La ₂O ₃ 掺杂对 FeCoNiCrAl 高熵合金激光熔覆涂层组织与性能的影响

Effect of La ₂O ₃ doping on microstructure and properties of laser-clad FeCoNiCrAl high-entropy alloy coating

摘要

[目的] 为提高 FeCoNiCrAl 高熵合金涂层的耐磨性与耐蚀性，采用激光熔覆技术在 H13 模具钢表面制备了不同 La ₂O ₃掺杂量(0%、0.5%或 1.0%)的 FeCoNiCrAl 高熵合金涂层。[方法] 通过 X 射线衍射(XRD)、扫描电镜(SEM)、显微硬度测试、摩擦磨损试验、电化学测量及中性盐雾试验，研究了 La ₂O ₃对涂层组织与性能的影响。[结果] La ₂O ₃的添加可调控涂层的相组成：未掺杂涂层为单一 BCC 结构，而 La ₂O ₃的引入促进了 FCC 相的形成，获得 BCC+FCC 双相结构，并显著细化了晶粒,消除了缺陷。随着 La ₂O ₃含量增加，涂层的显微硬度由 220 HV 提升至 551 HV，摩擦因数降低至约 0.25。动电位极化曲线及中性盐雾腐蚀测试表明，1.0% La ₂O ₃掺杂涂层的耐蚀性最优。[结论] La ₂O ₃通过相组成调控、细晶强化与组织致密化的协同作用，显著提升了激光熔覆 FeCoNiCrAl 高熵合金涂层的综合性能。

Abstract

[Objective] To enhance the wear and corrosion resistance of FeCoNiCrAl high-entropy alloy coatings, FeCoNiCrAl high-entropy alloy coatings with varying La ₂O ₃ amounts (0%, 0.5%, and 1.0%) were prepared on the surface of H13 die steel by laser cladding. [Method] The effect of La ₂O ₃ doping on the microstructure and properties of the coatings were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), microhardness testing, friction and wear testing, electrochemical measurements, and neutral salt spray testing. [Result] The addition of La ₂O ₃ regulated the phase composition of laser-clad FeCoNiCrAl high-entropy alloy coating: the undoped coating exhibited a single BCC structure, while the introduction of La ₂O ₃ promoted the formation of an FCC phase, resulting in a BCC+FCC dual-phase structure, significantly refined the grains, and eliminated defects. With the increasing of La ₂O ₃ content, the microhardness of the coating increased from 220 HV to 551 HV, and the friction coefficient decreased to approximately 0.25. Potentiodynamic polarization curves and neutral salt spray corrosion tests indicated that the coating doped with 1.0% La ₂O ₃ exhibited the optimal corrosion resistance. [Conclusion] La ₂O ₃ significantly enhanced the comprehensive performance of the laser-clad FeCoNiCrAl high-entropy alloy coating through the synergistic effects of phase composition regulation, grain refinement strengthening, and microstructural densification.

关键词

铁−钴−镍−铬−铝高熵合金 / 激光熔覆 / 氧化镧 / 掺杂 / 微观组织 / 耐磨性 / 耐蚀性

Key words

iron–cobalt–nickel–chromium–aluminum high-entropy alloy / laser cladding / lanthanum oxide / doping / microstructure / wear resistance / corrosion resistance

参考文献

[1] 李天昕, 王书道, 卢一平, 等. 高熵合金材料研究进展与展望[J]. 中国工程科学, 2023, 25(3): 170-181.

[2] LI T X , WANG S D , LU Y P , et al. Research progress and prospect of high-entropy alloy materials[J]. Strategic Study of CAE, 2023, 25(3): 170-181.

[3] 赵雪柔, 吕煜坤, 石拓. 高熵合金相形成理论研究进展[J]. 材料导报, 2019, 33(7): 1174-1181.

[4] ZHAO X R , LYU Y K , SHI T. Advances in the study of phase formation theory of high entropy alloys[J]. Materials Reports, 2019, 33(7): 1174-1181.

[5] STRAUMAL B B , KLINGER L , KUZMIN A , et al. High entropy alloys coatings deposited by laser cladding: a review of grain boundary wetting phenomena[J]. Coatings, 2022, 12(3): 343.

[6] 姜凤阳, 艾根根, 思芳, 等. 合金成分对高熵合金涂层耐磨性影响的研究进展[J]. 中国表面工程, 2024, 37(4): 18-43.

[7] JIANG F Y , AI G G , SI F , et al. Research progress of the effect of alloy composition on the wear resistance of high-entropy alloy coatings[J]. China Surface Engineering, 2024, 37(4): 18-43.

[8] 李怀博, 王子乐, 杨伟, 等. 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.

[9] LI H B , WANG Z L , YANG W , et al. 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.

[10] 张红霞, 蔡志龙, 李永斌, 等. 激光熔覆 TiC 增强的 TiNiCoCrVSi 高熵合金涂层组织结构与性能[J]. 电镀与涂饰, 2025, 44(11): 55-62.

[11] ZHANG H X , CAI Z L , LI Y B , et al. Microstructure and properties of TiC-reinforced TiNiCoCrVSi high-entropy alloy coating prepared by laser cladding[J]. Electroplating & Finishing, 2025, 44(11): 55-62.

[12] WENG F , CHEN C Z , YU H J. Research status of laser cladding on titanium and its alloys: a review[J]. Materials & Design, 2014, 58: 412-425.

[13] 李冬青, 郑树会, 顾建, 等. Sc/Y掺杂对FeCoNiCrAl高熵合金微观组织及高温氧化性能的影响[J]. 材料保护, 2025, 58(6): 65-73.

[14] LI D Q , ZHENG S H , GU J , et al. Effect of Sc/Y co-doping on microstructure and high-temperature oxidation properties of FeCoNiCrAl high-entropy alloys[J]. Materials Protection, 2025, 58(6): 65-73.

[15] LU Q L , WANG Y F , XIAO L J , et al. Effects of La ₂O ₃ on microstructure and properties of laser clad Fe-based amorphous composite coatings [J]. Materials Science Forum, 2013, 749: 583-588.

[16] ZHANG H , PAN Y , HE Y Z. Synthesis and characterization of FeCoNiCrCu high-entropy alloy coating by laser cladding[J]. Materials & Design, 2011, 32(4): 1910-1915.

[17] LI Z Y , CHEN W G , LI D Y , et al. Frictional wear properties of different nano La ₂O ₃ composite FeCoNiCrMo high-entropy alloy coatings under soil conditions [J]. Journal of Materials Research and Technology, 2025, 35: 6874-6888.

[18] 豆微, 陈冲, 张国赏, 等. 高熵合金涂层的研究现状[J]. 电镀与涂饰, 2023, 42 (16): 33-42.

[19] DOU W , CHEN C , ZHANG G S , et al. Research status of high-entropy alloy coatings[J]. Electroplating & Finishing, 2023, 42 (16): 33-42.

[20] VENKATESH L , SAMAJDAR I , TAK M , et al. Microstructure and phase evolution in laser clad chromium carbide-NiCrMoNb[J]. Applied Surface Science, 2015, 357: 2391-2401.

[21] MA H C , TIAN J W , LU C P , et al. Revealing the beneficial effect and mechanism of rare earth La on the corrosion resistance of weathering steels[J]. Journal of Materials Science & Technology, 2026, 252: 283-300.

[22] 孙又银, 高玉新, 程虎. La ₂O ₃ 对电火花沉积 Fe 基涂层组织和耐磨性能的影响 [J]. 材料保护, 2022, 55(3): 93-97, 114.

[23] SUN Y Y , GAO Y X , CHENG H. Effect of La ₂O ₃ on microstructure and wear properties of Fe-based coating by electro-spark deposition [J]. Materials Protection, 2022, 55(3): 93-97, 114.

[24] WEERTMAN J R. Hall-Petch strengthening in nanocrystalline metals[J]. Materials Science & Engineering A, 1993, 166(1/2): 161-167.

[25] LIU Y , XU M N , XIAO L R , et al. Dislocation array reflection enhances strain hardening of a dual-phase heterostructured high-entropy alloy[J]. Materials Research Letters, 2023, 11(8): 638-647.

[26] 张海浪. 稀土元素 La 对 AlCoCrFeNi _2.1 高熵合金力学性能、耐腐蚀性能和磁性能的影响 [D]. 合肥: 安徽建筑大学, 2025.

[27] ZHANG H L. Effect of rare earth element La on the mechanical properties, corrosion resistance, and magnetic properties of AlCoCrFeNi _2.1 high-entropy alloy [D]. Hefei: Anhui Jianzhu University, 2025.

[28] GUO K T , SUN Y N , CHENG W J , et al. Effect of rare earth La ₂O ₃ on the microstructure and corrosion resistance of CoCrFeNiMoSi high entropy alloys [J]. Surfaces and Interfaces, 2024, 44: 103683.

基金资助

黑龙江省教育厅基本科研业务费(2023-KYYWF-0566)