目的 海工装备关键件表面长期承受腐蚀与磨损等损伤,为进一步提升其表面耐磨耐蚀性能,延长服役寿命并提高服役可靠性,制备Fe基非晶粉末改性的NiCrMo高熵合金复合涂层。方法 实验采用激光熔覆技术制备了Fe基非晶粉末改性的NiCrMo高熵合金涂层,通过硬度测试、摩擦磨损试验和电化学测试,分别表征了涂层的硬度、耐磨性、耐蚀性及磨损-腐蚀耦合作用后钝化膜的稳定性,结合扫描电镜及三维形貌仪对涂层的微观结构及磨损形貌进行分析。结果 适量Fe基非晶粉末引入NiCrMo基体后,涂层硬度显著提高,相较于NiCrMo涂层提升1.3倍,最高可达1 200HV0.2,而硬度的提升与非晶粉末加入量并非呈线性关系,当非晶粉末含量增加到20%（质量分数）时,平均硬度降低至723HV0.2;室温干滑动磨损条件下,加入非晶粉末后涂层摩擦系数较NiCrMo更稳定,磨痕形貌由表面的大量剥落转变为光滑的犁沟;在保持开路电位稳定状态下,维钝电流密度从1 mA降低至100 μA,降低了一个数量级;磨损-腐蚀耦合条件下,钝化膜稳定性得到显著提升。干滑动摩擦磨损与腐蚀磨损条件下涂层摩擦系数变化趋势一致。结论 Fe基非晶粉末改性的NiCrMo高熵合金涂层结合了NiCrMo的耐蚀性能和非晶的高硬度,使涂层体系兼具良好的耐磨与耐蚀性能。
Abstract
The surface of key components in marine engineering equipment is continuously exposed to corrosion, wear, and other damages, which directly determine service life and reliability. High-entropy alloys (HEAs), due to their tendency to form a single solid solution phase, can simultaneously offer excellent mechanical properties as well as wear and corrosion resistance. Laser cladding features a rapid cooling rate, and the powder experiences rapid melting/solidification, which is similar to a short-term artificial aging treatment, thus increases the coating hardness but may also introduce higher residual stress. In this work, Fe-based amorphous alloy powder is selected as the binder to reduce cracking and improve compatibility between the coating and the steel substrate. Thus, a NiCrMo HEA coating modified with Fe-based amorphous powder is prepared via laser cladding. The hardness, wear resistance, corrosion resistance, and the stability of the passive film under wear-corrosion coupling are characterized by Vickers hardness tests, sliding wear tests, and three-electrode electrochemical tests. The microstructure and wear scar morphology are analyzed by scanning electron microscopy (SEM) and three-dimensional profilometer. Ni, Cr, and Mo powders (99.99% purity) and Fe-based amorphous alloy powder (Fe77Si9B14) at 0, 10, and 20wt.% are mixed by ball milling, followed by vacuum drying for 24 h. Before cladding, the substrate is degreased using a Mopa laser. The main cladding parameters are as follows: laser power of 2 000 W, scan speed of 600 mm/min; the laser head is tilted by 10° with -6 mm defocus; spot diameter of 3 mm, overlap rate of 50%, powder feeding rate of 10 g/min, protective gas pressure of 10 L/min, and protective gas flow rate of 10 L/min. After cladding, the samples are air-cooled to room temperature, cut by wire cutting, and ground and polished to a mirror surface for microstructural observation and phase identification by SEM and X-ray diffraction (XRD). The wear behavior is tested with a reciprocating tribometer, and the corrosion behavior is tested with an electrochemical workstation. The stability of the passive film under wear-corrosion coupling is tested by coupling the electrochemical workstation with the tribometer (detailed parameters and equipment information will be given later). XRD and microstructural observation indicate that the coating mainly contains FCC, BCC, and σ phases, with a typical dendrite-interdendrite structure and an obvious eutectic structure evolution. The introduction of an appropriate amount of Fe-based amorphous powder into the NiCrMo matrix significantly increases hardness and reaching 1 200HV0.2, which is 1.3 times higher than that of the NiCrMo coating. However, the hardness increase is not linear with Fe-based amorphous powder content. When the Fe-based amorphous powder content increases to 20wt.%, the average hardness decreases to 723HV0.2. Under room-temperature dry sliding, the friction coefficient becomes more stable after adding Fe-based amorphous powder, and the wear scar changes from severe spalling to smooth furrows, indicating that the wear mechanism changes from adhesive wear to abrasive wear. Under a stable open-circuit potential, the passive current density decreases from 1 mA to 100 μA, reducing by one order of magnitude. The double-layer structure increases charge transfer resistance and thereby reduces the corrosion current density. The coating with 10wt.% Fe-based amorphous powder shows the response closest to an ideal capacitor and exhibits the best corrosion resistance. In the passive film, Cr2O3 serves as a protective framework and reacts with water to form Cr(OH)3, contributing to film stability. Mo4+ (MoO2) enhances passive film stability, while Mo6+ (MoO42-) can migrate to defect sites to inhibit pitting corrosion. The formation of SiO2-Cr2O3 composite oxides by Si and Cr further enhances film stability. Under wear-corrosion coupling, the stability of the passive film is significantly improved, and the friction coefficient trends in electrolyte are consistent with those under dry sliding conditions. The NiCrMo/ Fe-based amorphous powder system combines the hardness of Fe-based amorphous and the corrosion resistance of NiCrMo, resulting in excellent wear and corrosion resistance.
关键词
激光熔覆 /
NiCrMo /
非晶粉末 /
磨损腐蚀
Key words
laser cladding /
NiCrMo /
amorphous powder /
wear and corrosion resistance
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基金
山东省重点研发计划（2023CXGC010406,2023ZLGX05）; 国家自然科学基金重点项目（52331004）; 国家自然科学基金山东海洋科学研究中心联合基金（U2106216）; 国家自然科学基金（52101188）; 山东省自然科学基金重点项目（ZR2022ZD12,ZR2024ZD14）; 青岛海洋科技创新项目（25-1-1-gjgg-44-hy）; 泰山学者攀登计划（tspd20230603）
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