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

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

Abstract

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

CLC Number:

TG171

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.

Figures/Tables 9

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]

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

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.)

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

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.)

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

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

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

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

References 57

1	WILLIAMS J C , STARKE Jr E A . Progress in structural materials for aerospace systems[J]. Acta Materialia, 2003, 51 (19): 5775- 5799. DOI
2	HUDA Z , EDI P . Materials selection in design of structures and engines of supersonic aircrafts: A review[J]. Materials and Design, 2013, 46 (4): 552- 560.
3	BIRBILIS N , BUCHHEIT R G . Electrochemical characteristics of intermetallic phases in aluminum alloys an experimental survey and discussion[J]. J Electrochem Soc, 2005, 152 (4): B140- B151. DOI
4	CHEN C T , CONG S , CHEN H F , et al. First-principles study of electronic structure and optical properties of Bi doped ZnO[J]. Chinese Journal of Computational Physics, 2018, 35 (6): 720- 728.
5	ZHANG X Y , FENG L . Electronic structure and magnetic properties of carbon doped Mn₃Ge[J]. Chinese Journal of Computational Physics, 2019, 36 (6): 742- 748.
6	GAO H , YANG Z F , ZHAO J F , et al. Effect of Nb, Sn, Cu, Fe and Cr on Zr (0001) surface nodular corrosion resistence: First-principles study[J]. Chinese Journal of Computational Physics, 2022, 39 (1): 101- 108.
7	王健. 电子功函数的计算及其在材料表面电化学问题研究中的应用[D]. 合肥: 中国科学技术大学, 2016.
8	LI J F , ZIQIAO Z , NA J , et al. Localized corrosion mechanism of 2×××-series Al alloy containing S(Al₂CuMg) and θ'(Al₂Cu) precipitates in 4.0% NaCl solution at pH 6.1[J]. Materials Chemistry and Physics, 2005, 91 (2/3): 325- 329.
9	王晓欢, 张胜寒, 狄杰. 金属电偶腐蚀影响因素研究综述[J]. 广东化工, 2022, 49 (19): 142- 147.
10	张国英, 张辉, 方戈亮, 等. Bi, Sb合金化对AZ91镁合金组织、性能影响机理研究[J]. 物理学报, 2005, 54, 5288- 5292.
11	张国英, 张辉, 赵子夫, 等. 杂质对镁合金耐蚀性影响的电子理论研究[J]. 物理学报, 2006, 55 (5): 2439- 2443.
12	张国英, 张辉, 方戈亮, 等. Al-Zn-Mg-Cu系铝合金中不同区域电子结构及应力腐蚀机理分析[J]. 金属学报, 2009, 45 (6): 687- 691. DOI
13	LI W , LI D Y . On the correlation between surface roughness and work function in copper[J]. J Chem Phys, 2005, 122 (6): 064708. DOI
14	LI D Y , LI W . Electron work function: A parameter sensitive to the adhesion behavior of crystallographic surfaces[J]. Appl Phys Lett, 2001, 79 (26): 4337- 4338. DOI
15	ALCHAGIROV A B , ALCHAGIROV B B , SIZHAZHEV T A , et al. Work function of sodium-rubidium alloys[J]. Russ J Electrochem, 2004, 40 (1): 102- 104. DOI
16	王铀, 王亮. 电子功函数在材料磨损及腐蚀方面的研究进展[J]. 中国材料科技与装备, 2011, 7 (5): 1- 5.
17	王健, 王邵青. 铝合金表面电偶腐蚀与电子功函数的关系[J]. 物理化学学报, 2014, 30 (3): 551- 558.
18	THIERRY D , LEBALLEUR C , LARCHÉ N . Galvanic series in seawater as a function of temperature, oxygen content, and chlorination[J]. Corrosion, 2017, 74 (2): 147- 152.
19	陈兴伟, 吴建华, 王佳, 等. 电偶腐蚀影响因素研究进展[J]. 腐蚀科学与防护技术, 2010, 22 (4): 363- 366.
20	薪魏, 董超芳, 徐奥妮, 等. 金属腐蚀的多尺度计算模拟研究进展[J]. 中国材料进展, 2018, 37 (1): 1- 8.
21	ZHANG C , WANG J , LI X , et al. Rapid screening alloying elements for improved corrosion resistance on the Mg(0001) surface using first principles calculations[J]. Phys Chem Chem Phys, 2021, 23 (47): 26887- 26901. DOI
22	KNIPLING K E. Development of a nanoscale precipitation-strengthened creep-resistant aluminum alloy containing trialuminide precipitates[D]. Xi'an: Northwestern University, 2006.
23	张永志. Al-Zr-RE(Yb_Y)合金中L1₂结构相的时效析出机制与作用[D]. 上海: 上海交通大学, 2015.
24	姜慧丽, 陈送义, 陈康华, 等. Zr质量分数对7003铝合金组织与腐蚀性能的影响[J]. 中南大学学报, 2017, 48 (10): 2614- 2621. DOI
25	HE Y D , ZHANG X M , YOU J H . Effect of minor Sc and Zr on microstructure and mechanical properties of Al-Zn-Mg-Cu alloy[J]. Trans Nonferrous Met Soc China, 2006, 16 (5): 1228- 1235. DOI
26	YU K , LI W X , LI S R , et al. Mechanical properties and microstructure of aluminum alloy 2618 with Al₃(Sc, Zr) phases[J]. Mater Sci Eng A, 2004, 368 (1/2): 88- 93.
27	LI J H , WIESSNER M , ALBU M , et al. Correlative characterization of primary Al₃(Sc, Zr) phase in an Al-Zn-Mg based alloy[J]. Mater Charact, 2015, 102 (Apr.): 62- 70.
28	FANG H C , LUO F H , CHEN K H . Effect of intermetallic phases and recrystallization on the corrosion and fracture behavior of an Al-Zn-Mg-Cu-Zr-Yb-Cr alloy[J]. Mater Sci Eng A, 2017, 684 (Jan.): 480- 490.
29	张文毓. 电偶腐蚀与防护的研究进展[J]. 全面腐蚀控制, 2018, 32 (12): 52- 56.
30	肖毅. 异种金属的电偶腐蚀行为及防护技术研究[D]. 北京: 华北电力大学, 2006.
31	ZHANG F , ÖRNEK C , NILSSON J O , et al. Anodisation of aluminium alloy AA7075-influence of intermetallic particles on anodic oxide growth[J]. Corros Sci, 2020, 164, 1- 34.
32	AO M , LIU H M , DONG C F , et al. Degradation mechanism of 6063 aluminium matrix composite reinforced with TiC and Al₂O₃ particles[J]. J Alloys Compd, 2021, 859 (Apr.): 157838.
33	ZUO E , DOU X , CHEN Y , et al. Electronic work function, surface energy and electronic properties of binary Mg-Y and Mg-Al alloys: A DFT study[J]. Surface Science, 2021, 712 (9): 121880.
34	FANG J X , LU D . Solid state physics[M]. Shanghai: Shanghai Science and Technology Press, 1980.
35	ZHOU P , ZHOU C , GONG H R . Chlorine adsorption on Mg, Ca, and MgCa surfaces[J]. Mater Sci Eng C, 2013, 33 (7): 3826- 3831. DOI
36	YUWONO J A , BIRBILIS N , WILLIAMS K S , et al. Electrochemical stability of magnesium surfaces in an aqueous environment[J]. J Phys Chem C, 2016, 120 (47): 26922- 26933. DOI
37	LIU Y , HUANG Y C , XIAO Z B , et al. Study of adsorption of hydrogen on Al, Cu, Mg, Ti surfaces in Al alloy melt via first principles calculation[J]. Metals, 2017, 7 (1): 1- 9.
38	陈伟, 李云阔, 李耀, 等. 钢中NbC夹杂粒子表面性质的第一性原理[J]. 材料与冶金学报, 2022, 21 (6): 422- 427.
39	韩星, 王健, 何志军, 等. 稀土四硼化物表面性质的第一性原理研究[J]. 辽宁科技大学学报, 2022, 45 (3): 216- 220.
40	GAULT B , CUI X Y , MOODY M P , et al. Atom probe microscopy investigation of Mg site occupancy within δ' precipitates in an Al-Mg-Li alloy[J]. Scr Mater, 2012, 66 (11): 903- 906. DOI
41	KRESSE G , FURTHMÜLLER J . Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set[J]. Comput Mater Sci, 1996, 6 (1): 15- 50. DOI
42	KRESSE G , HAFNER J . Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements[J]. J Phys: Condens Matter, 1994, 6 (40): 8245- 8257. DOI
43	GONZE X . Towards a potential-based conjugate gradient algorithm for order-N self-consistent total energy calculations[J]. Phys Rev B, 1996, 54 (7): 4383- 4386. DOI
44	FEYNMAN R P . Forces in molecules[J]. Phys Rev, 1939, 56 (4): 340- 343. DOI
45	PAN R K , WANG H C , SHI T T , et al. Thermal properties and thermoelasticity of L1₂ ordered Al₃RE (RE=Er, Tm, Yb, Lu) phases: A first-principles study[J]. Mater Des, 2016, 102 (15): 100- 105.
46	MONKHORST H J , PACK J D . Special points for Brillouin-zone integrations[J]. Phys Rev B, 1976, 13 (12): 5188- 5192. DOI
47	GREPSTAD J K , GARTLAND P O , SLAGSVOLD B J . Anisotropic work function of clean and smooth low-index faces of aluminium[J]. Surface Science, 1976, 57 (1): 348- 362. DOI
48	SINGH-MILLER N E , MARZARI N . Surface energies, work functions, and surface relaxations of low-index metallic surfaces from first principles[J]. Phys Rev B, 2009, 80 (23): 1- 9.
49	SMOLUCHOWSKI R . Anisotropy of the electronic work function of metals[J]. Phys Rev, 1941, 60 (9): 661- 674. DOI
50	LI H Y , LI D W , ZHU Z X , et al. Grain refinement mechanism of as-cast aluminum by hafnium[J]. Transactions of Nonferrous Metals Society of China, 2016, 26 (12): 3059- 3069. DOI
51	王郁, 王俊升, 薛程鹏, 等. 微合金化对铝合金高温析出相影响的研究进展[J]. 航空制造技术, 2021, 64 (15): 68- 77.
52	王旭东, 聂祚仁, 林双平, 等. Er对Al-Zn-Mg-Cu合金抗腐蚀性能的影响[J]. 特种铸造及有色合金, 2009, 29 (1): 76- 78.
53	韩剑, 戴起勋, 李桂荣, 等. 稀土钇对7055铝合金铸态组织的影响[J]. 材料工程, 2009, (4): 67- 70.
54	赖人铭, 计熊, 赵国忠, 等. 稀土元素La对6063铝合金组织和性能的影响[J]. 轻合金加工技术, 2007, 35 (10): 28- 32.
55	孔敏. 第一性原理研究铝合金中间相的腐蚀机理[D]. 桂林: 桂林理工大学, 2020.
56	袁汉杰. 电负性的研究-原子的电负性[J]. 化学学报, 1964, (3): 103- 109.
57	张敏刚, 梁志彬, 闫时建, 等. Nb金化Mg₂Ni及其氢化物能量和电子结构的第一性原理研究[J]. 稀有金属材料与工程, 2015, 44 (2): 386- 390.

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

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 9

References 57

Related Articles 0

Recommended Articles

Metrics

Authors

Reviewers

Journal Online

About Journal