H13钢表面激光定向能量沉积AlCoCrFeNi2.1高熵合金涂层的组织与性能

doi:10.13251/j.issn.0254-6051.2025.10.048

摘要/Abstract

摘要： 采用同轴送粉激光定向能量沉积方法在H13钢基体上制备AlCoCrFeNi_2.1高熵合金涂层,对其进行不同温度和保温时间的退火处理,采用光学显微镜、XRD、SEM、EDS和EBSD对涂层组织进行表征,测试涂层的硬度,并分析其热稳定性。结果表明,涂层第一层组织为呈柱状的FCC相及分布其晶间的BCC(B2)相,在其与H13钢界面处存在一薄层FCC相;第二层组织为FCC与BCC(B2)两相共晶组织,呈层片状和非规则状。第一层沉积态硬度为260 HV0.2,稍低于第二层的硬度290 HV0.2。在500~800 ℃退火处理后,组织较沉积态的形态没有明显变化,硬度随退火温度升高先升高后下降,700 ℃时硬度最高,为388 HV0.2,保温时间对硬度影响不大;在700~800 ℃保温2~6 h后,涂层硬度保持在320 HV0.2以上,高于H13钢基体的硬度,且没有随着保温时间延长而明显下降,说明该涂层有较好的热稳定性。

关键词: 激光定向能量沉积, 高熵合金涂层, H13钢, 组织, 硬度

Abstract: AlCoCrFeNi_2.1 high-entropy alloy coating was fabricated on H13 steel substrate by coaxial powder feeding laser directed energy deposition. The coating was subjected to annealing at different temperatures and holding time. The microstructure of the coating was characterized by optical microscopy, XRD, SEM, EDS and EBSD, and the hardness of the coating was tested, and its thermal stability was analyzed. The results show that the microstructure of the first layer of the coating is composed of columnar FCC phase and BCC (B2) phase distributed at the grain boundaries, and a thin layer of FCC phase exists at the interface with H13 steel substrate. The microstructure of the second layer is a eutectic structure of FCC and BCC (B2) phases with lamellar and irregular morphologies. The hardness of the first layer in the as-deposited state is 260 HV0.2, slightly lower than that of the second layer, which is 290 HV0.2. After annealing at 500-800 ℃, the microstructure morphology of the coating does not change significantly compared with the as-deposited state. The hardness increases first and then decreases with the increase of annealing temperature, reaching the maximum of 388 HV0.2 at 700 ℃. The holding time has little effect on the hardness. After holding at 700-800 ℃ for 2-6 h, the hardness of the coating remains above 320 HV0.2, which is higher than that of the H13 steel substrate, and does not decrease significantly with the increase of holding time, indicating that the coating has good thermal stability.

Key words: laser directed energy deposition, high entropy alloy coating, H13 steel, microstructure, hardness

中图分类号:

TG174.44

李怀博, 王子乐, 杨伟, 曾大新, 史秋月. H13钢表面激光定向能量沉积AlCoCrFeNi_2.1高熵合金涂层的组织与性能[J]. 金属热处理, 2025, 50(10): 302-309.

Li Huaibo, Wang Zile, Yang Wei, Zeng Daxin, Shi Qiuyue. Microstructure and properties of AlCoCrFeNi_2.1 high entropy alloy coating prepared by laser directed energy deposition on H13 steel[J]. Heat Treatment of Metals, 2025, 50(10): 302-309.

参考文献

[1] Yeh J W, Chen S K, Lin S J, et al. Nanostructured high-entropy alloys with multiple principal elements: Novel alloy design concepts and outcomes[J]. Advanced Engineering Materials, 2004, 6(5): 299-303.
[2] Cantor B, Chang I T H, Knight P. Microstructural development in equiatomic multicomponent alloys[J]. Materials Science and Engineering A, 2004, 375: 213-218.
[3] Wang J, Kuang S, Yu X, et al. Tribo-mechanical properties of CrNbTiMoZr high-entropy alloy film synthesized by direct current magnetron sputtering[J]. Surface and Coatings Technology, 2020, 403: 126374.
[4] Xiao L, Zheng Z, Huang P, et al. Superior anticorrosion performance of crystal-amorphous FeMnCoCrNi high-entropy alloy[J]. Scripta Materialia, 2022, 210: 114454.
[5] Jiang D, Cui H, Zhao X, et al. Synchronous improvement of wear and corrosion resistance of CoCrNiMoCB coatings obtained by laser cladding: Role of Mo concentration[J]. SSRN Electronic Journal, 2022, 219: 110751.
[6] Rao Ziyuan, Wang Xun, Wang Qinjia, et al. Microstructure, mechanical properties, and oxidation behavior of Al_xCr_0.4CuFe_0.4MnNi high entropy alloys[J]. Advanced Engineering Materials, 2017, 19(5): 1600726.
[7] Li J, Huang Y, Meng X, et al. A review on high entropy alloys coatings: Fabrication processes and property assessment[J]. Advanced Engineering Materials, 2019, 21(8): 1900343.
[8] Duchaniya R K, Pandel U, Rao P. Coatings based on high entropy alloys: An overview[J]. Materials Today: Proceedings, 2021, 44: 4467-4473.
[9] Meghwal A, Anupam A, Murty B S, et al. Thermal spray high-entropy alloy coatings: A review[J]. Journal of Thermal Spray Technology, 2020, 29: 857-893.
[10] 张泽疆, 李新梅. 激光熔覆CoCrFeNiSi_x高熵合金涂层的耐磨和耐蚀性能[J]. 材料研究学报, 2024, 38(10): 741-750.
Zhang Zejiang, Li Xinmei. Wear and corrosion resistance of laser cladding CoCrFeNiSi_x high entropy alloy coating[J]. Chinese Journal of Materials Research, 2024, 38(10): 741-750.
[11] 杨成康, 程晓农, 张洁, 等. W-Mo-V改进型H13模具钢的力学性能与磨损行为[J]. 金属热处理, 2021, 46(4): 30-36.
Yang Chengkang, Cheng Xiaonong, Zhang Jie, et al. Mechanical properties and wear behavior of W-Mo-V modified H13 tool steel[J]. Heat Treatment of Metals, 2021, 46(4): 30-36.
[12] Zhu J, Zhang Z, Xie J. Improving strength and ductility of H13 die steel by pre-tempering treatment and its mechanism[J]. Materials Science and Engineering A, 2019, 752(3): 101-114.
[13] 姜高强, 崔承云, 魏礼桢, 等. 激光熔覆Fe基合金涂层强化H13热作模具钢[J]. 材料科学与工艺, 2022, 30(2): 35-42.
Jiang Gaoqiang, Cui Chengyun, Wei Lizhen, et al. Laser cladding Fe-based alloy coating for strengthening H13 hot work die steel[J]. Materials Science and Technology, 2022, 30(2): 35-42.
[14] Chen C R, Wang Y, Ou H G, et al. A review on remanufacture of dies and moulds[J]. Journal of Cleaner Production, 2014, 64: 13-23.
[15] Hawryluk M. Review of selected methods of increasing the life of forging tools in hot die forging processes[J]. Archives of Civil and Mechanical Engineering, 2016, 16: 845-866.
[16] 杜学芸, 许金宝, 宋健. 激光熔覆再制造技术研究现状及发展趋势[J]. 表面工程与再制造, 2020, 20(6): 18-22.
Du Xueyun, Xu Jinbao, Song Jian. Research status and development trend of laser cladding remanufacturing technology[J]. Surface Engineering and Remanufacturing, 2020, 20(6): 18-22.
[17] 卫广智, 温书涛, 李宝增, 等. 航空发动机制件热锻模激光熔覆修复层组织性能研究[J]. 热加工工艺, 2008, 37(17): 29-31, 34.
Wei Guangzhi, Wen Shutao, Li baozeng, et al. Study on microstructure and properties of repaired laser cladding on high-temperature forging mould for aeroengine pieces[J]. Hot Working Technology, 2008, 37(17): 29-31, 34.
[18] Lu Y, Dong Y, Guo S, et al. A promising new class of high-temperature alloys: Eutectic high-entropy alloys[J]. Scientific Reports, 2014, 4(1): 6200.
[19] Arif Z U, Khalid M Y, Ur Rehman E, et al. A review on laser cladding of high-entropy alloys, their recent trends and potential applications[J]. Journal of Manufacturing Processes, 2021, 68: 225-273.
[20] 吴韬, 吴濛婷, 陈云祥, 等. H13钢表面激光熔覆AlCoCrFeNiW_x高熵合金涂层及其性能[J]. 金属热处理, 2021, 46(11): 241-244.
Wu Tao, Wu Mengting, Chen Yunxiang, et al. Properties of laser clad AlCoCrFeNiW_x high entropy alloy coatings on H13 steel[J]. Heat Treatment of Metals, 2021, 46(11): 241-244.
[21] Wall M T, Pantawane M V, Joshi S, et al. Laser-coated CoFeNiCrAlTi high entropy alloy onto a H13 steel die head[J]. Surface and Coatings Technology, 2020, 387: 125473.
[22] Shi F K, Zhang Q K, Xu C, et al. In-situ synthesis of NiCoCrMnFe high entropy alloy coating by laser cladding[J]. Optics and Laser Technology, 2022, 151: 108020.
[23] Li Z, Jing C, Feng Y, et al. Phase evolution and properties of Al_xCoCrFeNi high-entropy alloys coatings by laser cladding[J]. Materials Today: Communications, 2023, 35: 105800.
[24] Shu F, Wang B, Zhao H, et al. Effects of line energy on microstructure and mechanical properties of CoCrFeNiBSi high-entropy alloy laser cladding coatings[J]. Journal of Thermal Spray Technology, 2020, 29: 789-797.
[25] Liu X T, Lei W B, Li J, et al. Laser cladding of high-entropy alloy on H13 steel[J]. Rare Metals, 2014, 33: 727-730.
[26] Yang C, Jing C, Fu T, et al. Effect of CeO₂ on the microstructure and properties of AlCoCrFeNi_2.1 laser cladding coatings[J]. Journal of Alloys and Compounds, 2024, 976: 172948.
[27] Dong Z, Feng L, Long H, et al. A multi-objective optimization of laser cladding processing parameters of AlCoCrFeNi_2.1 eutectic high-entropy alloy coating[J]. Optics and Laser Technology, 2024, 170: 110302.
[28] Zhang L, Ji Y, Yang B. Thermal stability and hot corrosion performance of the AlCoCrFeNi_2.1 high-entropy alloy coating by laser cladding[J]. Materials, 2023, 16(17): 5747.
[29] 熊婷, 郑士建, 马秀良. 高熵合金AlCoCrFeNi_2.1的共晶组织及析出相研究[J]. 电子显微学报, 2020, 39(5): 470-475.
Xiong Ting, Zheng Shijian, Ma Xiuliang. An investigation on the eutectic structure and precipitates in the high-entropy alloy AlCoCrFeNi_2.1[J]. Journal of Chinese Electron Microscopy Society, 2020, 39(5): 470-475.
[30] Yang W, Zhang K, Zeng D, et al. Microstructure evolution and wear behavior of Stellite12 coating prepared by laser-directed energy deposition on H13 steel[J]. Materials Today: Communications, 2024, 41: 110960.
[31] Li Y, Zhou J, Liu Y, et al. Microstructural evolution and mechanical characterization for the AlCoCrFeNi_2.1 eutectic high entropy alloy under different temperatures[J]. Fatigue and Fracture of Engineering Materials and Structures, 2023, 46(5): 1881-1892.
[32] Wang X, Zhang Q, Pan X, et al. On the microstructural evolution and mechanical property development of additively manufactured AlCoCrFeNi_2.1 eutectic high-entropy alloy with aging temperature[J]. Materials Science and Engineering A, 2024, 913: 147060.
[33] Shen Q, Kong X, Chen X. Significant transitions of microstructure and mechanical properties in additively manufactured Al-Co-Cr-Fe-Ni high-entropy alloy under heat treatment[J]. Materials Science and Engineering A, 2021, 815: 141257.
[34] An J, Zhou Y, Yan M, et al. Effect of heat treatment on microstructure and mechanical properties of direct energy deposited AlCoCrFeNi_2.1[J]. Journal of Thermal Spray Technology, 2022, 31(5): 1634-1648.
[35] Lan L, Zhang H, Yang Z, et al. Significant transitions of microstructure and mechanical properties in laser additive manufacturing AlCoCrFeNi_2.1 eutectic high-entropy alloy under heat treatment[J]. Journal of Materials Research and Technology, 2023, 25: 6250-6262.
[36] Cheng Q, Zhang Y, Xu X D, et al. Mechanistic origin of abnormal annealing-induced hardening in an AlCoCrFeNi_2.1 eutectic multi-principal-element alloy[J]. Acta Materialia, 2023, 252: 118905.
[37] Miao J, Yao H, Wang J, et al. Surface modification for AlCoCrFeNi_2.1 eutectic high-entropy alloy via laser remelting technology and subsequent aging heat treatment[J]. Journal of Alloys and Compounds, 2022, 894: 162380.