合金原子对L12型Al-Zr-X三元铝合金表面电偶腐蚀影响的第一性原理研究

doi:10.19596/j.cnki.1001-246x.8678

摘要/Abstract

摘要：

本文在AlZr二元合金的基础上, 利用第一性原理计算方法, 全面计算19种L1₂-Al_xZr_yX_z(X=Pd、Pt、Au、K、Rb、Sr、Ba、Ca、Yb、La、Ce、Y、Er、Sc、Zr、Ti、Cd、Hf、In)三元析出相的(100)、(110)和(111)三种晶面作为表面时的功函数, 并分析其与掺杂原子电负性之间的关系, 从电子层面阐明掺杂原子对L1₂型Al-Zr-X三元铝合金表面电偶腐蚀性能影响的根本原因。通过计算发现不同掺杂晶面暴露为表面时, 由于功函数各异, 与基体的本征电位差也各不相同。Hg、Cd、Zr、Ti和Hf等掺杂原子能增加析出相(100)表面的功函数, Hg、Cd、In、Ti和Hf等原子能增加析出相(110)面的功函数, 而Pd、Pt、Au、In、Sc、Rb、Sr、Yb、Y、Er、K、Ba、La、Ce和Ca原子能降低(111)面的功函数, 这些均导致析出相与铝基体的本征电位差进一步减小。此外, 结果揭示了掺杂原子电负性与其化合物功函数之间的线性正相关规律。相较而言, 电负性与Al接近且替代Al的In、Cd和Hg原子, 以及电负性与Zr接近且替代Zr的Ti和Hf原子对析出相功函数影响较小, 且其化合物与铝基体的电势差较小, 对提升材料抗腐蚀能力有益, 其他掺杂原子则对析出相功函数有较大影响。研究解释了部分耐蚀性实验结果, 为优化合金成分设计、提升铝合金材料耐腐蚀性提供了理论参考。

关键词: 电偶腐蚀, 铝合金, L1₂析出相, 合金原子, 第一性原理计算

Abstract:

The galvanic corrosion of aluminum alloy mainly depends on the potential difference between the second phase and matrix. The greater the potential difference, the stronger the corrosion driving force. Based on AlZr binary alloy, we calculated the work functions of the (100), (110) and (111) planes of 19 ternary precipitates L1₂-Al_xZr_yX_z(X=Pd, Pt, Au, K, Rb, Sr, Ba, Ca, Yb, La, Ce, Y, Er, Sc, Zr, Ti, Cd, Hf, In) comprehensively by using the first principle calculations. The relationship between the work functions and the electronegativity of doped atoms was analyzed, and the fundamental reason for the influence of doped atoms on the surface galvanic corrosion performance of L1₂ type Al-Zr-X ternary aluminum alloy is clarified from the electronic level. Through calculation, we find that when different doped crystal surfaces are exposed to the surface, the potential difference between the phase and the matrix is also different due to the varying work functions. The doped atoms Hg, Cd, Zr, Ti, Hf can increase the work functions of the (100) surface of L1₂-Al_xZr_yX_z ternary precipitates, Hg, Cd, In, Ti, Hf can increase the work function of the (110) surface, and Pd, Pt, Au, In, Sc, Rb, Sr, Yb, Y, Er, K, Ba, La, Ce and Ca could decrease the work function of the (111) surface. These will lead to the further reduction of the potential difference between the phase and matrix. In addition, the linear positive correlation between the electronegativity of doped atoms and the work function of the compound is revealed. In contrast, In, Cd, Hg atoms whose electronegativity is close to Al and doping the site of Al, and Ti, Hf atoms whose electronegativity is close to Zr and doping the site of Zr have less influence on the work function of the phase, and the potential difference between their compounds and aluminum matrix is small, which is beneficial to improving the corrosion resistance of materials. Other doped atoms have greater influence on the work function of the phase. Research results have explained some of the experimental results of corrosion resistance studies, which provided a theoretical reference for optimizing the design of alloy composition and improving the corrosion resistance of aluminum alloy materials.

Key words: galvanic corrosion, aluminum alloys, L1₂ phase, alloy atoms, first-principles computations

中图分类号:

TG171

张庆洲, 范大伟, 刘凌虹. 合金原子对L1₂型Al-Zr-X三元铝合金表面电偶腐蚀影响的第一性原理研究[J]. 计算物理, 2023, 40(6): 699-711.

Qingzhou ZHANG, Dawei FAN, Linghong LIU. First-principles Study on the Influence of Alloying Elements on Galvanic Corrosion of Ternary L1₂-Al-Zr-X Aluminum Alloys Surface[J]. Chinese Journal of Computational Physics, 2023, 40(6): 699-711.

图/表 9

表1 铝基体不同表面的功函数(W)和表面能(Esurf)

Table 1 Work function (W) and surface energy (Esurf) of different surfaces of Al matrix

Surface	W/eV		W_exp/eV	E_surf/(J·m^-2)
(100)	4.34	4.30^[48]	4.41^[47]	1.03	0.96^[17]
(110)	4.09	4.09^[48]	4.28^[47]	1.04	1.02^[17]
(111)	4.02	4.02^[48]	4.24^[47]	0.84	0.73^[17]

图1 X原子取代L12-Al3Zr二元析出相中Al/Zr位的替换形成焓Ef(虚线表示Ef=0) (a) X原子取代Al/Zr原子位置；(b) X原子未取代Al/Zr原子位置

Fig.1 Substitution formation enthalpy Ef of the Al/Zr sites in the precipitated phase of L12-Al3Zr binary by X atoms (the dotted line indicates Ef=0) (a) the substitution of Al/Zr atoms by X atom; (b) the substitution of Al/Zr atoms not by X atoms

图2 包含(100)、(110)和(111)3个不同表面的L12-AlxZryXz超胞模型(Ⅰ、Ⅱ、Ⅲ分别表示掺杂前、X原子低浓度掺杂和X原子高浓度掺杂的情况。每个超胞都包含一个1.2 nm的真空层。)

Fig.2 L12-AlxZryXz supercell structure with (100) (110) (111) three different surfaces Ⅰ, Ⅱ and Ⅲ the conditions before doping, doping of X atom with low concentration and doping of X atom with high concentration respectively (Each supercell with a vacuum layer of 1.2 nm.)

图3 不同掺杂条件下L12-AlxZryXz结构的表面能(a) X原子占据L12-Al3Zr析出相的Al位；(b) X原子占据L12-Al3Zr析出相的Zr位

Fig.3 Surface energy of L12-AlxZryXz structures under different doping conditions (a) the Al sites in the L12-Al3Zr precipitated phase by X atoms; (b) the Zr sites in the L12-Al3Zr precipitated phase by X atoms

图4 不同掺杂条件下L12-AlxZryXz结构的功函数(a)、(b)和(c)分别为L12-AlxZryXz结构的(100)、(110)和(111)面(X原子在L12-Al3Zr析出相中占据Al位。)；(d)、(e)和(f)分别为L12-AlxZryXz结构的(100)、(110)和(111)面(X原子在L12-Al3Zr析出相中占据Zr位。黑色虚线为图中Al矩阵对应曲面的功函数值，红色/蓝色虚线分别为高于/低于黑色虚线功函数250 meV的参考线。)

Fig.4 Work function of L12-AlxZryXz structure under different doping conditions (a) (100), (b) (110) and (c) (111) surfaces of the L12-AlxZryXz structure (X atoms occupy the Al sites in the L12-Al3Zr precipitated phase.); (d) (100), (e) (110) and (f) (111) surfaces of the L12-AlxZryXz structure (X atoms occupy the Zr sites in the L12-Al3Zr precipitated phase. The black dashed line represents the work function value of the corresponding surface of Al matrix in the figure, and the red/blue dashed line respectively represents the reference line higher than/lower than the black dashed line work function of 250 meV.)

表2 不同原子的电负性

Table 2 Electronegativity of different atoms

atom	electronegativity^[56]	atom	electronegativity^[56]
In	1.49	Er	1.11
Al	1.47	Y	1.11
Cd	1.46	La	1.08
Hg	1.44	Yb	1.06
Pt	1.44	Ce	1.06
Au	1.42	Ca	1.04
Pd	1.35	Sr	0.99
Ti	1.32	Ba	0.97
Hf	1.23	K	0.91
Zr	1.22	Rb	0.89
Sc	1.20

图5 L12-AlxZryXz结构Ⅲ表面功函数与掺杂原子电负性关系(掺杂原子的电负性从左到右逐渐增大，其中黑色/红色/蓝色虚线分别代表L12-Al3Zr析出相(100)Ⅲ、(110)Ⅲ和(111)Ⅲ的表面功函数值。) (a) X原子占据L12-Al3Zr析出相的Al位；(b) X原子占据L12-Al3Zr析出相的Zr位。

Fig.5 Relation between the Ⅲ surface work function of L12-AlxZryXz structure and electronegativity of doping atoms (The electronegativity of doping atoms gradually increases from left to right, where the black/red/blue dashed lines represent the surface work function values of (100)Ⅲ, (110)Ⅲ and (111)Ⅲ of L12-Al3Zr precipitated phases, respectively.) (a) the Al sites in the L12-Al3Zr precipitated phase by X atoms; (b) the Zr sites in the L12-Al3Zr precipitated phase by X atoms

图6 L12-AlxZryYz析出相(100)Ⅲ表面的总态密度(TDOS)和部分态密度(PDOS)(a)L12-Al-Zr-Y析出相的(100)Ⅲ表面结构; (b)为赝能隙的放大视图

Fig.6 Total density of states (TDOS) and partial density of states (PDOS) on the (100)Ⅲ surface of L12-AlxZryYz precipitated phase (a) (100)Ⅲ surface structure of L12-Al-Zr-Y precipitated phase; (b) enlarged views of the pseudogap

图7 L12-AlxZryTiz析出相(100)Ⅲ表面的总态密度(TDOS)和部分态密度(PDOS)(a)L12-Al-Zr-Ti析出相的(100)Ⅲ表面结构; (b)为赝能隙的放大视图

Fig.7 Total density of states (TDOS) and partial density of states (PDOS) on the (100)Ⅲ surface of L12-AlxZryTiz precipitated phase (a) (100)Ⅲ surface structure of L12-Al-Zr-Ti precipitated phase; (b) enlarged views of the pseudogap

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合金原子对L1₂型Al-Zr-X三元铝合金表面电偶腐蚀影响的第一性原理研究

First-principles Study on the Influence of Alloying Elements on Galvanic Corrosion of Ternary L1₂-Al-Zr-X Aluminum Alloys Surface

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