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
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