57 Fe-substituted Ni-Mn-Sn Metamagnetic Shape Memory Alloys

In order to investigate the Fe substituted effects on the magnetic properties of the Ni-Mn-Sn metamagnetic shape memory alloys, magnetization and the Mossbauer spectroscopy measurements were carried out with using 57Fe-doped specimens of Ni2Mn1.48−x57FexSn0.52 (x = 0.02, 0.04 and 0.08). Singlet-type Mossbauer spectra were clearly observed for x = 0.02 and 0.04 just below the martensitic transformation temperature, TM, and above the Curie temperature, TC, in the austenite phase. It was clear that the magnetic state in the martensite phase just below TM was paramagnetic for x = 0.02 and 0.04. In further doped 57Fe to Ni2Mn1.48Sn0.52, TC in the austenite phase slightly increased. However, the value of TM significantly decreased. As a result, martensite phase with small spontaneous magnetization directly transformed to the ferromagnetic austenite phase during heating for x = 0.08. These results obtained from the Mossbauer spectra were consistent with the results of the magnetic measurements in this study and the phase diagram reported by Fukushima et al. for normal Fe-doped Ni2Mn1.48−xFexSn0.52 alloys. The breakdown of the general rule, in which the ferromagnetic shape memory alloys with larger value of the valence electrons per atom, e/a, showed higher TM, was also appeared in Ni2Mn1.48−xFexSn0.52 alloys, being similar to Ni2Mn1−xFexGa alloys.


Introduction
Ferromagnetic shape memory alloys (FSMAs) have become very attractive candidates for high performance magnetic actuator materials because they show a large magnetic-field-induced strain by the rearrangement of twin variants in the martensite phase [1,2].Ni 2 MnGa has the cubic L2 1 -type Heusler structure at room temperature, and orders ferromagnetically at the Curie temperature, T C , of 365 K. On cooling below a martensitic transformation temperature, T M , of about 200 K, a superstructure forms [3].A number of investigations on Ni-Mn-Ga FSMAs have been described in the literature because T C and T M can be tuned by changing the constituent elements of Ni, Mn and Ga.Many topics relating to the Ni-Mn-Ga FSMAs have been reviewed by Entel et al. [4] and Brown et al. [5] in recent articles.
In 2004, Sutou et al. found new series of FSMAs, such as Ni-Mn-Z (Z = In, Sn, Sb) alloys, which show a drastic change of magnetization due to the martensitic transformation, MT, in where the magnetization of the martensite phase is considerably smaller than that of the austenite phase [6].In contrast to the Ni-Mn-Ga FSMAs, where MT occurs from ferromagnetic austenite phase to ferrimagnetic martensite phase, the magnetization in the Ni-Mn-Z alloys drastically changes associated with the transformation because the magnetization is low in the martensite phase.The value of T M of Ni-Mn-Z alloys and its Co-substituted series is significantly decreased by applied magnetic field; therefore, the magnetic-field-induced reverse MT has been confirmed below T M [7][8][9].Umetsu et al. have investigated Mössbauer spectroscopy in 57 Fe-doped Ni 2 Mn 1.48 Sn 0.52 and reported that the magnetic feature of the martensite phase just below the transformation temperature is paramagnetic [10].Subsequently, it has also been confirmed that the martensite phase of 57 Fe substituted Ni 2 Mn 1.392In 0.608 is paramagnetic by Khovaylo et al. [11].These results became one of powerful key to clarify the mechanism of MT for these FSMAs.Kikuchi et al. and Fukushima et al. have reported the phase diagrams of Ni 2 (Fe,Mn)Ga and Ni 2 (Fe,Mn) 1.48 Sn 0.52 FSMAs, respectively [12,13].Substitution of Fe for Mn has to be known to enhance the ductility of Ni-Mn-Ga and Ni-Mn-Sn alloys, and the way is significantly effective for the applications [14,15].Furthermore, the phase diagrams of Ni 2 (Mn,Fe)Ga and Ni 2 (Mn,Fe) 1.48 Sn 0.52 open question to behavior of the concentration dependence of T M because it has been thought that the variation of T M follows the general rule related to the number of the valence electrons.That is, T M increases with increasing the number of the valence electrons per atoms, e/a, [16,17].There have been many reports on the variation of T M on e/a for many kinds of FSMAs, such as Ni-Mn-Ga, Ni-Mn-Z (Z = In, Sn, Sb), and their element doping systems [18][19][20][21].In these systematic studies, it has been pointed out that the behavior of T M on e/a is different only for the Fe-doping system.Fe substitution for Mn in Ni 2 MnGa and Ni 2 Mn 1.48 Sn 0.52 FSMAs increases e/a, however, T M decreases with increasing the Fe content in both Ni 2 MnGa and Ni 2 Mn 1.48 Sn 0.52 FSMAs [11,12].Clarifying the role of the Fe substitution in Ni-Mn-Ga and Ni-Mn-Sn FSMAs is very important from the both aspects of the applications and academics.In our previous study for the Mössbauer spectroscopy in 57 Fe-doped Ni 2 Mn 1.48 Sn 0.52 , only 0.5 at.% of 57 Fe was doped.In this study, we first establish that the magnetic properties of 57 Fe doped Ni 2 Mn 1.48 Sn 0.52 system follows the reported phase diagram for the normal Fe-doped system.Furthermore, we report the experimental results of Mössbauer spectroscopy measurements for Ni 2 Mn 1.48 Sn 0.52 FSMA with various 57 Fe contents.It is clear that information of this type is essential to an understanding of the mechanism of the magnetic-field-induced reverse MT observed on Ni-Mn-Sn FSMAs.

Experimental Section
Polycrystalline samples of Ni 2 Mn 1.48−x 57 Fe x Sn 0.52 (x = 0.02, 0.04 and 0.08) alloys were prepared by repeated arc-melting of the appropriate quantities of the constituent elements in an argon atmosphere.
To obtain the homogenized samples, the alloys were heated at 1123 K for 3 days and then quenched in water.Powder specimens were obtained by grinding and annealed at 1123 K for 2 min to remove the induced strain.The phase characterization of the specimens was confirmed by X-ray powder diffraction measurements with using Cu-Kα radiation.The dc magnetization measurements were carried out with using a commercial superconducting quantum interference device magnetometer. 57Fe Mössbauer spectroscopy measurements were carried out in the 80 to 312 K temperature range in transmission geometry using a conventional spectrometer with a 57 Co-Rh source.Fittings with the obtained spectra were performed with MossWinn 3.0 program (Klencsár, Z.: Budapest, Hungary).

Results and Discussion
Figure 1 indicates phase diagram of Fe substituted Ni 2 Mn 1.48−x Fe x Sn 0.52 alloys reported by Fukushima et al. [13].In the figure, A and M indicate the austenite and martensite phases, respectively, and T C and T C ' indicate the Curie temperature, T C , of the austenite phase and the martensite phase, respectively.T Ms means the martensitic transformation starting temperature during cooling process.T C slightly increases with increasing the Fe concentration, whereas T Ms drastically decreases.In the figure, PM and FM mean paramagnetic and ferromagnetic states, respectively.It has been commonly thought that the martensitic transformation temperature, T M , is significantly sensitive to the concentration and the behavior is explained as a function of the number of the valence electrons per atoms, e/a, namely, T Ms increases with increasing e/a [16,17].The explanation has been known to be a general rule to indicate the behavior of T Ms of the Ni-based FSMAs.However, it has been recently reported that this rule does not hold when Fe is substituted for Mn in Ni 2 MnGa [12,22,23].Here, valence electrons of Fe is larger than that of Mn, thus, the Fe substitution for Mn means an increase of e/a.Such a break has also been observed in Ni-Mn-Sn alloys as shown in the Figure 1 [13].Again,the experimental facts throw a question of an origin of the martensitic transformation, MT.The dashed lines in the Figure mean the Fe composition of x = 0.02, 0.04 and 0.08, they are the 57 Fe compositions that the Mössbauer spectroscopy measurements were performed in the present study in order to investigate the microscopic magnetic properties, where 57 Fe is doped instead of the normal Fe element in the Ni 2 Mn 1.48−x Fe x Sn 0.52 alloys.M-T curve for x = 0.02 at 500 Oe is same as the reported previously [10].The arrows with ZFC and FC along the curves in (a), (b) and (c) show the zero-field-cooling and field-cooling processes, respectively.
Thermomagnetization (M-T) curves measured under the magnetic fields of 500 Oe and 10 kOe for 57 Fe-doped Ni 2 Mn 1.48−x 57 Fe x Sn 0.52 alloys with x = 0.02, 0.04 and 0.08 are indicated in Figure 2a-c, respectively.Here, M-T curve of x = 0.02 measured at 500 Oe is the same as the reported one [10].
From the M-T curves, it is shown that the magnetic transformation from the ferromagnetic to paramagnetic state in the austenite phase and MT occurs at almost the same time for x = 0.02.The temperature difference between T C and T Ms gradually expands with increasing 57 Fe content, being similar to the behavior indicated in the phase diagram in the Figure 1.That is, it is confirmed that the 57 Fe concentration dependence of T C and T Ms follows the phase diagram of the normal Fe-doped Ni 2 Mn 1.48−x FeSn 0.5 system.The zero field-cooled (ZFC) and field-cooled (FC) M-T curves were measured during heating after the specimen was cooled down to low temperature in a zero applied magnetic field and during cooling in the applied magnetic field, respectively.In the all of the specimens for x = 0.02, 0.04 and 0.08, FC effects, that is, ZFC and FC curves do not coincide, are observed in low temperature range when the magnetic field is 500 Oe.T i ' is the temperature of the inflection point, and it is observed around 235 and 255 K for x = 0.02 and 0.04, respectively.In the phase diagram [13], although T i ' is treated as a magnetic transition temperature from the ferromagnetic state to the paramagnetic state in the martensite phase, the existence of the long-rang ferromagnetic ordering in the martensite phase is controversial even now.It will be discussed later.The value of T C in the austenite phase, here T C is defined as the temperature with showing the largest negative slope in the cooling M-T curve, was determined to be 309, 311 and 315 K for x = 0.02, 0.04 and 0.08, respectively, indicating tiny increase with increasing 57 Fe concentration.The values of T Ms for x = 0.02, 0.04 and 0.08 confirmed by the M-T curves under 500 Oe are about 303, 300 and 220 K, respectively, being in good agreement with the phase diagram reported by Fukushima et al. [13].
The 57 Fe Mössbauer spectra taken at 80, 199, 264, 293 and 312 K for x = 0.02 and x = 0.04 are shown in Figure 3a-e [10] and in Figure 4a-e, respectively.Here, the measurement was performed at fixed temperatures in the heating process from 80 to 312 K. Whole of the aspects of the spectra are similar in both compositions.The spectra at 80 K of x = 0.02 in Figure 3a and of x = 0.04 in Figure 4a show a broad sextet arising from the wide distribution of hyperfine fields and the spectra at 199 K of x = 0.02 in Figure 3b and of x = 0.04 in Figure 4b exhibit a considerably wide line intensity distribution around maximum absorption due to the presence of the internal magnetic fields, indicating the existence of magnetic components.It should be noted that the magnetization on ZFC process shows a clear increase with increasing temperature up to around 200 K, while the magnetization on FC process indicates relatively plateau-like behavior under 500 Oe.Recently, ac susceptibility studies were performed and it was concluded that the magnetic feature of the ground state of Ni 2 Mn 1.54 Sn 0.46 alloy is magnetic blocking state because frequency dependence of the ac susceptibility is clearly observed, whereas no divergence in the non-linear term of the as susceptibility is observed [24].The magnetic properties of the ground state of the Ni 2 Mn 1.54 Sn 0.46 alloy are different from that of the Ni 2 Mn 1.6 Sb 0.4 alloy, which shows a negative peak in the non-linear ac susceptibility.On the basis of the experimental results, it was concluded that the magnetic ground state of the Ni 2 Mn 1.6 Sb 0.4 alloy is spin-glass.Although the concentration of the specimens with x = 0.02 and 0.04 in this study are different from the Ni 2 Mn 1.54 Sn 0.46 alloy, the magnetic ground state of the specimens with x = 0.02 and 0.04 may be the blocking state.The spectra of 312 and 264 K in Figure 3c,d, in Figure 4c,d, are composed of a singlet with a narrow line width, while those at 293 K in Figure 3d and Figure 4d include a weak and broad sub-spectrum around the base of the sharp singlet, indicating the coexistence of magnetically ordered and disordered phases.From the M-T curves in Figure 2a,b, the specimens at 293 K for both x = 0.02 and x = 0.04 are seemed to be in a coexistent state with the martensite phase and the austenite phase.As shown in Figure 3c,e, and Figure 4c,e, both full widths at half maximum of the singlet spectra at 312 K and 264 K are almost equal in x = 0.02 and x = 0.04.The result means that the hyperfine field distribution of the spectrum taken from the nonmagnetic martensite phase at 264 K is almost the same as that from the paramagnetic austenite state at 312 K.It is strongly suggested that the martensite phase is paramagnetic in the temperature region just below T M , and the paramagnetic region also exists for the specimen with x = 0.04.The paramagnetic and the ferromagnetic components in the spectra at 293 K will be brought from the paramagnetic martensite and ferromagnetic austenite phases.On the other hand, the spectra at 199 K become broader and the spectra at 80 K suggest the existence of the hyperfine field.As mentioned above, the FC effect is observed in the low temperature region for the specimens with x = 0.02 and 0.04.Concluding the results of the ac susceptibility measurements for the Ni 2 Mn 1.54 Sn 0.46 alloy [24], the magnetic state below T i ' would be blocking-state or spin glass-like state.Further study is needed to confirm whether the magnetically ordered state exists or not.   Fe Mössbauer spectra and their fitting curves for x = 0.08 (Ni 2 Mn 1.40 Fe 0.08 Sn 0.52 ) measured at 80, 212, 262, 293 and 326 K, respectively.Although the aspects of the spectra at the each temperature of the specimens with x = 0.02 and 0.04 are similar, the spectra for x = 0.08 seem to differ from them.Spectrum of the singlet type is observed at only 326 K and it is due to the paramagnetism of the austenite phase from the result of the M-T curves in the Figure 2c, in where T C is found to be about 315 K. On the other hand, sextet-like behavior is observed in the spectra measured at 262 and 293 K, and these are associated with the ferromagnetism in the austenite phase because the reverse T M is about 200 K for x = 0.08 (See the Figure 2c).The spectra at 80 K and 212 K are also very broad and exhibit a wide distribution of hyperfine field.A distinct feature of the spectra at 80 K is that this shows an almost symmetric pattern in spite of the existence of electric quadrupole interactions.The symmetric pattern of the spectra may be attributed to the blocking of iron moments in random directions to the axis of the electric field gradient.shows monotonic decreases with increasing temperature for all specimens, and no composition dependence is observed.Because the I.S. relates to the position of the nuclei and the charge density, the monotonic behavior as a function of the temperature in this case is natural.In addition, concentration dependence of Q.S. is also not sensitive.In general, Q.S. reflects the symmetry of the crystal, with including the meaning of the magnetic configuration.The absolute values of Q.S. are comparatively small in the whole temperature range.It has been reported that the structure of the martensite phase of Ni 2 Mn 1.44 Fe 0.04 Sn 0.52 is four-layered orthorhombic (4O) structure [12] and the symmetry of the crystal in the martensite phase becomes lower than that of the L2 1 -type cubic structure in the austenite phase.
Although the value of the Q.S. for x = 0.02 at 199 K is somewhat distributed, there is a trend that the absolute value of the Q.S. in the austenite phase may be slightly larger than those in the martensite phase.These behaviors, such as the monotonic decrease of I.S. with the temperature and slight change of the Q.S. between the martensite phase and austenite phase, have been also reported in 57 Fe-doped Ni 2 Mn 1−x 57 Fe x Ga alloys [25].Such a comparatively small absolute values of the Q.S. in the martensite phase, even though the structure of the martensite phase has lower symmetry, would also be correlated to the magnetic state of the martenstite phase.It has been reported from the studies of the ac magnetic susceptibility that the magnetic state of Ni 2 Mn 1.54 Sn 0.46 alloy in the martensite phase is blocking-state [24].This may mean that the magnetic configuration of the blocking-state, where the magnetic spins are frozen to direct randomly, is rather symmetric than the magnetic state of the certain magnetic ordering with low symmetric structure.As shown in Figure 6c, the values of hf B at 80 K for all specimens are found to be about 15 T. In this study, we confirmed that the magnetic state just below T M of the specimens with x = 0.02 and 0.04 is paramagnetic from the Mössbauer spectroscopy measurements.The magnetic-field-induced reverse MT observed in Ni-Mn-Sn FSMAs may be attributed to the large difference of magnetization between the paramagnetic martensite phase and the ferromagnetic austenite phase.In the Ni-Mn-Sn FSMAs, there is some information in the literature on the giant magnetocaloric effect [27,28].The origin of the giant magnetocaloric effect would be caused by the large entropy change between the paramagnetic martensite phase and the ferromagnetic austenite phase.As mentioned above, the number of the valence electrons per atom, e/a, is closely related to T M : a large e/a indicates a higher T M .However, such a correlation breaks down for the Ni 2 Mn 1.48−x Fe x Sn 0.52 and Ni 2 Mn 1-x Fe x Ga

Figure 1 .
Figure 1.Phase diagram of Fe substituted Ni 2 Mn 1.48 Sn 0.52 alloys reported by Fukushima et al. [13].A and M indicate the austenite and martensite phases, respectively.T C and T C ' indicate the Curie temperature of the austenite phase and the martensite phase, respectively.T Ms means the martensitic transformation starting temperature during cooling process.PM and FM mean paramagnetic and ferromagnetic states, respectively.

Figure 5a-e are
Figure5a-e are57 Fe Mössbauer spectra and their fitting curves for x = 0.08 (Ni 2 Mn 1.40 Fe 0.08 Sn 0.52 ) measured at 80, 212, 262, 293 and 326 K, respectively.Although the aspects of the spectra at the each temperature of the specimens with x = 0.02 and 0.04 are similar, the spectra for x = 0.08 seem to differ from them.Spectrum of the singlet type is observed at only 326 K and it is due to the paramagnetism of the austenite phase from the result of the M-T curves in the Figure2c, in where T C is found to be about 315 K. On the other hand, sextet-like behavior is observed in the spectra measured at 262 and 293 K, and these are associated with the ferromagnetism in the austenite phase because the reverse T M is about 200 K for x = 0.08 (See the Figure2c).The spectra at 80 K and 212 K are also very broad and exhibit a wide distribution of hyperfine field.A distinct feature of the spectra at 80 K is that this shows an almost symmetric pattern in spite of the existence of electric quadrupole interactions.The

Figure 6 .
Figure 6.Temperature dependences of the isomer shift, I.S., the quadrupole splitting, Q.S., and the absolute average 57 Fe hyperfine field, hf B , obtained from the fitting in Figures 3-5.