W1 - x Ir x 固溶合金几何结构、电子结构、力学和热力学性能的第一性原理计算

doi:10.11900/0412.1961.2020.00418

金属学报

2022, Vol. 58

Issue (2): 231-240 DOI: 10.11900/0412.1961.2020.00418

研究论文

本期目录 | 过刊浏览

W₁_-_x Ir _x 固溶合金几何结构、电子结构、力学和热力学性能的第一性原理计算

皇甫顥¹, 王子龙¹, 刘永利¹(

), 孟凡顺², 宋久鹏³, 祁阳¹

^1.东北大学材料科学与工程学院沈阳 110819
^2.辽宁科技大学理学院锦州 121001
^3.厦门钨业有限公司国家钨材料工程技术研究中心厦门 361021

A First Principles Investigation of W₁_-_x Ir _x Alloys: Structural, Electronic, Mechanical, and Thermal Properties

HUANGFU Hao¹, WANG Zilong¹, LIU Yongli¹(

), MENG Fanshun², SONG Jiupeng³, QI Yang¹

^1.College of Materials Science and Engineering, Northeastern University, Shenyang 110819, China
^2.School of Science, Liaoning University of Technology, Jinzhou 121001, China
^3.China National R&D Center for Tungsten Technology, Xiamen Tungsten Co. Ltd. , Xiamen 361021, China

引用本文:

皇甫顥, 王子龙, 刘永利, 孟凡顺, 宋久鹏, 祁阳. W₁_-_x Ir _x 固溶合金几何结构、电子结构、力学和热力学性能的第一性原理计算[J]. 金属学报, 2022, 58(2): 231-240.
Hao HUANGFU, Zilong WANG, Yongli LIU, Fanshun MENG, Jiupeng SONG, Yang QI. A First Principles Investigation of W₁_-_x Ir _x Alloys: Structural, Electronic, Mechanical, and Thermal Properties[J]. Acta Metall Sin, 2022, 58(2): 231-240.

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摘要:

利用基于密度泛函理论的第一性原理方法结合声子谱计算和价键作用分析，研究了Ir含量对W_{1 -}_x Ir _x (x = 0~12.96，原子分数，%)合金几何结构、相稳定性、力学性能以及热力学稳定性的影响，构建了Ir的添加量与W-Ir合金的相稳定性、力学以及热力学性能的变化关系。发现W-Ir合金的相稳定性随着Ir含量的增加而逐渐降低，这与W—Ir价键中部分反键态占据Fermi能级以下区域有关；Ir在W中的添加量小于7.4%时，W-Ir合金满足基态相稳定性要求；随着温度的升高以及Ir含量的增加，W-Ir合金的热力学稳定性得到提升，表明Ir适合添加到高温条件下应用的W中；Ir的加入能降低剪切模量，改善钨合金韧性，与实验观察一致，但Ir也能提升平面抗剪切变形能力。本征脆性的Ir对W的强韧化作用与W—Ir原子键合时轨道电子的转移和重叠方式有关。

关键词 ： W, Ir, 弹性性能, 热力学性能, 基态稳定性, 电子结构

Abstract：

Tungsten (W) possess comprehensive physical and chemical properties that are suitable for aerospace and space nuclear power applications, including the highest melting temperature (3410^oC) among metals, high elastic modulus, thermal shock resistance, and high temperature strength. However, its poor ductility at room temperatures significantly hinders its fabricability and potential use in the above-mentioned fields. Accordingly, to improve the ductility of W, solid solution strengthening is the primary method considered besides grain refining and deformation strengthening. Experimental studies have shown that Ir is a brittle metal with an fcc structure, but it can greatly improve the ductility of W; however, the corresponding mechanism is still unclear. Thus, using the first principles method based on density functional theory together with phonon spectrum calculations, the effect of the addition of different contents of Ir on the structure, phase stability, mechanical properties, and thermodynamic properties of W were studied. The relation between the addition of different contents of Ir and above-mentioned properties of W-Ir alloys were theoretically investigated. It was found that Ir can induce instability in the W-Ir alloy in the ground state due to the occupation of its antibonding electrons below the Fermi level. When content of Ir added is less than 7.4%, the formation of the W-Ir alloy becomes stable in the ground state. With an increase in temperature and the content of Ir, the thermodynamic stability is improved, implying that Ir is suitable for incorporation with W for application at high temperature. The addition of Ir helps to improve the toughness of the W alloy, which is consistent with the experimental observation. Besides, Ir can simultaneously improve the planar shear resistance. Furthermore, the pCOHP analysis revealed that the inherent mechanism of the ductile effect of brittle Ir in W is attributed to their different modes of electron transition and overlapping. For Ir, electrons transfer from its higher energy orbital of $d x 2 - y 2$ to the lower energy d _xz and d _yz orbitals. In contrast, for W, the electrons transfer from its low energy orbital of $d z 2$ to the d _xzand d _yz orbitals. The d _xzand d _yzorbitals of Ir and W form a metallic bond, which is further enhanced with an increase in the content of Ir added. Therefore, Ir acts as a toughness-enhancing element in W-Ir alloys.

Key words： W Ir elastic property thermodynamic property ground state stability electronic structure

收稿日期: 2020-10-26

ZTFLH:

TG131

作者简介: 皇甫顥，男，1995年生，硕士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2020.00418 或 https://www.ams.org.cn/CN/Y2022/V58/I2/231

图1 W-Ir固溶合金模型示意图(a) W (b) W98.15Ir1.85 (c) W96.30Ir3.70 (d) W92.59Ir7.41 (e) W88.89Ir11.11 (f) W87.04Ir12.96

图2 W-Ir二元合金形成能(ΔE)与Ir添加量的变化关系

图3 W-Ir二元合金的晶格常数与Ir含量的关系

图4 W-Ir二元合金和纯W[35~41]的弹性常数(C11、C12、C44)、弹性模量(B、G、E)、G / B和Cp随Ir添加量的变化曲线

图5 不同W-Ir合金中Ir与第一近邻W原子所成的Ir—W1键以及Ir与第二近邻W原子所成的Ir—W2键的投影晶体轨道Hamilton布局(pCOHP)曲线(a) W98.15Ir1.85 (b) W96.30Ir3.70 (c) W87.04Ir12.96

图6 不同W-Ir二元合金的平面及三维差分电荷密度分布Color online(a) W98.15Ir1.85, (001ˉ) plane (b) W96.30Ir3.70, (001ˉ) plane(c) W87.04Ir12.96, (001ˉ) plane (d) W87.04Ir12.96, 3D distribution

图7 W-Ir合金的第一近邻原子间(W—W1、Ir—Ir1、Ir—W1)平均键长以及纯金属Ir和W的第一近邻原子间(Ir—Ir1和W—W1)平均键长

图8 不同W-Ir二元合金的自由能(F)、熵(S)、焓(H)和比热容(cV)与温度的依赖关系

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