铝合金表面激光沉积AlCrFeCoNiCu涂层的组织及耐蚀性能

李彦洲; 石岩

doi:10.3788/CO.20191202.0344

铝合金表面激光沉积AlCrFeCoNiCu涂层的组织及耐蚀性能

doi: 10.3788/CO.20191202.0344

李彦洲^{1, 3,},
石岩^{1, 2, ,}

1.
长春理工大学机电工程学院, 吉林长春 130022
2.
长春理工大学国家国际科技合作基地(光学), 吉林长春 130022
3.
吉林工业职业技术学院机电与智能技术学院吉林吉林 132000

基金项目:

国家重点研发计划"增材制造与激光制造"专项 22017YFB1104601

吉林省科技厅重点科技攻关项目 220170204065GX

吉林省科技厅重点科技攻关项目 20180201063GX

详细信息

作者简介:
李彦洲(1988-), 男, 吉林吉林人, 博士研究生, 讲师, 2014年于长春工业大学获得硕士学位, 现为长春理工大学机电工程学院博士研究生, 主要从事激光加工技术方面的研究。E-mail:2721589336@qq.com

石岩(1972-), 男, 吉林长春人, 教授, 博士生导师, 1995年于长春光学精密机械学院获得学士学位, 2002年于长春光学精密机械学院获得硕士学位, 2007年于长春理工大学获得博士学位, 现为长春理工大学激光加工技术研究中心主任, 主要从事激光加工技术方面的研究。E-mail:shiyan@cust.edu.cn

中图分类号: TG141.1
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出版历程
- 收稿日期: 2018-11-29
- 修回日期: 2019-01-09
- 刊出日期: 2019-04-01

Microstructure and corrosion resistance of AlCrFeCoNiCu high-entropy coating by laser deposition on an aluminum alloy

LI Yan-zhou^{1, 3
,},
SHI Yan^{1, 2
, ,}

1.
College of Electromechanical Engineering, Changchun University of Science and Technology, Changchun 130022, China
2.
National Base of International Science and Technology Cooperation in Optics, Changchun 130022, China
3.
College of Electromechanical and Intellectual Technology, Jilin Vocational College of Industry and Technology, Changchun 132000, China

Funds:

the National Program of Key Research in Additive Manufacturing and Laser Manufacturing of China 22017YFB1104601

the financial aids from the Scientific and Technological Planning Project of Jilin Province 220170204065GX

the financial aids from the Scientific and Technological Planning Project of Jilin Province 20180201063GX

More Information

Corresponding author: SHI Yan, E-mail:shiyan@cust.edu.cn

摘要

摘要: 为了提高铝合金表面的力学和耐腐蚀性能，利用激光沉积技术在铝合金表面制备了AlCrFeCoNiCu高熵合金涂层。使用X射线衍射仪（XRD）、扫描电子显微镜（SEM）、能谱分析仪（EDS）、显微硬度计和电化学工作站，研究了涂层的相结构、微观组织、元素分布、硬度及耐腐蚀性能。结果表明，涂层与基材结合良好，基材中Al元素在熔池搅拌作用下上浮，使沉积层呈FCC相和BCC相；显微组织为典型的枝晶结构，Cu元素在枝晶间富集；涂层平均显微硬度为528HV_0.2，约是基材的5倍；AlCrFeCoNiCu涂层在3.5% NaCl溶液中的腐蚀特征为点蚀和晶间腐蚀，耐腐蚀性优于基材。激光沉积制备的AlCrFeCoNiCu高熵合金可以改善铝合金表面性能。
- 激光技术 /
- 激光沉积 /
- 高熵合金 /
- 耐腐蚀性 /
- 铝合金
Abstract: To improve the mechanical and corrosion resistance of an aluminum alloys, laser deposition(LDP) was used to form an AlCrFeCoNiCu high-entropy alloy(HEA) coating on an aluminum alloy surface. The phase structure, microstructure, micro-hardness and corrosion resistance of the HEA coating were investigated using X-ray diffraction(XRD), scanning electronic microscopy with energy-dispersive spectroscopy(SEM-EDS), a microhardness tester and an electrochemical workstation. The experiment revealed that the coating had excellent adhesion to the substrate. The HEA coating consisted of body-centered cubic(BCC) and face-centered cubic(FCC) phases, while the microstructure was shown to be a typical dendritic structure. The coating had an average micro hardness of 528Hv_0.2, which is five times greater than that of the substrate. Corrosion of the samples was shown to be pitting and intercrystalline corrosion in a 3.5%NaCl solution, and the corrosion resistance was superior to that of the substrate. Thus, AlCrFeCoNiCu HEA coating has been demonstrated to be an effective way of improving the surface properties of aluminum alloys.
- laser technology /
- laser deposition /
- high-entropy alloy /
- corrosion resistance /
- aluminum alloy

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图 1 激光沉积原理示意图

Figure 1. Schematic diagram of laser deposition

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图 2 FeCrCoNiCu粉末与涂层XRD图谱

Figure 2. XRD patterns of FeCrCoNiCu powder and the coating

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图 3 AlCrFeCoNiCu涂层横截面SEM图.(a)涂层宏观形貌；(b)沉积层顶部; (c)沉积层中部; (d)沉积层底部

Figure 3. SEM images of cross-section of AlCrFeCoNiCu coating. (a)Overall morphology of the coating, (b)top zone of the cladding, (c)middle zone of the cladding, (d)bottom zone of the cladding

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图 4 涂层的显微硬度分布

Figure 4. Microhardness distribution of the coating

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图 5 AlCrFeCoNiCu涂层和基材在3.5%NaCl溶液中的动电位极化曲线

Figure 5. Potentiodynamic polarization curves of AlCrFeCoNiCu coating and the substrate in 3.5%NaCl solution

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图 6 AlCrFeCoNiCu涂层和基材在3.5%NaCl溶液中动电位极化后的SEM图. (a)基材形貌, (b)AlCrFeCoNiCu涂层形貌, (c)图(b)中A区域的局部放大图, (d)图(b)中B区域的局部放大图

Figure 6. SEM images of AlCrFeCoNiCu coating and the substrate after polarization tests in 3.5%NaCl solution. (a)Morphology of the substrate, (b)morphology of AlCrFeCoNiCu coating, (c)magnification of region A in Fig. 6(b), (d)magnification of region B in Fig. 6(b)

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图 7 AlCrFeCoNiCu涂层和基材在3.5%NaCl溶液中Nyquist曲线

Figure 7. Nyquist plots of AlCrFeCoNiCu coating and the substrate in 3.5%NaCl solution

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图 8 AlCrFeCoNiCu涂层和基材在3.5%NaCl溶液中的波特图

Figure 8. Bolt plots of AlCrFeCoNiCu coating and the substrate in 3.5%NaCl solution

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图 9 电化学阻抗谱的等效电路图

Figure 9. Equivalent circuit of EIS

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表 1 AlxCrFeCoNiCu(x=0, 0.5, 1, 1.5, 2)的混合熵、混合焓、原子半径比、价电子浓度比、电负性差

Table 1. Parameters of δ, H_mix, ΔS_mix, VEC and χ for AlxCrFeCoNiCu(x=0, 0.5, 1, 1.5, 2)

Alloys	δ/%	ΔH_mix/(kJ·mol^-1)	ΔS_mix/(J·K^-1·mol^-1)	VBC	χ
FeCoNiCrCu	1.07	3.2	13.3	8.80	0.12
Al_0.5CrFeCoNiCu	3.90	-1.52	14.7	8.27	0.13
AlCrFeCoNiCu	4.82	-4.87	14.9	7.83	0.14
Al_1.5CrFeCoNiCu	5.48	-7.05	14.8	7.46	0.14
Al₂ CrFeCoNiCu	5.98	-8.65	14.5	7.14	0.15

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表 2 图 3中各区域的EDS结果(原子分数)

Table 2. EDS results of each area in Fig. 3(at/%)

Areas	Al	Cr	Fe	Co	Ni	Cu
Nominal	0	20	20	20	20	20
1(Dendrite)	10.94	17.37	17.37	19.41	19.21	15.7
1(Interdentic)	8.78	16.30	17.73	19.73	16.21	21.25
2(Dendrite)	10.36	17.81	17.85	17.54	17.75	18.69
2(Interdendritic)	9.68	17.2	17.27	16.53	17.31	22.01
3(Dendrite)	13.26	19.25	17.58	19.15	15.23	15.53
3(Interdendritic)	11.21	17.23	15.21	17.21	16.26	20.88

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表 3 AlCrFeCoNiCu涂层和基材在3.5%NaCl溶液中的电化学参数

Table 3. Eletrochemical parameters of AlCrFeCoNiCu coating and the substrate in 3.5%NaCl solution

Solution	Samples	E_corr/V	I_corr/μA
3.5%NaCl	AlCrFeCoNiCu coating Substrate	-1.13 -1.40	9.22 35.4

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表 4 图 6中各点的EDS结果(原子分数)

Table 4. EDS results of each point in Fig. 6(at%)

Areas	Al	Cr	Fe	Co	Ni	Cu
1(Dendrite)	8.7	20.63	19.27	19.42	19.59	12.39
1(Interdentic)	10.96	15.31	18.75	19.76	18.01	17.21

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表 5 AlCrFeCoNiCu涂层在3.5%NaCl溶液中的等效电路参数

Table 5. Equivalent circuit parameters of AlCrFeCoNiCu coating in 3.5%NaCl solution

	R_s/(kΩ·cm²)	CPE1/(μF·cm^-2)	n	R_c/(kΩ·cm²)
HEA coating	3.12	17.2	0.892	2 982

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