A2BTi型磁性功能合金相稳定性、磁性与力学性能的第一性原理计算和实验研究

doi:10.11900/0412.1961.2022.00412

金属学报

2024, Vol. 60

Issue (12): 1701-1709 DOI: 10.11900/0412.1961.2022.00412

研究论文

本期目录 | 过刊浏览

A₂BTi型磁性功能合金相稳定性、磁性与力学性能的第一性原理计算和实验研究

杨谨菡¹, 闫海乐¹(

), 刘昊轩¹, 赵莹¹, 杨一俏², 赵骧¹, 左良¹

1 东北大学材料科学与工程学院材料各向异性与织构教育部重点实验室沈阳 110819
2 东北大学分析测试中心沈阳 110819

Phase Stability, Magnetism, and Mechanical Properties of A₂BTi: First-Principles Calculations and Experimental Studies

YANG Jinhan¹, YAN Haile¹(

), LIU Haoxuan¹, ZHAO Ying¹, YANG Yiqiao², ZHAO Xiang¹, ZUO Liang¹

1 Key Laboratory for Anisotropy and Texture of Materials (Ministry of Education), School of Materials Science and Engineering, Northeastern University, Shenyang 110819, China
2 Analytical and Testing Center, Northeastern University, Shenyang 110819, China

引用本文:

杨谨菡, 闫海乐, 刘昊轩, 赵莹, 杨一俏, 赵骧, 左良. A₂BTi型磁性功能合金相稳定性、磁性与力学性能的第一性原理计算和实验研究[J]. 金属学报, 2024, 60(12): 1701-1709.
Jinhan YANG, Haile YAN, Haoxuan LIU, Ying ZHAO, Yiqiao YANG, Xiang ZHAO, Liang ZUO. Phase Stability, Magnetism, and Mechanical Properties of A₂BTi: First-Principles Calculations and Experimental Studies[J]. Acta Metall Sin, 2024, 60(12): 1701-1709.

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摘要:

探究新型磁性Heusler合金对于开发新一代智能传感材料具有重要的意义。本工作采用第一性原理计算对8种新型A₂BTi型磁性功能合金，包括3种钴基合金(Co₂MnTi、Co₂FeTi和Co₂NiTi)、3种铁基合金(Fe₂MnTi、Fe₂CoTi和Fe₂NiTi)以及2种镍基合金(Ni₂FeTi、Ni₂CoTi)，在四方晶格畸变过程中的相稳定性演化进行了理论计算，并对其L2₁相稳定性演变规律及背后机制进行了探讨。研究发现，价电子浓度和磁性是决定A₂BTi型合金L2₁相结构稳定性的关键参数。针对理论计算筛选出的L2₁相为非最稳定结构的Co₂NiTi、Fe₂NiTi和Ni₂CoTi，分别制备了合金样品并对其晶体结构、相变行为、磁性能、电阻和力学性能进行了实验研究。结果表明，室温下Co₂NiTi由有序面心立方L1₂结构基体相和六方Co₃Ti型第二相构成，Fe₂NiTi由六方Fe₂Ti型基体相和四方FeNi型第二相构成，Ni₂CoTi为单一的Ni₃Ti型六方结构。Co₂NiTi、Fe₂NiTi和Ni₂CoTi均不存在一阶结构相变，这可能与其L2₁结构低的晶格稳定性致使其难以被形成有关。Fe₂NiTi和Ni₂CoTi具有较强的磁性且存在二阶Curie磁性转变。Fe₂NiTi具有高的压缩强度(1280 MPa)、中等压缩应变(5%)及较大电阻(120 μΩ·cm)，而Co₂NiTi和Ni₂CoTi具有优异的压缩塑性和较小的电阻，这3种合金不同的功能行为可能与其价电子浓度差异带来的化学键中金属键和共价键组分比例不同有关。

关键词 ：磁性功能材料, 磁性形状记忆合金, Heusler合金, 马氏体相变, 第一性原理计算

Abstract：

Exploring novel magnetic Heusler alloys is of great significance for the development of a new generation of smart sensing materials. The A₂BC type magnetic alloy, which comprises transition magnetic metal elements A and B and III-V main group element C (p-block element), has gained significant attention due to its various physical and chemical properties, including semimetallic magnetism, ferromagnetic shape memory effect, multicaloric effect, and superconductive effect. In this study, eight new A₂BTi type magnetic functional alloys, including three Co-based alloys (Co₂MnTi, Co₂FeTi, and Co₂NiTi), three Fe-based alloys (Fe₂MnTi, Fe₂CoTi, and Fe₂NiTi), and two Ni-based alloys (Ni₂FeTi and Ni₂CoTi), were investigated for their phase stability against tetragonal distortion using first-principles calculation. The underlying mechanism for the stability of the L2₁ phase was discussed. The results show that valence electron concentration and magnetism are the key parameters in determining the structural stability of L2₁ phase in A₂BTi type alloys. Co₂NiTi, Fe₂NiTi, and Ni₂CoTi alloy samples, whose L2₁ structure is an unstable phase, were prepared, and their crystal structure, phase transformation, magnetic properties, electrical resistance, and mechanical properties were investigated experimentally. The results show that at 298 K, Co₂NiTi is composed of an ordered face-centered cubic L1₂ structured matrix phase and a hexagonal Co₃Ti-type second phase, Fe₂NiTi is composed of a hexagonal Fe₂Ti-type matrix phase and a tetragonal FeNi-type second phase, and Ni₂CoTi has a single hexagonal Ni₃Ti-type structure. The fact that no compound undergoes a first-order structural phase transition may be due to the weak stabilities of their L2₁ phases. Fe₂NiTi and Ni₂CoTi have strong magnetic properties and undergo a second-order Curie magnetic transition during cooling. Fe₂NiTi has high compressive strength (1280 MPa), moderate compressive strain (5%), and large resistance (120 μΩ·cm), while Co₂NiTi and Ni₂CoTi have excellent compressive plasticity and small resistance. This phenomenon may be related to the different proportions of metallic and covalent bonding caused by the difference in valence electron concentration of the three alloys.

Key words： magnetic functional material magnetic shape memory alloy Heusler alloy martensitic transformation first-principles calculation

收稿日期: 2022-08-25

ZTFLH:

TG139.6

基金资助:中央高校基本科研业务费项目(N2202015);中央高校基本科研业务费项目(N2230002)

通讯作者: 闫海乐，yanhaile@mail.neu.edu.cn，主要从事相变功能材料的理论与实验研究

Corresponding author: YAN Haile, associate professor, Tel: 13909823853, E-mail: yanhaile@mail.neu.edu.cn

作者简介: 杨谨菡，女，1997年生，博士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2022.00412 或 https://www.ams.org.cn/CN/Y2024/V60/I12/1701

图1 Co2BTi (B = Mn、Fe和Ni)、Fe2BTi (B = Mn、Co和Ni)和Ni2BTi (B = Mn、Co和Fe)合金晶格总能量随着晶格四方畸变度c / a的变化曲线

表1 所研究元素的价电子配置及价电子数

图2 平均原子磁矩与平均价电子浓度分布图

图3 Co2NiTi、Fe2NiTi和Ni2CoTi室温XRD谱和背散射电子(BSE)像

图4 Co2NiTi、Fe2NiTi和Ni2CoTi合金磁化强度-温度(M(T))曲线以及DSC曲线

图5 Co2NiTi、Fe2NiTi和Ni2CoTi合金磁化强度随磁场强度变化(M(H))曲线、电阻及压缩曲线

1	Zuo L, Li Z B, Yan H L, et al. Texturation and functional behaviors of polycrystalline Ni-Mn-X phase transformation alloys [J]. Acta Metall. Sin., 2021, 57: 1396
1	左良, 李宗宾, 闫海乐等. 多晶Ni-Mn-X相变合金的织构化与功能行为 [J]. 金属学报, 2021, 57: 1396
2	Karaca H E, Karaman I, Basaran B, et al. Magnetic field-induced phase transformation in NiMnCoIn magnetic shape-memory alloys——A new actuation mechanism with large work output [J]. Adv. Funct. Mater., 2009, 19: 983
3	Graf T, Felser C, Parkin S S P. Simple rules for the understanding of Heusler compounds [J]. Prog. Solid State Chem., 2011, 39: 1
4	Yan H L, Zhang Y D, Esling C, et al. Determination of strain path during martensitic transformation in materials with two possible transformation orientation relationships from variant self-organization [J]. Acta Mater., 2021, 202: 112
5	Yan H L, Zhang Y D, Xu N, et al. Crystal structure determination of incommensurate modulated martensite in Ni-Mn-In Heusler alloys [J]. Acta Mater., 2015, 88: 375
6	Kainuma R, Imano Y, Ito W, et al. Magnetic-field-induced shape recovery by reverse phase transformation [J]. Nature, 2006, 439: 957
7	Ullakko K, Huang J K, Kantner C, et al. Large magnetic-field-induced strains in Ni₂MnGa single crystals [J]. Appl. Phys. Lett., 1996, 69: 1966
8	Li Z, Xu C, Xu K, et al. Study of martensitic transformation and strain behavior in Ni_{50 -} _x Co _x Mn₃₉Sn₁₁ (x = 0, 2, 4, 6) Heusler alloys [J]. Acta Metall. Sin., 2015, 51: 1010
8	李哲, 徐琛, 徐坤等. Ni_{50 -} _x Co _x Mn₃₉Sn₁₁ (x = 0, 2, 4, 6) Heusler合金的马氏体相变和应变行为研究 [J]. 金属学报, 2015, 51: 1010
9	Yan H L, Liu H X, Zhao Y, et al. Impact of B alloying on ductility and phase transition in the Ni-Mn-based magnetic shape memory alloys: Insights from first-principles calculation [J]. J. Mater. Sci. Technol., 2021, 74: 27
10	Wei Z Y, Liu E K, Chen J H, et al. Realization of multifunctional shape-memory ferromagnets in all-d-metal Heusler phases [J]. Appl. Phys. Lett., 2015, 107: 022406
11	Wei Z Y, Liu E K, Li Y, et al. Magnetostructural martensitic transformations with large volume changes and magneto-strains in all-d-metal Heusler alloys [J]. Appl. Phys. Lett., 2016, 109: 071904
12	Wei Z Y, Sun W, Shen Q, et al. Elastocaloric effect of all-d-metal Heusler NiMnTi(Co) magnetic shape memory alloys by digital image correlation and infrared thermography [J]. Appl. Phys. Lett., 2019, 114: 101903
13	Yan H L, Wang L D, Liu H X, et al. Giant elastocaloric effect and exceptional mechanical properties in an all-d-metal Ni-Mn-Ti alloy: Experimental and ab-initio studies [J]. Mater. Des., 2019, 184: 108180
14	de Paula V G, Reis M S. All-d-metal full Heusler alloys: A novel class of functional materials [J]. Chem. Mater., 2021, 33: 5483
15	Liu S L, Xuan H C, Cao T, et al. Magnetocaloric and elastocaloric effects in all-d-metal Ni₃₇Co₉Fe₄Mn₃₅Ti₁₅ magnetic shape memory alloy [J]. Phys. Status Solidi, 2019, 216A: 1900563
16	Aznar A, Gràcia-Condal A, Planes A, et al. Giant barocaloric effect in all-d-metal Heusler shape memory alloys [J]. Phys. Rev. Mater., 2019, 3: 044406
17	Cong D Y, Xiong W X, Planes A, et al. Colossal elastocaloric effect in ferroelastic Ni-Mn-Ti alloys [J]. Phys. Rev. Lett., 2019, 122: 255703
18	Shen Y, Wei Z Y, Sun W, et al. Large elastocaloric effect in directionally solidified all-d-metal Heusler metamagnetic shape memory alloys [J]. Acta Mater., 2020, 188: 677 doi: 10.1016/j.actamat.2020.02.045
19	Ni Z N, Ma Y X, Liu X T, et al. Electronic structure, magnetic properties and martensitic transformation in all-d-metal Heusler alloys Zn₂ YMn (Y = Fe, Co, Ni, Cu) [J]. J. Magn. Magn. Mater., 2018, 451: 721
20	Liu K, Ma S C, Ma C C, et al. Martensitic transformation and giant magneto-functional properties in all-d-metal Ni-Co-Mn-Ti alloy ribbons [J]. J. Alloys Compd., 2019, 790: 78
21	Zhang F Q, Batashev I, van Dijk N, et al. Reduced hysteresis and enhanced giant magnetocaloric effect in B-doped all-d-metal Ni-Co-Mn-Ti-based Heusler materials [J]. Phys. Rev. Appl., 2022, 17: 054032
22	Taubel A, Beckmann B, Pfeuffer L, et al. Tailoring magnetocaloric effect in all-d-metal Ni-Co-Mn-Ti Heusler alloys: A combined experimental and theoretical study [J]. Acta Mater., 2020, 201: 425
23	Xiong C C, Bai J, Li Y S, et al. First-principles investigation on phase stability, elastic and magnetic properties of boron doping in Ni-Mn-Ti alloy [J]. Acta Metall. Sin. (Engl. Lett.), 2022, 35: 1175
24	Sun X M, Cong D Y, Ren Y, et al. Magnetic-field-induced strain-glass-to-martensite transition in a Fe-Mn-Ga alloy [J]. Acta Mater., 2020, 183: 11
25	Hafner J. Ab-initio simulations of materials using VASP: Density-functional theory and beyond [J]. J. Comput. Chem., 2008, 29: 2044
26	Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple [J]. Phys. Rev. Lett., 1996, 77: 3865 doi: 10.1103/PhysRevLett.77.3865 pmid: 10062328
27	Blöchl P E. Projector augmented-wave method [J]. Phys. Rev., 1994, 50B: 17953
28	Yan H L, Liu H X, Huang X M, et al. First-principles investigation of Mg substitution for Ga on martensitic transformation, magnetism and electronic structures in Ni₂MnGa [J]. J. Alloys Compd., 2020, 843: 156049
29	Huang X M, Zhao Y, Yan H L, et al. A first-principle assisted framework for designing high elastocaloric Ni-Mn-based magnetic shape memory alloy [J]. J. Mater. Sci. Technol., 2023, 134: 151
30	Monkhorst H J, Pack J D. Special points for Brillouin-zone integrations [J]. Phys. Rev., 1976, 13B: 5188
31	Petříček V, Dušek M, Palatinus L. Crystallographic computing system JANA2006: General features [J]. Z. Kristallogr. Cryst. Mater., 2014, 229: 345
32	Grimvall G, Magyari-Köpe B, Ozoliņš V, et al. Lattice instabilities in metallic elements [J]. Rev. Mod. Phys., 2012, 84: 945
33	Yan H L, Zhao Y, Liu H X, et al. Ab-initio revelation on the origins of Ti substitution for Ga, Mn and Ni on ferromagnetism, phase stability and elastic properties in Ni₂MnGa [J]. J. Alloys Compd., 2020, 821: 153481
34	Bhattacharya K, Conti S, Zanzotto G, et al. Crystal symmetry and the reversibility of martensitic transformations [J]. Nature, 2004, 428: 55
35	Guo S, Ng C, Lu J, et al. Effect of valence electron concentration on stability of fcc or bcc phase in high entropy alloys [J]. J. Appl. Phys., 2011, 109: 103505
36	Nguyen-Manh D, Pettifor D G. Electronic structure, phase stability and elastic moduli of AB transition metal aluminides [J]. Intermetallics, 1999, 7: 1095
37	Mizutani U. Hume-Rothery rules for structurally complex alloy phases [J]. MRS Bull., 2012, 37: 169
38	Massalski T B, Laughlin D E. The surprising role of magnetism on the phase stability of Fe (Ferro) [J]. Calphad, 2009, 33: 3
39	Körmann F, Hickel T, Neugebauer J. Influence of magnetic excitations on the phase stability of metals and steels [J]. Curr. Opin. Solid State Mater. Sci., 2016, 20: 77
40	Yan H L, Sánchez-Valdés C F, Zhang Y D, et al. Correlation between crystallographic and microstructural features and low hysteresis behavior in Ni_50.0Mn_35.25In_14.75 melt-spun ribbons [J]. J. Alloys Compd., 2018, 767: 544
41	Yan H L, Zhao Y, Liu H X, et al. Occupation preferences and impacts of interstitial H, C, N, and O on magnetism and phase stability of Ni₂MnGa magnetic shape memory alloys by first-principles calculations [J]. J. Appl. Phys., 2022, 131: 205101
42	Naohara T, Inoue A, Minemura T, et al. Microstructures, mechanical properties, and electrical resistivity of rapidly quenched Fe-Cr-Al alloys [J]. Metall. Mater. Trans., 1982, 13A: 337
43	Liu H X, Yan H L, Jia N, et al. Machine-learning-assisted discovery of empirical rule for inherent brittleness of full Heusler alloys [J]. J. Mater. Sci. Technol., 2022, 131: 1
44	Massalski T B, Mizutani U. Electronic structure of Hume-Rothery phases [J]. Prog. Mater. Sci., 1978, 22: 151

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