The effect of hydrostatic pressure on martensitic transition and magnetocaloric effect of Mn44.7Ni43.5Sn11.8 ribbons

Journal Pre-proof The Effect of Hydrostatic Pressure on Martensitic Transition and Magnetocaloric Effect of Mn44.7Ni43.5Sn11.8 Ribbons

Wenjian Shi, Fenghua Chen, Jian Liu, Haicheng Xuan, Rui Zhang, Qingmei Zhang, Yong Jiang, Mingang Zhang PII:

S0038-1098(19)30614-3

DOI:

https://doi.org/10.1016/j.ssc.2020.113821

Reference:

SSC 113821

To appear in:

Solid State Communications

Received Date:

12 July 2019

Accepted Date:

07 January 2020

Please cite this article as: Wenjian Shi, Fenghua Chen, Jian Liu, Haicheng Xuan, Rui Zhang, Qingmei Zhang, Yong Jiang, Mingang Zhang, The Effect of Hydrostatic Pressure on Martensitic Transition and Magnetocaloric Effect of Mn44.7Ni43.5Sn11.8 Ribbons, Solid State Communications (2020), https://doi.org/10.1016/j.ssc.2020.113821

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The Effect of Hydrostatic Pressure on Martensitic Transition and Magnetocaloric Effect of Mn44.7Ni43.5Sn11.8 Ribbons Wenjian Shi, Fenghua Chen,* Jian Liu, Haicheng Xuan, Rui Zhang, Qingmei Zhang, Yong Jiang, Mingang Zhang

Keywords: Hydrostatic pressure, Ni-Mn-Sn, Martensitic transition, Magnetocaloric effect.

Abstract: The effect of hydrostatic pressure on the martensitic transformation and magnetocaloric effect has been systematically studied in Mn44.7Ni43.5Sn11.8 ribbons. The melt-spun ribbons crystallize along the [400] direction, which is perpendicular to the surface of the ribbon. The martensitic transformation temperatures shift from 266.5 K to 281.0 K by applying hydrostatic pressure of 0.75GPa. Under the magnetic field of 30 kOe, the value of dTM dP is about 19.3 K GPa-1, indicating a broadening of working temperature span for magnetic refrigeration at room temperature. At ambient pressure, a relatively large entropy change value of 35.9 J kg-1 K-1 is obtained under a magnetic field of 30 kOe, which would be related to the orientation of crystal

Wenjian Shi, Fenghua Chen, Jian Liu, Rui Zhang, Qingmei Zhang, Yong Jiang, Mingang Zhang. The Key Laboratory of Magnetic and Electric Functional Materials and Applications of Shanxi Province, Taiyuan University of Science and Technology, Taiyuan 030024, Shanxi, China. *Corresponding

Author. E-mail: [email protected]

Haicheng Xuan, College of Materials Science and Engineering, Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, PR China. 1

Journal Pre-proof structure.

1. Introduction Currently, conventional refrigeration techniques are still based on the compression and expansion cycle of hazardous gases. The heavy use of these refrigerants inevitably has created and exacerbated many global environmental problems. In order to solve these problems, great efforts are being made to develop new solid-state refrigeration technologies that promise to be more efficient and environmentally friendly. The potential magnetic refrigeration materials such as the intermetallic Gd-Si-Ge,[1] La(Fe13-xSix),[2] other rare-earth compounds,[3] and Ni-Mn-based Heusler alloys,[4]

[5] [6] [7]

have been extensively studied in recent years. These caloric materials show

reversible thermal changes in response to changes of applied external fields, such as magnetocaloric, electrocaloric and mechanocaloric (elastocaloric or barocaloric) effects.[8] Due to the fact that hydrostaticc pressure is easier to achieve than strong magnetic field, the barocaloric materials have attracted considerable attention, such as Ni44.6Co5.5Mn35.5In14.4,[9] Ni-Mn-In(Ga),[10] Mn3NiN,[11] AgI.[12] It is found that the barocaloric effect of these compounds is accompanied by the first-order structural phase transformation. At the same time hydrostatic pressure can act as a parameter to tune the martensitic transition temperature[13]. In non-stoichiometric Ni-Mn-based Heusler family, a magneto-structural coupled state leads to a temperature-induced martensitic transition, which is between two crystallographic phases with significantly different magnetic structures. However, the change of high magnetic entropy is always concentrated in a small temperature range under the state of magnetic structure coupling, which is obviously not conductive to practical applications. So far, some methods have prominent effect on tuning working temperature interval, such as applying external fields, introducing doping element 2

Journal Pre-proof or sample fragmentation.[14] [15] [16] Our previous research has been reported that a large magnetoresistance in highly textured Mn44.7Ni43.5Sn11.8 melt spun ribbons. Under a lower magnetic field of 10 kOe, a giant MR of 25% was obtained at 276 K,[17] which was twice larger than that of polycrystalline alloys. The process is also accompanied by the first-order structural phase transformation. More interestingly, when the magnetic field decreases, the large negative MR of the ribbons from the field-induced transition remains constant at 273 K. The reason of above properties may be that magnetocrystalline anisotropy causes the domain walls displacement or twin variants reorientation to be frozen in a certain angle. As we know, in ferroic materials, such as ferroelastic, ferroelectric, and ferromagnetic materials, large caloric effects are expected in the region where the ferroic property spontaneously emerges.[18] These novel properties evoke us to further investigate hydrostatic pressure effect on the martensitic transformation(MT) and magnetocaloric effect(MCE) of Mn44.7Ni43.5Sn11.8 ribbons.

2. Experiment The precursor ingot was prepared by induction melting with nominal composition of Mn44.7Ni43.5Sn11.8 under a high-purity argon atmosphere. Subsequently, the ingot was induction melted in a quartz tube and melt-spun at a wheel surface speed of 15.0 m s-1. At the same time, the copper wheel was cooled by circulating cooling water system. The resulting ribbons were annealed at 1073 K for 1 h and cooled in the vacuum furnace. Microstructure and chemical composition of the ribbons were determined by field emission scanning electron microscopy (FE-SEM) (Hitachi S4800) attached with an x-ray energy dispersive spectroscopy (EDS) (Thermo System 7). The 3

Journal Pre-proof crystal structure of ribbons was analyzed by using a panalytical X'Pert pro type XRD with Cu Kα radiation at room temperature. The lattice parameters were calculated by using Jade 5.0 XRD analytical software. The magnetic properties of ribbons were measured by using a Quantum Design multi-use vibrating sample magnetometer VersaLab system equipped with the copper beryllium clamp type pressure cell (a maximum pressure of 13 GPa). The direction of external magnetic field was perpendicular to the free surface of the ribbons during the test, which was consistent with our previous research on MR.

3.

Results and discussion The typical SEM image on the cross section of the annealed Mn44.7Ni43.5Sn11.8 ribbon is shown

in Figure 1(a). The annealed fracture morphology shows that the longer axis of the columnar grain has a tendency to align perpendicularly to the free surface of the ribbon. The XRD patterns of melt-spun and annealed ribbons measured at room temperature are presented in Figure 1(b). It is clear that both of the samples have the cubic L21-type structure and crystal directions [400] are preferentially oriented perpendicular to the ribbon surface. The crystallographic texture exhibited in the XRD patterns is consistent with their grain-oriented columnar microstructure in SEM image. The lattice constants calculated from the XRD pattern are 5.994 and 5.985 Å for melt-spun and annealed ribbons, respectively. The change of lattice parameter and cell volume in annealed ribbon could be attributed to the increased atomic degree of order and the relaxing of internal stress.

4

(400)

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Intensity (a.u)

(b)

(422)

(220)

annealed

as-spun

30

40

50

60

70

80

90

2θ (deg.)

Figure 1. (a) The SEM on the cross section of Mn44.7Ni43.5Sn11.8 alloy ribbon. (b) The XRD patterns of Mn44.7Ni43.5Sn11.8 ribbons as-spun and annealed at room temperature.

Figure 2(a) displays the temperature dependence of the magnetization M(T) in magnetic field of 0.5 kOe under ambient pressure. The thermomagnetic curves were taken in field cooling (FC) and field heating (FH) sequences. In the process of FC, the value of magnetization gradually increases to 33.6 emu g-1 and a sudden drop of magnetization appears in the vicinity of martensitic starting temperature ( Ms ). Besides, the value of magnetization almost keeps steady around martensitic finishing temperature ( Mf ), indicating that the studied alloy undergoes a forward MT from the ferromagnetic(FM) austenitic phase with high-symmetry structure transforming into the paramagnetic martensitic phase with low-symmetry structure.[19] As shown in curve of FH, an abrupt jump of magnetization occurs near the austenitic starting temperature ( As ), and then it returns to 24.5 emu g-1 at austenitic finishing temperature ( Af ), implying that it experiences a reverse MT. According to the M-T curves, the values of the Ms , Mf ,

As and

Af

are

approximately determined to be 271 K, 269 K, 275 K and 277 K, respectively. As shown in M-T curves, a thermal hysteresis is about 6 K around the MT temperature, which is attributed to the first-order structural transition. The temperature dependence of the magnetization M(T) under selected magnetic fields is shown in Figure 2(b). It can be seen that the MT temperature shifts 5

Journal Pre-proof towards lower temperature region as the magnetic field increases. The temperature of the phase transition ( TM ) was determined by the maximum of the derivative of magnetization with respect to temperature. The driving rate dTM dH

is only about 0.13 K kOe-1, which indicates that the

change of magnetic field has little effect on MT temperature in the studied ribbons.

Figure 2. (a) Thermomagnetic curves of Mn44.7Ni43.5Sn11.8 ribbons under magnetic field of 0.5 kOe. (b) Thermomagnetic curves of Mn44.7Ni43.5Sn11.8 ribbons under selected magnetic fields.

In order to study the effect of applying hydrostatic pressure on MT for Mn44.7Ni43.5Sn11.8 ribbon, the thermomagnetic curves at different hydrostatic pressures were measured under magnetic field of 0.5 kOe and 30 kOe, respectively. Figure 3(a-b) present that the applied hydrostatic pressure almost has no impact on the transition width and transition slope, but the maximum value of magnetization decreases obviously as the hydrostatic pressure increases, especially under a low magnetic field. The above result is consistent with the model of uncompensated disordered-local moment (uDLM) proposed for the Ni-Mn-based alloys.[20] Among the Mn-rich compound, the surplus Mn(referred to as Mn2) atoms occupied the lattice positions of Sn. The antiferromagnetic(AFM) Mn-Mn interaction can be induced by the shorter Mn-Mn interatomic 6

Journal Pre-proof distances under the pressure. Therefore, the Mn2 atoms can be turned to anti-parallel direction with respect to the Mn(referred to as Mn1) moments in situ, which leads to a decrease in the total magnetization. According to the above analysis, the extreme sensitivity of magnetization to external pressure essentially results from the substitution of excess Mn for Sn. On the other hand, as shown in Figure 3(a), the Curie temperature( TC ) remains constant under hydrostatic pressure, and the MT temperature is closer to TC , which may also lead to the decline of magnetization. So it can be expected that the hydrostatic pressure has more obvious effect on magnetization at low magnetic fields.

Figure 3. Thermomagnetic curves of Mn44.7Ni43.5Sn11.8 ribbons measured at selected hydrostatic pressures under magnetic field of 0.5 kOe(a) and 30 kOe(b). The insets in Figure 3(a) and 3(b): the hydrostatic pressure dependence of martensitic transition temperature( TM ), the red solid lines are their best linear fitting.

The insets in Figure 3(a) and 3(b) show the hydrostatic pressure dependence of TM under magnetic fields of 0.5 kOe and 30 kOe, respectively. It can be seen that the TM present linear increasing within the measured range, indicating that hydrostatic pressure tends to stabilize the martensitic structure. It has been reported that the Ni-Mn hybridization and the effect of Sn lone 7

Journal Pre-proof pair on Ni lead to the cubic structure unstable and consequently triggers the structural transformation for Ni-Mn-Sn systems.[21] As mentioned before, in our high-Mn compound, there are Mn1 atoms in situ and excessive Mn2 atoms replacing Sn atoms. Due to that Mn has a smaller atomic radius than Sn, the Ni atom moves towards both Mn1 and Mn2 when Mn2-Ni bond replaces Sn-Ni bond, which is achieved by moving along the resultant force. Besides, the existence of the lone pair electrons on Sn also forces the movement of Ni atoms away from Sn to Mn. Further energy lowering is possible by an elongation of the lattice vector which results in the martensitic transition. Therefore, the value of TM is expected to increase, which is similar to the results of Ni-Mn-Z based shape memory alloys.[13]

[22] [23] [24]

The martensitic transition temperature( TM )

under different external fields are listed in Table 1. By calculating the data in table 1, we can get

dTM dP H 0.5 kOe =17.7 K GPa-1, dTM dP H 30 kOe =19.3 K GPa-1， dTM dH dTM dH

P  0.25GPa

=0.12 K kOe-1， dTM dH

P  0.5GPa

P  0 GPa

=0.10 K kOe-1， dTM dH

=0.13 K kOe-1， P  0.75GPa

=0.09 K

kOe-1. We can see that the value of dTM dH decreases as the hydrostatic pressure increases, which can be attributed to the fact that the hydrostatic pressure tends to stabilize martensite, and the external magnetic field-induced austenite is suppressed. For the same reason that dTM dP H 30 kOe is larger than dTM dP H 0.5 kOe . Moreover, it can be seen that the pressure-induced crystallographic change is easier to drive the MT than the external magnetic field. Table 1. Martensitic transition temperature( TM ) under different external fields for the studied alloy. H (kOe)

P (GPa)

0.5

0 (1 atm)

8

TM

(K)

270.4

Journal Pre-proof 0.25

273.0

0.50

277.5

0.75

283.7

0 (1 atm)

266.5

0.25

269.5

0.50

274.5

0.75

281.0

30

The isothermal magnetization M(H) loops at ambient pressure is shown in Figure 4(a). The isothermal magnetization M(H) loops were derived from the field heating thermomagnetic sequence. The plots were recorded during both increasing and decreasing magnetic field. The isothermal magnetization curves under other pressures are not listed. At 266 K, below As (275 K), no austenite is induced by magnetic field up to 30 kOe. At 272 K, a large jump in magnetization at about 15 kOe, due to the occurrence of magnetic-field-induced austenite, can be observed. After removing the magnetic field, the sample transformed back to martensite, but the magnetic hysteresis is beginning to be noticeable. As the temperature increases to 274 K, the magnetic hysteresis reaches the maximum, which is attributed to the first-order structural transition. At 276 K, the magnetization of the sample reaches the maximum value under 30 kOe, the magnetic hysteresis has disappeared, and the sample is completely austenite. The MCE in the vicinity of the magnetostructural martensitic transition can be quantified from the entropy change ( S ) induced from the isothermal application or removal of a given magnetic field.[25] From magnetization curves, it can be determined as:  M    dH 0 ( H ) T  H

S  

H (0)

9

Journal Pre-proof Where S denotes the entropy change for the change in H from 0 (H) to H (0). It should be noticed that the magnetic entropy change S includes the structural contribution (the structural entropy change during phase transformation) and the magnetic contribution. The values of S max under the selected pressures are summarized in Table 2. Table 2. The calculated maximum isothermal entropy changes S max was determined from the isothermal magnetization curves. P (GPa)

S max

(J kg−1 K−1)

0 (1 atm)

0.25

0.50

0.75

Field heating

35.9

31.7

27.6

18.5

Field cooling

-39.9

-37.2

-30.0

-26.1

Figure 4(b) shows the variation of S around TM in the field heating sequences, which was derived by the application of magnetic field. It is found that the maximum value( S max ) of magnetic entropy change attains to 35.9 J kg-1 K-1 under ambient pressure, which exceeds that previously reported in lots of Ni-Mn based Heusler alloys, such as Ni41Co9Mn40Sn10(25 J kg-1 K-1, 3 T),[26] Ni51.2Mn32.8In16(16 J kg-1 K-1, 5 T), Ni51Mn35Sn14(12.5 J kg-1 K-1, 5 T),[6] Ni48Mn39Sn13(13.5 J kg-1 K-1, 5 T), Ni47Mn40Sn13(34 J kg-1 K-1, 5 T),[27] Ni42Mn47.5Sn10.5(10.8 J kg-1 K-1, 2 T).[28] The S max significantly decreases to 18.5 J kg-1 K-1 under hydrostatic pressure of 0.75 GPa. Figure 4(c)

shows the variation of S around TM in the field cooling sequences, which was derived by the removal of magnetic field. It can be seen that the values of S derived by the removal of the magnetic field has opposite sign. Under the same pressure, the value of S max

is slightly larger

than that in the field heating sequence, which can be attributed to the fact that the phase transition temperature is lower in the cooling sequence. In addition, the value of

S max

decreases

significantly with the application of pressure. As mentioned previous, the magnetic entropy change S

includes the structural contribution ( Sstr ) and the magnetic contribution ( S M ). The 10

Journal Pre-proof structural entropy change in our studied alloys is mainly caused by the phase transition induced by external magnetic field. However, the hydrostatic pressure tends to stabilize martensite. Therefore, the application of hydrostatic pressure leads to the decrease of the ratio of the austenite induced by magnetic fields, which means that the value of

Sstr

decreases. In addition, the hydrostatic

pressure pushes up the phase transition temperature, which is closer to the Curie temperature, leading to a decrease in the value of S M . So the value of S max decreases with the application of hydrostatic pressure. Among the previous research, most of the Ni-Mn-Z systems show a decrease in the magnitude of MCE as well as the magnetization under pressure, such as Ni45Mn43CrSn11,[13] Ni45.5Co2Mn37.5Sn15,[29] Ni45Mn43CoSn11,[30] Ni50Mn35In15.[24] It is clear that the S (T) curve moves to higher temperature under pressure, indicating that a continuous change of

hydrostatic pressure can broaden the working temperature range for magnetic refrigeration.

Figure 4. (a) The isothermal magnetization M(H) loops of Mn44.7Ni43.5Sn11.8 ribbons under magnetic fields up to 30 kOe at ambient pressure. (b) The isothermal entropy changes as a function of temperature S (T) by the application of magnetic field. (c) The isothermal entropy changes as a function of temperature S (T) by the removal of magnetic field.

11

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Conclusions In summary, highly textured Heusler alloy Mn44.7Ni43.5Sn11.8 ribbons were prepared by melt

spinning. The XRD patterns indicate that the crystal directions [400] are preferentially oriented perpendicular to the ribbon surface. The dTM dP of 19.3 K GPa-1 is obtained in the vicinity of room temperature due to the strong correlation of magnetic exchange interaction with the Mn-Mn distances in our Mn-rich ribbons. As a result, a broadening of working temperature range for magnetic refrigeration was obtained by the application of hydrostatic pressure. The S max achieve 35.9 J kg-1 K-1 and 18.5 J kg-1 K-1 at 0 GPa and 0.75 GPa, respectively. The result is much higher than that in lots of Ni-Mn-based Heusler alloy, even those with similar compositions. In our previous research on MR, the magnetocrystalline anisotropy is caused by the orientation of crystal structure, which leads to the domain wall displacement or twin reorientation freezing to a certain angle at 273K. The result indicates that such orientation of crystal structure may lead to a larger S max during the process of magneto-structural coupled phase transition.

Acknowledgments This work is supported by the Scientific Activities of Selected Returned Overseas Professionals in Shanxi Province, Shanxi Scholarship Council of China (Grant No.2016-092), China Postdoctoral Science Foundation funded project (Grant No. 2015M571285), The Emerging Industry Leadership Talent Program of Shanxi Province (No. 2019042), The Recruitment Program of Global Experts of Shanxi Province (No. 091736) and Scientific and Technological Innovation Projects for Excellent Researchers of Shanxi Province (No. 201805D211042, 201805D111002), the 12

Journal Pre-proof National Natural Science Foundation of China (NSFC) (Nos. 11705124, 11704274).

(In this work, all figures don not need color in print.)

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Journal Pre-proof December 5, 2019 Dear Editors: No conflict of interest exits in the submission of this manuscript, and manuscript is approved by all authors for publication. I would like to declare on behalf of my co-authors that the work described was original research that has not been published previously, and not under consideration for publication elsewhere, in whole or in part. All the authors listed have approved the manuscript that is enclosed.

We deeply appreciate your consideration of our manuscript, and we look forward to receiving comments from the reviewers. If you have any queries, please contact me at the address below. Thank you and best regards. Yours sincerely, Fenghua Chen

Corresponding author: Name: Fenghua Chen E-mail: [email protected]

Journal Pre-proof In this work, the highlights are in the following: 1) Highly textured Heusler alloy Mn44.7Ni43.5Sn11.8 ribbons were prepared by melt spinning. 2) In contrast with other non-stoichiometric Ni-Mn-Sn compounds, a relatively lager value of dTMS dP of 19.3 K GPa-1 is obtained, which means a broadening of working temperature span for magnetic refrigeration. 3) A relatively large entropy change value of 35.9 J kg-1 K-1 is obtained under a magnetic field of 30 kOe, which would be related to the orientation of crystal structure. I hope this paper is suitable for “Solid State Communications”.