Sie sind auf Seite 1von 5
Large magnetic field-induced work output in a NiMnGa seven-layered modulated martensite E. Pagounis , ,

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

Citation: Appl. Phys. Lett. 107, 152407 (2015); doi: 10.1063/1.4933303 View online: View Table of Contents: Published by the American Institute of Physics

View Table of Contents: Published by the American Institute of Physics

APPLIED PHYSICS LETTERS 107, 152407 (2015)

APPLIED PHYSICS LETTERS 107 , 152407 (2015) Large magnetic field-induced work output in a NiMnGa seven-layered

E. Pagounis, 1, a) M. J. Szczerba, 2 R. Chulist, 2 and M. Laufenberg 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/m 3 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/m 3 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.


2015 AIP Publishing LLC . [ ]

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. 1 3 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 Straka 10 reported that the large lattice distortion of around 10% is the reason that MFIS

a) Author to whom correspondence should be addressed. Electronic mail:

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/m 3 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 T A ¼ 351 K, T M ¼ 343 K, and T C ¼ 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/2 h 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


the scans, a large range of 2 h angles 0003-6951/2015/107(15)/152407/4/$30.00 107 , 152407-1 V C 2015

107, 152407-1


2015 AIP Publishing LLC


Pagounis et al.

(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 PERMAGRAPH V R -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 r M , the MFIS, the twinning stress r tw , as well as the work output and efficiency of the material. The strain vs. field curve was also derived according to the experimen- tal procedure described in Ref. 17. Prior to the magneto-mechanical measurements the Ni- Mn-Ga samples were trained to achieve the single variant state. Various training techniques have been reported in Ni- Mn-Ga martensites, depending on their structure. In 10M mar- tensites, a simple magnetic or mechanical compression (< 3 MPa) has proven sufficient to achieve the single variant state with the [001] axis along the field or stress. 17 In 14M martensites, the training has been more complicated so far. It includes repeated compression along the three main crystallo- graphic directions, 8 cooling from the austenite parent phase under high compressive stress, 12 training within a rotating magnetic field, 9 or a combination of mechanical and magnetic treatments. 10 ,18 In the present study, a simple compression

along the 15 mm edge with a stress of 7–10 MPa was suffi- cient to obtain the (nearly) single variant state, with the [001] direction along the stress. Correct selection of the compressive stress is important because larger stress caused the loss of the 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: a 14M ¼ 6.23 A , b 14M ¼ 5.73 A , and c 14M ¼ 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 a 14M and b 14M 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

between the lattice parameters of a 14M and c 14M yields a huge




of a 1 4 M and c 1 4 M yields a huge ˚ ˚ ˚

Appl. Phys. Lett. 107, 152407 (2015)

a huge ˚ ˚ ˚ Appl. Phys. Lett. 107 , 152407 (2015) FIG. 1. XRD measurements

FIG. 1. XRD measurements of the Ni-Mn-Ga single crystal obtained after mechanical training. (a) Combined h/2h scans at different orientations of the crystal showing the {004} reflections from which the lattice parameters of the Ni-Mn-Ga martensitic structure can be calculated. The S 14M is a satellite reflection due to lattice modulation. (b) Scattering intensity distribution in the reciprocal space revealing six extra satellite reflections coming from the lattice modulations.

lattice distortion of e 0 ¼ 1 c =a ¼ 11: 4%, which also sets the maximum theoretical MFIS. Magnetization curves measured along the [100], [010], and [001] directions of the fully compressed nearly single var- iant sample are shown in Fig. 2. Accordingly, the [001] is the easy magnetization c-axis (short), [100] is the hard a-axis (long) and [010] the intermediate b-axis. The two anisotropy constants, typical for 14M martensites, can be deduced as K a ¼ 195 kJ/m 3 and K b ¼ 84 kJ/m 3 . The small amount of hys- teresis in all curves indicates that reversible rotation processes are occurring. 19 The magneto-crystalline anisotropy energy K a in the present alloy is larger than the 160–170 kJ/m 3

in the present alloy is larger than the 160–170 kJ/m 3 FIG. 2. Magnetization curves measured

FIG. 2. Magnetization curves measured along different crystallographic directions of the fully compressed Ni-Mn-Ga single crystal.


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 W M ¼ 70 kJ/m 3 .

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/m 3 was produced. The widely used MSM model proposed by Likhachev and Ullakko combines the magneto-crystalline anisotropy energy K a with lattice parameters and the magneto-stress of

an MSM material as follows: 20

K a ¼ r



e 0 ;


is the maximum magneto-stress and e 0 is the lat-

tice distortion. Using the experimentally measured anisotropy

K a ¼ 195 kJ/m 3 and the lattice distortion of 11.4%, a maxi-

¼ 1: 71 MPa is calculated. This

mum magnetic stress of r

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

where r





due to the influence of external where r max M max M FIG. 3. Stress vs.

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 ¼ 1 T), and returns to its original shape by mechani-

, the twin-

ning stress r tw at half the maximum strain, and the effective work output W eff ¼ 20 kJ/m 3 are indicated, too. In the inset, the strain vs. field curve at zero pre-stress further demonstrates the giant MFIS of 11.2%.

cal compression at zero field. The maximum magnetic stress r



at zero field. The maximum magnetic stress r max M Appl. Phys. Lett. 107 , 152407

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

K a =e 0 > 2r tw :


In Ni-Mn-Ga alloys with a 10M martensitic structure, it is well established that the Equation (2) is fulfilled when

r tw < 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 K a =e 0 1.6 MPa. In the present alloy, however, a considerably lower twinning stress of r tw ¼ 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 r tw 1.5 MPa was measured in the 14M martensite, while the magnetic stress

can be calculated as r


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 r

and r tw 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 T M , 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 T M . 16 , 22 The same applies also for the 14M structure, however, the increase in lattice distortion with T M

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.



1.5 MPa. Taking into account the

widely accepted condition for the MSM effect (r tw < r






4(a). The measured lattice parameters were a 10M ¼ 5.98 A ,

b 10M ¼ 5.94 A , and c 10M ¼ 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




Pagounis et al.

152407-4 Pagounis et al. FIG. 4. Combined h /2 h scans at different orientations of the

FIG. 4. Combined h /2h scans at different orientations of the crystal showing the {004} reflections from which the lattice parameters of the Ni-Mn-Ga martensitic structure can be calculated. (a) Measurements performed in the self-accommodated (non-trained) state indicating the 10M structure. The inset shows a scan in the reciprocal space revealing four extra satellite reflections resulting from the lattice modulations. (b) Measurement after fur- ther compressing the trained 14M structure with a stress of over 15 MPa, revealing a mixture of 14M and NM martensites.

the 14M martensite. The structure and magneto-mechanical properties of a stress-induced martensite as compared to those of a thermally induced one have not been thoroughly investigated so far in Ni-Mn-Ga crystals. A stress-induced 14M martensite may possess a larger lattice distortion than a thermally induced one. In a direct comparison of thermally- and stress-induced 10M martensites using XRD techniques Martynov 23 found that crystal structure and lattice parame- ters are almost identical for both of them. When the 14M martensite sample was further com-

pressed with a stress larger than 15 MPa, an intermartensitic transformation to the NM structure took place (Fig. 4(b) ). A mixture of 14M and NM martensites was observed within the whole sample, which effectively blocked the MFIS. The lattice parameters of the two structures in the mixture are

a 14M ¼ 6.18 A , b 14M ¼ 5.73 A and c 14M ¼ 5.52 A for the 14M




structure, and a NM ¼ b NM ¼ 5.52 A , and c NM ¼ 6.61 A for the NM structure, respectively. When comparing Figs. 1(a) and 4(b) , it is seen that the reflections “ a” and “ b” of the 14M phase are broader in the mixed structure. It suggests that the modulated phase is more adaptive than the NM phase. 16 Structural details of the thermally and of the stress induced 14M ! NM transformation were recently revealed by Li et al. 24 and by Ge et al. , 25 respectively. In the latter case, it has been demonstrated that the 14M to NM transition is a



been demonstrated that the 14M to NM transition is a ˚ ˚ Appl. Phys. Lett. 107

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. S oderberg, I. Aaltio, Y. Ge, O. Heczko, and S. P. Hannula, Mater. Sci. Eng. A 481–482, 80 (2008). 2 D. C. Dunand and P. Mullner, Adv. Mater. 23, 216 (2011). 3 J. Stephan, E. Pagounis, M. Laufenberg, O. Paul, and P. Ruther, IEEE Sens. J. 11, 2683 (2011). 4 V. V. Martynov and V. V. Kokorin, J. Phys. III 2, 739 (1992). 5 V. A. Chernenko, C. Segu ı, E. Cesari, J. Pons, and V. V. Kokorin, Phys. Rev. B 57, 2659 (1998). 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.

Besseghini, C. Ritter, and F. Passaretti, Acta Mater. 56, 4529 (2008). 8 A. Sozinov, A. A. Likhachev, N. Lanska, and K. Ullakko, Appl. Phys.

Lett. 80, 1746 (2002). 9 P. Mullner, V. A. Chernenko, and G. Kostorz, J. Appl. Phys. 95, 1531 (2004). 10 L. Straka, Ph.D. thesis, Helsinki University of Technology, Finland, 2004. 11 A. Sozinov, A. A. Likhachev, N. Lanska, O. S oderberg, K. Ullakko, and V. K. Lindroos, Mater. Sci. Eng., A 378, 399 (2004). 12 L. Straka, O. Heczko, and K. Ullakko, J. Magn. Magn. Mater. 272–276,

2049 (2004).

13 B. Kiefer, H. E. Karaca, D. C. Lagoudas, and I. Karaman, J. Magn. Magn. Mater. 312, 164 (2007). 14 Y. Ganor, D. Shilo, T. W. Shield, and R. D. James, Appl. Phys. Lett. 93, 122509 (2008). 15 E. Pagounis and M. Laufenberg, in Proceedings of Actuator 2010 (Bremen, 2010), p. 731. 16 E. Pagounis, R. Chulist, M. J. Szczerba, and M. Laufenberg, Appl. Phys. Lett. 105, 052405 (2014). 17 E. Pagounis, A. Laptev, M. J. Szczerba, R. Chulist, and M. Laufenberg,

Acta Mater. 89, 32 (2015).

18 L. Straka, O. Heczko, and H. Hanninen, Acta Mater. 56, 5492 (2008).

19 R. Tickle and R. D. James, J. Magn. Magn. Mater. 195, 627 (1999). 20 A. Likhachev and K. Ullakko, Phys. Lett. A 275, 142 (2000). 21 E. Pagounis, A. Laptev, J. Jungwirth, M. Laufenberg, and M. Fonin, Scr. Mater. 88, 17 (2014). 22 N. Lanska, O. S oderberg, A. Sozinov, Y. Ge, K. Ullakko, and V. K. Lindroos, J. Appl. Phys. 95, 8074 (2004). 23 V. V. Martynov, J. Phys. IV 5, C8–C91 (1995). 24 Z. Li, B. Yang, Y. Zhang, C. Esling, N. Zou, X. Zhao, and L. Zuo, Acta Mater. 74, 9 (2014). 25 Y. Ge, N. Z arubov a, O. Heczko, and S. P. Hannula, Acta Mater. 90, 151