. Laptev, M. J. Szczerba, R. Chulist, and M. Laufenberg,
lattice parameters of the two structures in the mixture are
Acta Mater. 89, 32 (2015).
a14M 6.18 A, b14M 5.73 A and c14M 5.52 A for the 14M 18
L. Straka, O. Heczko, and H. Hanninen, Acta Mater. 56, 5492 (2008).
structure, and aNM bNM 5.52 A, and cNM 6.61 A for the 19
R. Tickle and R. D. James, J. Magn. Magn. Mater. 195, 627 (1999).
20
NM structure, respectively. When comparing Figs. 1(a) and A. Likhachev and K. Ullakko, Phys. Lett. A 275, 142 (2000).
21
E. Pagounis, A. Laptev, J. Jungwirth, M. Laufenberg, and M. Fonin, Scr.
4(b), it is seen that the reflections a and b of the 14M Mater. 88, 17 (2014).
phase are broader in the mixed structure. It suggests that the 22
N. Lanska, O. S oderberg, A. Sozinov, Y. Ge, K. Ullakko, and V. K.
modulated phase is more adaptive than the NM phase.16 Lindroos, J. Appl. Phys. 95, 8074 (2004).
23
Structural details of the thermally and of the stress induced V. V. Martynov, J. Phys. IV 5, C8C91 (1995).
24
Z. Li, B. Yang, Y. Zhang, C. Esling, N. Zou, X. Zhao, and L. Zuo, Acta
14M ! NM transformation were recently revealed by Li Mater. 74, 9 (2014).
et al.24 and by Ge et al.,25 respectively. In the latter case, it 25
Y. Ge, N. Zarubova, O. Heczko, and S. P. Hannula, Acta Mater. 90, 151
has been demonstrated that the 14M to NM transition is a (2015).