目的 针对碳钢和低合金钢在海洋环境中易腐蚀的问题,通过优化等离子喷涂工艺,采用低成本的晶态粉末制备兼具高致密度、高硬度与优异耐蚀性的铁基非晶涂层,并阐明粉末中B元素的牺牲脱氧作用及喷涂参数对涂层结构性能的调控机制。方法 以粒径为30~50 μm的FeCrNiBSi晶态粉末为原料,在80、100、120 mm等3种喷涂距离下于Q235钢表面制备涂层。采用扫描电镜（SEM）、X射线衍射（XRD）和电感耦合等离子体质谱（ICP-MS）表征涂层的微观结构、物相组成及B元素含量,通过显微维氏硬度测试和电化学工作站分别评价涂层的力学性能及其在3.5% NaCl溶液中的腐蚀行为。结果 随喷涂距离从80 mm增至120 mm,涂层非晶含量由53.7%提高至61.4%,同时B元素作为牺牲脱氧剂被持续消耗（质量分数从2.16%降至1.47%）,有效抑制了金属氧化,使涂层孔隙率均低于0.5%。涂层最高硬度达752.1HV,但随着喷涂距离增加,因高硬度硼化物相含量显著减少,硬度呈下降趋势。涂层的耐蚀性与孔隙率紧密相关,当喷涂距离为100 mm时,涂层孔隙率最低（0.36%）,展现出最优的综合耐蚀性,其腐蚀电位为-0.52 V,较Q235基体提升约30%;自腐蚀电流密度为2.51×10-7 A/cm2,较基体降低1个数量级。结论 本研究通过采用含B晶态粉末并优化喷涂距离,利用B元素的牺牲脱氧效应与等离子喷涂的高冷却速率,在Q235钢上成功制备出高硬度、高致密且耐蚀性显著提升的铁基非晶涂层,为低成本、高性能海洋防腐涂层的工程化应用提供了理论与试验依据。
Abstract
To address the corrosion susceptibility of Q235 low-carbon steel in marine environments, the work aims to produce Fe-based amorphous coatings with high density, high hardness, and superior corrosion resistance by optimizing plasma spraying process with low-cost crystalline powders. The mechanisms of boron (B) as a sacrificial deoxidizer and the effect of spraying parameters on coating structure and properties are elucidated.
Coatings were fabricated on Q235 steel substrates with FeCrNiBSi crystalline powder at three spraying distances (80 mm, 100 mm, and 120 mm). The microstructure, phase composition, and B content of the coatings were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and inductively coupled plasma mass spectrometry (ICP-MS). Mechanical properties and corrosion behavior in 3.5wt.% NaCl solution were evaluated via micro-Vickers hardness tests and electrochemical workstation analysis, respectively.
The original FeCrNiBSi powder was spherical or ellipsoidal, with a particle size ranging from 30 μm to 50 μm. XRD patterns revealed that the powder mainly consisted of Fe-based austenite phase, accompanied by a small amount of metallic boride phases. XRD patterns of the Fe-based amorphous coatings prepared by plasma spraying at different spraying distances showed that the coatings were dominated by an amorphous structure with a small amount of crystalline phases. As the spraying distance increased from 80 mm to 120 mm, the amorphous content in the coating increased from 53.7% to 61.4%. The inter-splat bonding in the coatings was sound, with only a small amount of banded and particulate oxides. The content of dark-contrast oxides remained unchanged with spraying distance, further verifying that no obvious oxidation occurred in the coatings. Boron, acting as a sacrificial deoxidizer, was continuously consumed (its content decreased from 2.16wt.% to 1.47wt.%), which effectively suppressed metallic oxidation and resulted in all coatings having a porosity below 0.5%. The relatively small powder size (30-50 μm) used in this work also contributed to the high amorphous fraction and remarkably low oxide content and porosity. On the one hand, droplets with smaller particle size had lower heat capacity and higher cooling rate during impact, spreading, and solidification, which favored the suppression of heterogeneous nucleation and growth of crystals, thus promoting the formation of amorphous phase. On the other hand, a smaller particle size allowed the mass transfer of B from the interior to the oxygen-exposed surface of the droplet to change from diffusion to convection, providing sufficient B at the droplet surface to ensure an effective oxidation-resistant effect. The maximum coating hardness reached 752.1HV. However, hardness exhibited a decreasing trend with the increasing spraying distance, attributable to a significant reduction in the content of high-hardness boride phases. The corrosion resistance of the coatings was closely related to porosity. The coating prepared at 100 mm spraying distance exhibited the lowest porosity (0.36%) and the optimal overall corrosion resistance: its corrosion potential was -0.52 V (approximately 30% higher than that of the Q235 substrate), and its self-corrosion current density was 2.51×10-7 A/cm2 (one order of magnitude lower than that of the substrate).
By employing B-containing crystalline powders and optimizing the spraying distance, this work has successfully prepared Fe-based amorphous coatings on Q235 steel with high hardness, high density, and significantly enhances corrosion resistance. This achievement leverages the sacrificial deoxidation effect of B and the high cooling rate of plasma spraying, providing theoretical and experimental support for the engineering application of low-cost, high-performance anti-corrosion coatings in marine environments.
关键词
铁基非晶涂层 /
等离子喷涂 /
显微组织 /
硬度 /
耐蚀性
Key words
Fe-based amorphous coatings /
plasma spraying /
microstructure /
hardness /
corrosion resistance
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