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
Cite this article:
YANG Jinhan, YAN Haile, LIU Haoxuan, ZHAO Ying, YANG Yiqiao, ZHAO Xiang, ZUO Liang. Phase Stability, Magnetism, and Mechanical Properties of A2BTi: First-Principles Calculations and Experimental Studies. Acta Metall Sin, 2024, 60(12): 1701-1709.
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.
Fig.1 Evolutions of total energy for Co2BTi (B = Mn, Fe, Ni) (a), Fe2BTi (B = Mn, Co, Ni) (b), and Ni2BTi (B = Mn, Co, Fe) (c) plotted as a function of tetragonal ratio c / a (a, c are lattice constants. For comparison, the total energies of the L21 structure for all systems are normalized to 0. The structures with c / a = 1.0 and c / a = 1.414 indicate the L21 (ordered bcc structure) and the ordered fcc structure, respectively. eV/f.u. means eV per formular unit. The arrows in Figs.1a and b indicate the c / a ratio of the tetragonal Ni2MnTi and Fe2NiTi lattices with the minimum total energy, respectively)
Element
Configuration of valence electron
Number of valence electron
Ti
3d34s1
4
Mn
3d64s1
7
Fe
3d74s1
8
Co
3d84s1
9
Ni
3d94s1
10
Table 1 Valence electron configurations and valence electron numbers of the studied elements
Fig.2 Distribution diagram of average atomic magnetic moment and average valence electron concentration (VEC) (Hollow dots and solid dots represent the alloy in which L21 phase is and isn't the most stable phase, respectively)
Fig.3 XRD spectra (a1-c1) and backscattered electron (BSE) images (a2-c2) for Co2NiTi (a1, a2), Fe2NiTi (b1, b2), and Ni2CoTi (c1, c2) alloys at room temperature (Insets in Figs.3a1, b1, and c1 show the crystal structural models of the matrix phase and the precipitated phases of Co2NiTi, Fe2NiTi, and Ni2CoTi alloys, respectively)
Fig.4 Temperature-dependent magnetization (M(T)) (a1-c1) and DSC (a2-c2) curves for Co2NiTi (a1, a2), Fe2NiTi (b1, b2), and Ni2CoTi (c1, c2) alloys (Inset in Fig.4a1 is an enlarged M(T) curve at the low-temperature range under the magnetic field interlity H = 0.01 T; insets in Figs.4a2-c2 are the DSC curves measured at the high-temperature range (300 K to the melting point). ZFC—zero-field-cooling, ZC—field-cooling, FH—field-heating)
Fig.5 Dependence of magnetization on magnetic field intensity (M(H)) curves (a), electronic resistance (b), and compression curves (c) for Co2NiTi, Fe2NiTi, and Ni2CoTi alloys
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
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 Ni50 - x Co x Mn39Sn11 (x = 0, 2, 4, 6) Heusler alloys [J]. Acta Metall. Sin., 2015, 51: 1010
李 哲, 徐 琛, 徐 坤 等. Ni50 - 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 Zn2YMn (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
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 Ni50.0Mn35.25In14.75 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