目的 系统研究了大型污损生物附着对高强度钢牺牲阳极保护效果及其氢渗透的影响。方法 通过在青岛胶州湾开展实海暴露实验,结合原位氢渗透监测、电化学测试、表面形貌分析及腐蚀产物表征等测试方法,对比研究了污损生物附着条件下对高强度钢的阴极防护效果以及氢渗透通量的影响。结果 大型污损生物的附着显著削弱了高强度钢的牺牲阳极保护效果并加剧了附着区域的局部腐蚀,不同污损生物造成的局部腐蚀形貌存在差异性。污损生物的附着改变了锈层的组成成分,促进了Fe3O4和FeS的形成。此外,污损生物的附着为氢渗透创造了更多的路径,使得高强度钢的平均氢渗透电流密度增大,从而提高了氢损伤的风险。结论 污损生物的遮蔽效应破坏钙质沉积层完整性,硬污损生物的紧密附着加剧局部腐蚀;紧密附着区域的厌氧环境促进腐蚀产物转化,同时该独特微区环境也增加了氢渗透的途径。这些发现为指导海洋环境中高强度钢结构大型污损生物腐蚀防护与安全评估提供了理论依据。
Abstract
The work aims to innovatively examine the impact of the attachment and detachment of large fouling organisms on the sacrificial anode protection efficiency and hydrogen permeation behavior of high-strength steel, revealing the underlying interaction mechanisms.
Unique real seawater exposure experiments were conducted in the semi-diurnal tidal area of Jiaozhou Bay, Qingdao, where the average temperature was 13.7 ℃, salinity was 31.5 psu, and pH was 8.3. High-strength steel samples were divided into two groups: one group was shielded with 200-mesh nylon nets to prevent the attachment of large fouling organisms, while the other group was exposed directly to the natural seawater environment. Both groups were equipped with zinc rods for sacrificial anode protection. An improved Devanathan-Stachurski double electrolytic cell was used for in situ hydrogen permeation monitoring in real seawater. Steel plates, 0.5 mm thick with nickel-plated inner surfaces, were sealed into sensors and exposed to seawater. A constant potential (0 V vs. Hg/HgO) was applied through a multi-channel potentiometer to record the hydrogen oxidation current density, which directly reflected the permeation flux. Electrochemical characterization included real-time electrochemical impedance spectroscopy (EIS) at -1.04 V vs. SCE (100 kHz-10 mHz, ±10 mV sine wave) and potentiodynamic polarization curves (±300 mV vs. open circuit potential) and the scan rate was 0.167 mV/s. The test conducted with a portable workstation confirmed that the attached organisms remained active during the tests. Corrosion products and morphologies were analyzed by X-ray diffraction (XRD, Cu Kα, 5°-80°), scanning electron microscopy (SEM), and confocal laser scanning microscopy (CLSM). Corroded surfaces were observed after ultrasonic pickling in 20vol% HCl + 1vol% C6H12N4 solution.
The experimental results revealed variations in localized corrosion caused by different types of fouling. The depths of corrosion pits resulting from soft fouling—ascidians and seagrass—were 47.155 μm and 28 μm, respectively. In contrast, the damage from hard fouling was more severe, with mussels causing pits of 58.45 μm, barnacles 68.4 μm, and oysters 90 μm. Additionally, there were distinct differences in pit morphology among these fouling types. The attachment of fouling organisms weakened the efficiency of sacrificial anode protection: the charge transfer resistance decreased from 9 953 Ω·cm2 to 1 939 Ω·cm2. Additionally, the corrosion current density of the non-fouling group (0.695 μA·cm2) was significantly lower than that of the fouling group (0.912 μA·cm2), confirming the reduced effectiveness of sacrificial anode protection. The presence of large fouling organisms also altered the composition of corrosion products: Fe3O4 and FeS increased significantly in fouled samples, whereas non-fouled samples were dominated by CaCO3 and Fe2O3. Notably, Fe3O4 acted as a "large cathode", accelerating corrosion in unprotected areas, while FeS was produced through anaerobic microbial metabolism (SO42- → HS- + Fe2+ → FeS). More importantly, fouling attachment significantly enhanced hydrogen permeation: the average hydrogen permeation current density increased from 0.638 μA·cm2 in the non-fouling group to 0.806 μA·cm2 in the fouling group, and the diffusible hydrogen concentration rose from 1.115 mmol/kg to 1.408 mmol/kg.
The main ways to increase the hydrogen permeation of high-strength steel by the adhesion of fouling organisms include microbial metabolism, hydrolysis of corrosion products and cathodic hydrogen evolution reaction caused by local acidification.
关键词
大型污损生物 /
高强度钢 /
氢渗透 /
牺牲阳极 /
海洋腐蚀 /
局部腐蚀
Key words
large fouling organisms /
high-strength steel /
hydrogen permeation /
sacrificial anode /
marine corrosion /
localized corrosion
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