Ni<sub>2</sub>Cu基Heusler合金的电子结构、弹性参数与马氏体相变的第一性原理研究

王家旭; 张一心; 马圣然; 李昊泽; 罗鸿志

doi:10.7498/aps.74.20241485

摘要

Heusler合金中的马氏体相变因其具有的诸多物性成为金属功能材料领域的研究热点. 本文对一类新的Ni₂CuZ (Z = Al, Ga, In, Si, Ge, Sn, Sb) Heusler合金的原子占位、电子结构、弹性参数和马氏体相变进行了第一性原理研究. 结果表明该系列材料中Cu均择优占据Heusler合金晶格B位从而形成L2₁结构, 其基态为顺磁态. Ni₂CuZ发生四方晶格畸变后马氏体基态能量低于立方奥氏体, 相变能够发生, 这与材料电子结构的Jahn-Teller效应和奥氏体晶格的力学不稳定性有关, 也使其成为一种潜在的Heusler型形状记忆合金. 计算发现Ni₂CuZ奥氏体与马氏体相能量差ΔE_M与主族元素Z关系密切, Z属同一主族时, ΔE_M随Z原子序数增加单调增大, Z属同一周期时, 变化趋势恰好相反. 这与Heusler型形状记忆合金中通常的价电子浓度e/a或电子密度n判据并不一致, 但可以通过材料剪切模量$ C' $以及弹性常数C₄₄随Z元素的周期性变化解释. 该结果揭示了Heusler合金中马氏体相变与弹性参数之间的紧密联系, 可以将其作为预测新型形状记忆合金和分析材料物性的一个重要指标.

关键词:

Abstract

Ni₂-based Heusler alloys have received increasing attention due to their shape memory effects and the relevant application properties. It is interesting to explore new Ni₂-based shape memory alloys with novel properties. In this work, the site preference, electronic structure, elastic parameters and martensitic transformation of new Ni₂Cu-based Heusler alloys Ni₂CuZ (Z = Al, Ga, In, Si, Ge, Sn and Sb) are investigated theoretically. Between the two highly-ordered structures of Heusler alloys, Ni₂CuZ alloy tends to crystallize in the L2₁ structure with Cu atom entering the B site in the cubic lattice. In contrast, the XA structure is higher in energy and lower in stability. This is different from the usual rule that transition metal atoms with more valence electrons tend to occupy the A, C sites at first and can be related to the strong covalent hybridization between Ni and main group elements Z in L2₁ type Ni₂CuZ.Ni₂CuZ martensites are all lower in energy than the corresponding austenites, which makes them candidates for shape memory alloys. This can be explained by the Jahn-Teller effect characterized by the reduced states near E_F in the DOS structure and the mechanical instability of the cubic austenite lattice. The martensite-austenite energy difference ΔE_M is strongly influenced by main group elements Z. When Z are in the same group, the ΔE_M increases with their atomic number increasing, but when Z are in the same period, an opposite trend is observed. The ΔE_M can be regarded as a driving force for the martensitic transformation: a larger ΔE_M corresponds to a higher martensitic transformation T_M. In Heusler alloys, electron concentration e/a and electron density n are usually used to discuss the variation of T_M. An increase of e/a or n tends to increase T_M. However, this is in discrepancy with the results in Ni₂CuZ, which can be explained by using, the new factors, the negative shear modulus $ C' $ and softening of the elastic constant C₄₄ and their variations with Z elements. These results reveal the close relation between the martensitic transformation and mechanical parameters and indicate that they are important factors to predict new shape memory alloys and analyse their properties in Heusler alloys. It is also found that the Young’s modulus and shear modulus increase and Poisson’s ratio decreases after the martensitic transformation. Thus, the Ni₂CuZ martensite has higher stiffness and rigidity but lower ductility than the austenite.

Keywords:

作者及机构信息

1.

2.

通信作者: 罗鸿志, luo_hongzhi@hebut.edu.cn

基金项目: 河北省自然科学基金(批准号: E2024202139)资助的课题.

Authors and contacts

1.

2.

Corresponding author: LUO Hongzhi, luo_hongzhi@hebut.edu.cn

Funds: Project supported by the Natural Science Foundation of Hebei Province, China (Grant No. E2024202139).

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施引文献

下载: 全尺寸图片幻灯片

成分	a/Å	ΔE/(eV·f.u.^–1)	C₁₁/GPa	C₁₂/GPa	C₄₄/GPa	B/GPa	G/GPa	E/GPa	ν	B/G_V
Ni₂CuAl	5.72	–0.29	145.9	176.3	124.3	166.1	11.0	32.4	0.47	2.42
Ni₂CuGa	5.73	–0.28	150.2	181.0	109.6	170.7	5.4	16.0	0.48	2.87
Ni₂CuGa	5.75^*	—	141.3^*	177.8^*	110.4^*	165.6^*	–0.81^*	—	0.34^*	2.78^*
Ni₂CuIn	6.00	–0.20	123.9	149.5	88.8	140.9	3.8	11.4	0.49	2.93
Ni₂CuSi	5.63	–0.46	192.8	195.6	93.8	194.6	26.1	74.9	0.44	3.49
Ni₂CuGe	5.74	–0.40	167.9	171.5	92.8	170.3	25.1	71.9	0.43	3.10
Ni₂CuSn	5.99	–0.33	143.3	149.7	89.4	147.6	21.9	62.8	0.43	2.82
Ni₂CuSb	5.99	–0.45	149.9	148.2	76.3	148.8	24.1	68.7	0.42	3.23
注: *数据引自参考文献[25]

下载: 导出CSV

成分	V/Å³	c/a	e/a	n/Å^–3	ΔE_M/(eV·f.u.^–1)
Ni₂CuAl	187.15	1.24	8.50	0.727	–0.082
Ni₂CuGa	188.13	1.26	8.50	0.723	–0.090
Ni₂CuIn	216.00	1.28	8.50	0.630	–0.101
Ni₂CuSi	178.45	1.28	8.75	0.785	–0.032
Ni₂CuGe	189.12	1.30	8.75	0.740	–0.047
Ni₂CuSn	214.92	1.30	8.75	0.650	–0.049
Ni₂CuSb	214.92	1.18	9.00	0.670	–0.003

下载: 导出CSV

成分	C₁₁/GPa	C₃₃/GPa	C₄₄/GPa	C₆₆/GPa	C₁₂/GPa	C₁₃/GPa	B/GPa	G/GPa	E/GPa	ν
Ni₂CuAl	243.3	196.1	118.9	86.4	100.9	148.6	164.3	71.4	187.1	0.31
Ni₂CuGa	236.8	198.2	104.1	76.7	112.5	150.6	166.6	64.8	172.1	0.33
Ni₂CuIn	194.6	178.8	80.2	65.4	104.8	126.2	142.5	54.1	144.2	0.33
Ni₂CuSi	232.9	234.5	95.8	83.9	155.7	165.4	186.0	63.0	169.7	0.35
Ni₂CuGe	220.8	203.7	77.1	69.2	135.3	157.5	171.7	51.9	141.3	0.36
Ni₂CuSn	189.8	176.7	77.8	42.7	83.6	123.8	134.8	49.3	131.7	0.34
Ni₂CuSb	217.3	153.1	76.6	16.1	79.9	147.3	148.4	28.7	81.0	0.41

下载: 导出CSV

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First principles study of electronic structure, mechanical properties and possible martensitic transformation in Ni₂Cu-based Heusler alloys

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作者及机构信息

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通信作者: 罗鸿志, luo_hongzhi@hebut.edu.cn

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Corresponding author: LUO Hongzhi, luo_hongzhi@hebut.edu.cn

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First principles study of electronic structure, mechanical properties and possible martensitic transformation in Ni2Cu-based Heusler alloys

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Abstract

作者及机构信息

1. 2.

通信作者: 罗鸿志, luo_hongzhi@hebut.edu.cn

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Corresponding author: LUO Hongzhi, luo_hongzhi@hebut.edu.cn

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First principles study of electronic structure, mechanical properties and possible martensitic transformation in Ni₂Cu-based Heusler alloys

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