激光熔覆CoCrFeNiSi<sub><i>x</i></sub>高熵合金涂层的组织与性能

田志刚; 李新梅; 秦忠; 杨现臣; 刘伟斌; 张培军

doi:10.12073/j.hjxb.20220305001

激光熔覆CoCrFeNiSi_x高熵合金涂层的组织与性能

新疆大学, 乌鲁木齐, 830017

基金项目: 国家自然科学基金资助项目(52161017，51865055)；新疆维吾尔自治区自然科学基金资助项目(2022D01C386).

详细信息

作者简介:
田志刚，硕士；主要研究方向为高熵合金涂层；Email: 770639674@qq.com

通讯作者:
李新梅，教授，博士；Email: 35335499@qq.com.

中图分类号: TG 401
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出版历程
- 收稿日期: 2022-03-04
- 网络出版日期: 2022-11-24
- 刊出日期: 2022-12-24

Microstructure and properties of CoCrFeNiSi_x high-entropy alloy coating by laser cladding

Xinjiang University, Urumqi, 830017, China

摘要

摘要: 为了探究Si元素含量对CoCrFeNiSi_x(x=0.5，1.0，1.5)高熵合金涂层的组织与性能的影响，采用激光熔覆技术制备高熵合金涂层，通过X射线衍射仪、扫描电子显微镜、能谱仪、显微硬度仪、摩擦磨损试验机、电化学工作站等表征了涂层的物相组成、微观组织以及元素分布、硬度值、耐磨性能和耐腐蚀性能. 研究表明，随着Si元素的含量增加，合金物相由单相面心立方结构转变为面心立方结构、Si元素化合物(σ)相结构，最后形成面心立方结构、体心立方结构和σ相混合结构.涂层的组织主要由柱状晶转变成树枝晶，最后形成胞状晶；同时，涂层的硬度不断提高，当Si含量为1.5时，涂层的平均硬度值达到最高，为619.04 HV0.2，约为基体的2.67倍.涂层的磨损量、摩擦系数随着Si含量的增加而减少，耐磨性能显著提高.涂层在3.5%NaCl溶液中腐蚀性能随着Si含量的增加先增加后降低，当Si含量为1.0时，涂层的耐腐蚀性能最优.
- 激光熔覆 /
- 高熵合金涂层 /
- 耐磨性能 /
- 耐腐蚀性能
Abstract: In order to investigate the effect of Si content on the microstructure and properties of CoCrFeNiSi_x (x=0.5, 1.0, 1.5) high-entropy alloy coating, the high-entropy alloy coating was prepared by laser cladding technology. The phase composition, microstructure, element distribution, hardness value, wear resistance and corrosion properties of the coating were characterized by X-ray diffraction, scanning electron microscopy (SEM), energy dispersive spectroscopy, microhardness tester, friction and wear tester, and electrochemical workstation. The results show that with the increase of Si content, the alloy phase changes from single-phase face-centered cubic structure to face-centered cubic structure, silicon compound (σ) phase structure, and finally form face-centered cubic structure, body-centered cubic structure and σ mixed structure. The microstructure of the coating mainly changes from columnar crystals to dendritic crystals and finally to cellular crystals. At the same time, the hardness of the coating also increases. When the Si content is 1.5, the average hardness of the coating reaches 619.04 HV0.2, which is about 2.67 times that of the substrate. The wear amount and friction coefficient of the coating decreased with the increase of Si content, and the wear resistance of the coating increased significantly. In 3.5%NaCl solution, the corrosion performance of the coating increases first and then decreases with the increase of Si content. When Si content is 1.0, the corrosion performance of the coating is optimal.
- laser cladding /
- high-entropy alloy coating /
- wear resistance /
- corrosion resistance

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图 1 CoCrFeNiSi_x (x = 0.5，1.0，1.5)高熵合金涂层的单道截面

Figure 1. Single channel cross section of CoCrFeNiSi_x (x=0.5, 1.0, 1.5) high-entropy alloy coating. (a) x = 0.5; (b) x = 1.0; (c) x = 1.5

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图 2 CoCrFeNiSi_x (x = 0.5，1.0，1.5)高熵合金涂层的XRD衍射图谱

Figure 2. XRD patterns of CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy coatings. (a) X-ray diffraction pattern; (b) partial magnification of the main peak

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图 3 CoCrFeNiSi_x (x = 0.5，1.0，1.5)高熵合金涂层原子的混合焓和原子半径

Figure 3. Mixing enthalpy and atomic radius of CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy coating atoms

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图 4 不同高熵合金的微观组织形貌

Figure 4. Microstructure morphology of different high-entropy alloy. (a) CoCrFeNiSi_0.5; (b) CoCrFeNiSi_0.5 (high magnification); (c) CoCrFeNiSi_1.0; (d) CoCrFeNiSi_1.0 (high magnification); (e) CoCrFeNiSi_1.5; (f) CoCrFeNiSi_1.5 (high magnification)

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图 5 CoCrFeNiSi_1.0高熵合金面扫描和元素分布

Figure 5. Surface scanning and element distribution of CoCrFeNiSi_1.0 high-entropy alloy. (a) CoCrFeNiSi_1.0; (b) Co element; (c) Cr element; (d) Fe element; (e) Ni element; (f) Si element

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图 6 CoCrFeNiSi_x (x = 0.5，1.0，1.5)高熵合金涂层硬度

Figure 6. Hardness of CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy coating

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图 7 基体和CoCrFeNiSi_x (x = 0.5，1.0，1.5) 高熵合金涂层磨损量与摩擦系数

Figure 7. Wear and friction coefficient of matrix and CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy coating

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图 8 CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) 高熵合金涂层磨损量与硬度关系

Figure 8. Relationship between wear amount and hardness of CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy coating

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图 9 基体和CoCrFeNiSi_x (x = 0.5, 1.0, 1.5)高熵合金磨损三维轮廓

Figure 9. Matrix and CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy wear 3D profile. (a) matrix; (b) x = 0.5; (c) x = 1.0; (d) x = 1.5

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图 10 基体和CoCrFeNiSi_x (x = 0.5, 1.0, 1.5)高熵合金涂层磨损形貌

Figure 10. Wear morphology of matrix and CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy coatings. (a) matrix; (b) matrix (high magnification); (c) CoCrFeNiSi_0.5; (d) CoCrFeNiSi_0.5 (high magnification); (e) CoCrFeNiSi_1.0; (f) CoCrFeNiSi_1.0 (high magnification); (g) CoCrFeNiSi_1.5; (h) CoCrFeNiSi_1.5 (high magnification)

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图 11 基体与CoCrFeNiSi_x (x = 0.5，1.0，1.5)高熵合金涂层的动电位极化曲线

Figure 11. Potentiodynamic polarization curves of matrix and CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy coating

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图 12 CoCrFeNiSi_x (x = 0.5，1.0，1.5)高熵合金涂层的Nyquist图、Bode图与拟合等效电路图

Figure 12. Nyquist diagram, Bode diagram and fitting equivalent circuit diagram of CoCrFeNiSi_x (x = 0.5，1.0，1.5) high-entropy alloy coating. (a) Nyquist diagram; (b) Bode diagram; (c) fitting equivalent circuit diagram

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图 13 基体和CoCrFeNiSi_x (x = 0.5，1.0，1.5)高熵合金涂层在3.5%NaCl溶液中电化学腐蚀形貌

Figure 13. Electrochemical corrosion morphology of substrate and CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy coating in 3.5%NaCl solution. (a) matrix; (b) matrix (high magnification); (c) CoCrFeNiSi_0.5; (d) CoCrFeNiSi_0.5 (high magnification); (e) CoCrFeNiSi_1.0; (f) CoCrFeNiSi_1.0 (high magnification); (g) CoCrFeNiSi_1.5; (h) CoCrFeNiSi_1.5 (high magnification)

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表 1 试验工艺参数

Table 1 Experimental process parameters

激光功率 P/kW	扫描速度 v/(mm·s⁻¹)	光斑直径 d/mm	搭接率 η(%)
1.1	6	2	50

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表 2 CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) 高熵合金涂层的价电子浓度

Table 2 Valence electron concentrations of CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy coatings

x	价电子浓度V_EC
0.5	7.78
1.0	7.40
1.5	7.09

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表 3 CoCrFeNiSi_x (x = 0.5, 1.0, 1.5)的EDS分析(原子分数, %)

Table 3 EDS analysis of CoCrFeNiSi_x (x = 0.5, 1.0, 1.5)

x值	区域	Co	Cr	Fe	Ni	Si
0.5	设计含量	22.22	22.22	22.22	22.22	11.10
	A	20.86	22.83	27.62	17.37	11.32
	B	18.11	22.56	22.51	20.84	15.98
1.0	设计含量	20	20	20	20	20
	C	16.49	16.30	42.93	13.26	11.02
	D	14.91	14.77	33.58	18.19	18.55
x = 1.5	设计含量	18.18	18.18	18.18	18.18	27.27
	E	6.31	6.81	33.63	5.26	47.99
	F	8.19	15.17	39.24	9.00	28.40

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表 4 CoCrFeNiSi_x (x = 0.5，1.0，1.5)高熵合金磨损形貌EDS分析(原子分数，%)

Table 4 EDS analysis of wear morphology of CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy

x值	位置	Co	Cr	Fe	Ni	Si	O
0.5	G	8.14	6.92	27.97	7.81	2.55	46.60
1.0	H	5.59	5.38	28.97	5.25	3.87	50.94
1.5	J	5.86	6.48	22.72	5.24	8.75	50.95

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表 5 CoCrFeNiSi_x (x = 0.5，1.0，1.5)高熵合金涂层的电化学参数

Table 5 Electrochemical parameters of CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy coating

合金	腐蚀电位 E_corr/mV	自腐蚀电流密度 i_corr/(10⁻²A·cm⁻²)
基体	−1 042.180	32.8
CoCrFeNiSi_0.5	−997.063	1.92
CoCrFeNiSi_1.0	−955.391	1.39
CoCrFeNiSi_1.5	−1 039.342	3.37

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表 6 CoCrFeNiSi_x (x = 0.5，1.0，1.5)高熵合金涂层电化学阻抗拟合结果

Table 6 Electrochemical impedance fitting results of CoCrFeNiSi_x (x = 0.5, 1.0, 1.5) high-entropy alloy coating

合金	溶液电阻R_s /Ω	钝化膜电容C_PE1 /10⁻⁶F	钝化膜电阻R_f /10³Ω	涂层的电容C_PE2 /10⁻⁶F	电荷转移电阻R_ct /10²Ω
基体	6.045	39.58	0.047 9	1.931	1.632
CoCrFeNiSi_0.5	1.392	16.83	0.011 0	8.507	39.62
CoCrFeNiSi_1.0	9.401	9.698	0.007 1	5.869	49.05
CoCrFeNiSi_1.5	8.83	13.43	0.513 5	31.96	38.35

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