Effects of Fe doping on Martensitic Transformation and magnetic properties of Ni-Mn-Ti All-d-metal Heusler Alloy

Jin Miao; Bai Jing; Xu Jia-Xin; Jiang Xin-Jun; Zhang Yu; Liu Xin; Zhao Xiang; Zuo Liang

doi:10.7498/aps.72.20222037

Abstract

Ni-Mn-Ti-based all-d-metal Heusler alloys have become a hot research topic in the field of metal functional materials due to their excellent mechanical properties and elastocaloric effect. However, the relatively large critical stress and transition hysteresis limit its practical applications. Some researchers have found that doping Fe in Ni-Mn-based alloys can not only reduce hysteresis, but also greatly improve the mechanical properties of alloys. Based on this, the effects of Fe doping on phase stability, martensitic transformation and magnetic properties of Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) Heusler alloys are systematically studied by first principles calculation. The corresponding magnetic states of the austenite and martensite of the alloy systems are determined according to the results of the formation energy. The variations of the lattice constants and the phase stability of the austenite and martensite with the increase of Fe content in the alloy systems are revealed, and the associated mechanism is elucidated. The atomic and total magnetic moments of the austenite and martensite in the Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) systems are calculated. Based on the results of electronic structure, the essential reasons for the magnetic state changes of the alloys are further explained.In the Ni_50–xMn_37.5Ti_12.5Fe_x alloy system, the lattice constant of austenite decreases gradually with the increase of Fe doping amount. The stability of austenite phase and martensite phase decrease with the increase of Fe doping amount. Under the different compositions, the formation energy of martensite is always lower than that of austenite, indicating that the alloy can undergo martensite transformation. The energy difference ΔE, electron concentration e/a and density of electrons n of the alloy show a decreasing trend, indicating that the driving force of martensitic transformation decreases, and the corresponding martensitic transformation temperature decreases with the increase of Fe atom doping.The austenite of the alloy is ferromagnetic and the martensite is antiferromagnetic. After the martensitic transformation, the distance between Mn-Mn atoms decreases, and the magnetic moments of Mn_Mn and Mn_Ti atoms are arranged in antiparallel manner, resulting in the total magnetic moments being almost zero. The magnetic properties of the two phases are little affected by the amount of Fe atom doping. The peak density of electronic states in the Fermi surface of martensite phase is lower than that of austenite phase, indicating that martensite phase has a more stable electronic structure than austenite phase. During the transition from austenite to martensite, there is a Jahn-Teller splitting effect at the peak of the down-spin density of states near the Fermi surface. The aim of this paper is to provide guidance for designing the composition design and optimizing the property of the Ni-Mn-Ti-Fe alloy.

Keywords:

Authors and contacts

1.
Key Laboratory for Anisotropy and Texture of Materials (Ministry of Education), School of Material Science and Engineering, Northeastern University, Shenyang 110819, China
2.
Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province, School of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao 066004, China

Corresponding author: Bai Jing, baijing@neuq.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 51771044), the Fundamental Research Funds for the Central Universities (Grant No. N2223025), and the Performance Subsidy Fund for Key Laboratory of Dielectric and Electrolyte Functional Material of Hebei Province, China (Grant No. 22567627H).

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References

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图 1 Ni_50–xMn_37.5Ti_12.5Fe_x(x = 3.125, 6.25, 9.375)合金系奥氏体相的原子占位方式　(a) x = 3.125; (b1) x = 6.25, 聚集分布; (b2) x = 6.25, 离散分布; (c) x = 9.375

Figure 1. Atomic occupancy of austenitic phase in Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) alloys: (a) x = 3.125; (b1) x = 6.25, aggregated distribution; (b2) x = 6.25, distant distribution; (c) x = 9.375.

DownLoad: Full-Size Img PowerPoint

图 2 Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375)合金系在铁磁性和反铁磁性下的形成能　(a) 奥氏体相; (b) 马氏体相

Figure 2. The E_f for Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) alloys in ferromagnetic and antiferromagnetic: (a) Austenite; (b) martensite.

DownLoad: Full-Size Img PowerPoint

图 3 (a) Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375)合金系的形成能随Fe掺杂含量的变化趋势; (b) Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375)合金系奥氏体和马氏体的能量差ΔE和电子浓度e/a随Fe掺杂量的变化

Figure 3. (a) E_f of Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) alloys; (b) variation of energy difference ΔE and e/a of Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) alloys with Fe doping content.

DownLoad: Full-Size Img PowerPoint

图 4 Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375)合金系的原子间距　(a) 奥氏体; (b) 马氏体

Figure 4. Atomic distance of Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) alloys: (a) Austenite; (b) martensite.

DownLoad: Full-Size Img PowerPoint

图 5 (a) Ni_50–xMn_37.5Ti_12.5Fe_x(x = 3.125, 6.25, 9.375)合金的总磁矩; (b) Ni_50–xMn_37.5Ti_12.5Fe_x(x = 3.125, 6.25, 9.375) 合金的原子磁矩

Figure 5. (a) Total magnetic moments of Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) alloys; (b) atomic magnetic moments of Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) alloys.

DownLoad: Full-Size Img PowerPoint

图 6 Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375)合金系的总态密度　(a) x = 3.125; (b) x = 6.25; (c) x = 9.375

Figure 6. TDOS of Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) alloys: (a) x = 3.125; (b) x = 6.25; (c) x = 9.375.

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图 7 Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375)合金系的分波电子态密度　(a) x = 3.125; (b) x = 6.25; (c) x = 9.375

Figure 7. PDOS of Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) alloys: (a) x = 3.125; (b) x = 6.25; (c) x = 9.375.

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表 1 Ni_50–xMn_37.5Ti_12.5Fe_x(x = 3.125, 6.25, 9.375)合金系的电子浓度e/a、晶胞体积V_cell和电子密度n

Table 1. Electron concentration (e/a), the cell volume (V_cell), and density of electrons (n) of Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) alloys.

成分 e/a V_cell n

x = 3.125 8.06 201.25 0.641
x = 6.25 8 200.31 0.639
x = 9.375 7.94 199.38 0.637

DownLoad: CSV

表 2 Ni_50–xMn_37.5Ti_12.5Fe_x(x = 3.125, 6.25, 9.375)合金系的平衡晶格常数

Table 2. Equilibrium lattice parameters of Ni_50–xMn_37.5Ti_12.5Fe_x (x = 3.125, 6.25, 9.375) alloys.

相晶格常数铁掺杂量
x = 3.125 x = 6.25 x = 9.375

Austenite a = b = c/Å 5.86 5.85 5.84
V/Å³ 201.25 200.31 199.38
Martensite a/Å 9.09 7.52 7.51
b/Å 4.14 3.76 3.76
c/Å 5.08 6.83 6.81
V/Å³ 190.94 193.41 192.49

DownLoad: CSV

[1]	Kainuma R, Oikawa K, Ito W, Sutou Y, Kanomata T, Ishida K 2008 J. Mater. Chem. 18 1837 Google Scholar
[2]	Kainuma R, Imano Y, Ito W, Sutou Y, Morito H, Okamoto S, Kitakami O, Oikawa K, Fujita A, Kanomata T, Ishida K 2006 Nature 439 7079
[3]	Oikawa K, Ito W, Imano Y, Sutou Y, Kainuma R, Ishida K, Okamoto S, Kitakami O, Kanomata T 2006 Appl. Phys. Lett. 88 122507 Google Scholar
[4]	Otsuka K, Shimizu K, Cornelis I, Wayman C M 1972 Scr. Metall. 6 5
[5]	Liu J, Gottschall T, Skokov K P, Moore J D, Gutfleisch O 2012 Nat. Mater. 11 620 Google Scholar
[6]	Pathak A K, Khan M, Dubenko I, Stadler S, Ali N 2007 Appl. Phys. Lett. 90 262504 Google Scholar
[7]	Mañosa L, González-Alonso D, Planes A, Bonnot E, Barrio M, Tamarit J, Aksoy S, Acet M 2010 Nat. Mater. 9 478 Google Scholar
[8]	Huang Y J, Hu Q D, Bruno N M, Chen J, Karaman I, Ross Jr J H, Li J G 2015 Scr. Mater. 105 42 Google Scholar
[9]	Xiao F, Fukuda T, Jin X, Liu J, Kakeshita T 2018 Phys. Status Solidi B 255 1700246 Google Scholar
[10]	Cong D, Xiong W, Planes A, Ren Y, Mañosa L, Cao P, Nie Z, Sun X, Yang Z, Hong X, Wang Y 2019 Phys. Rev. Lett. 122 255703 Google Scholar
[11]	Liu K, Han X, Yu K, Ma C, Zhang Z, Song Y, Ma S, Zeng H, Chen C, Luo X 2019 Intermetallics 110 106472 Google Scholar
[12]	Sarawate N, Dapino M 2006 Appl. Phys. Lett. 88 121923 Google Scholar
[13]	Karaman I, Basaran B, Karaca H E, Karsilayan A I, Chumlyakov Y I 2007 Appl. Phys. Lett. 90 172505 Google Scholar
[14]	Huang L, Cong D Y, Suo H L, Wang Y D 2014 Appl. Phys. Lett. 104 132407 Google Scholar
[15]	Wei Z Y, Liu E K, Chen J H, Li Y, Liu G D, Luo H Z, Xi X K, Zhang H W, Wang W H, Wu G H 2015 Appl. Phys. Lett. 107 022406 Google Scholar
[16]	Li G J, Liu E K, Wu G H 2022 J. Alloys Compd. 923 166369 Google Scholar
[17]	Wu M X, Zhou F, Khenata R, Kuang M Q, Wang X T 2021 Front. Chem. 8 546947
[18]	Wei Z Y, Liu E K, Li Y, Han X L, Du Z W, Luo H Z, Liu G D, Xi X K, Zhang H W, Wang W H, Wu G H 2016 Appl. Phys. Lett. 109 071904 Google Scholar
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[20]	Guan Z Q, Bai J, Gu J L, Liang X Z, Liu D, Jiang X J, Huang R K, Zhang Y D, Esling L D, Zhao X, Zuo L 2021 J. Mater. Sci. Technol. 68 103 Google Scholar
[21]	Liu S, Xuan H, Cao T, Wang L, Xie Z, Liang X, Li H, Feng L, Chen F, Han P 2019 Phys. Status Solidi A 216 1900563 Google Scholar
[22]	Taubel A, Beckmann B, Pfeuffer L, Fortunato N, Scheibel F, Ener S, Gottschall T, Skokov K P, Zhang H, Gutfleisch O 2020 Acta Mater. 201 425 Google Scholar
[23]	Li S H, Cong D Y, Xiong W X, Chen Z, Zhang X, Nie Z, Li S, Li R, Wang Y, Cao Y 2021 ACS Appl. Mater. Interfaces 13 31870 Google Scholar
[24]	Chang L C, Read T A 1951 J. Met. 1989 3 47
[25]	Buehler W J, Gilfrich J V, Wiley R C 1963 J. Appl. Phys. 34 1475 Google Scholar
[26]	Liu X, Bai J, Sun S D, Xu J X, Jiang X J, Guan Z Q, Gu J L, Cong D Y, Zhang Y D, Esling C, Zhao X, Zuo L 2022 J. Appl. Phys. 132 095101 Google Scholar
[27]	Liu K, Ma S C, Ma C C, Han X Q, Yu K, Yang S, Zhang Z S, Song Y, Luo X H, Chen C C, Rehman S U, Zhong Z C 2019 J. Alloys Compd. 790 78 Google Scholar
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[29]	Kresse G, Furthmuller J 1996 Phys. Rev. B 54 11169 Google Scholar
[30]	Kresse G, Hafner J 1994 J. Phys. Condens. Matter. 6 8245 Google Scholar
[31]	Froyen S 1989 Phys. Rev. B 39 3168 Google Scholar
[32]	Bai J, Raulot J M, Zhang Y D, Esling C, Zhao X, Zuo L 2010 J. Appl. Phys. 108 064904 Google Scholar
[33]	Kaufmann S, Rößler U, Heczko O, Wuttig M, Buschbeck J, Schultz L, Fahler S 2010 Phys. Rev. Lett. 104 145702 Google Scholar
[34]	Zayak A T, Adeagbo W A, Entel P, Rabe K M 2006 Appl. Phys. Lett. 88 111903 Google Scholar
[35]	Chen X Q, Yang F J, Lu X, Qin Z X 2007 Phys. Status Solidi B 244 1047 Google Scholar
[36]	Kundu A, Ghosh S, Ghosh S 2017 Phys. Rev. B 96 174107 Google Scholar
[37]	Biochl P E, Jepsen O, Andersen O K 1994 Phys. Rev. B 49 16223 Google Scholar
[38]	Xiao H B, Yang C P, Wang R L, Marchenkov V V, Bärner K 2012 J. Appl. Phys. 112 123723 Google Scholar
[39]	Tan C L, Huang Y W, Tian X H, Jiang J X, Cai W 2012 Appl. Phys. Lett. 100 132402 Google Scholar
[40]	Ye M, Kimura A, Miura Y, Shirai M, Cui Y T, Shimada K, Namatame H, Taniguchi M, Ueda S, Kobayashi K, Kainuma R, Shishido T, Fukushima K, Kanomata T 2010 Phys. Rev. Lett. 104 176401 Google Scholar

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