N80钢表面金属氮化物涂层的阻氢性能与机理研究

Study on the Hydrogen Permeation Resistance and Mechanism of Metal Nitride Coatings on N80 Steel

  • 摘要:
    目的 盐穴储氢场景下注采管面临严重的氢脆与腐蚀风险,亟需开发高效的阻氢防护涂层。系统性地评估并对比具有代表性的涂层,对于筛选和设计适用于盐穴储氢环境的涂层防护技术至关重要。
    方法 利用多弧离子镀法在N80钢上分别制备了TiN、AlCrN及(TiAlCrSiY)N涂层。采用Devanathan-Stachurski双电解池,在电化学监测的液相和气相两种充氢模式下,系统评价各涂层的阻氢渗透性能,并通过电化学极化曲线测试评估其耐腐蚀性。使用扫描电镜(SEM)、数码显微镜等对涂层的微观结构与性能进行表征。通过对比分析TiN、AlCrN与(TiAlCrSiY)N涂层的综合防护性能,探究其内在机理的差异,为盐穴储氢环境下的阻氢涂层选材与设计提供科学依据。
    结果 AlCrN涂层表现出最佳的综合性能,其表面最致密平整、缺陷最少,并具备最高硬度和最强结合力。(TiAlCrSiY)N涂层虽因多元素协同效应而耐腐蚀性最优,但存在较多表面团聚颗粒与微观缺陷,结合力在3种涂层中最差。氢渗透性能测试结果表明,AlCrN涂层阻氢效果最好,与N80基材相比,有效扩散系数降低了83.68%,在气相和液相条件下阻氢效率分别高达99.23%和84.76%。TiN、AlCrN及(TiAlCrSiY)N涂层均有较好的阻氢效果,同时可提高基材的表面强度,增强抗蚀性能。测试分析结果表明,涂层微观结构的致密性是决定其阻氢与力学性能的首要因素,而耐腐蚀性能主要受化学组分影响。
    结论 未来盐穴储氢库阻氢防护涂层开发应优先通过工艺优化来获得低缺陷的致密结构,其次为进行成分优化增强化学稳定性,同步提升其耐腐蚀特性与机械性能,对于保障盐穴储氢库安全运行具有重要工程意义。

     

    Abstract:
    Objective To address the severe risks of hydrogen embrittlement and corrosion facing injection-production tubing in salt cavern hydrogen storage, the development of high-efficiency hydrogen barrier coatings is imperative. Consequently, a systematic evaluation and comparison of representative coatings is crucial for the selection and design of protective technologies suitable for such environments.
    Methods Three types of nitride coatings were prepared on N80 steel substrates using multi-arc ion plating technology. The hydrogen permeation resistance of each coating was systematically evaluated under both liquid-phase and gas-phase hydrogen charging modes using a Devanathan-Stachurski dual electrochemical cell. Their corrosion resistance was assessed via electrochemical polarization curves. The microstructure and mechanical properties of the coatings were characterized by scanning electron microscopy (SEM), digital microscopy, microhardness testing, and micro-scratch testing. This study provides a comprehensive analysis and comparison of the protective performance and underlying mechanisms of the three coatings, offering a scientific basis for material selection and design in salt cavern hydrogen storage environments.
    Results The AlCrN coating exhibited the best overall performance, featuring the densest, flattest surface with the fewest defects, and it demonstrated the highest hardness and the strongest adhesion. Although the (TiAlCrSiY)N coating showed optimal corrosion resistance due to the synergistic effect of its multiple elements, it suffered from numerous surface agglomerates and micro-defects, resulting in the weakest adhesion among the three. Hydrogen permeation tests revealed that, regardless of the charging mode, the AlCrN coating provided the most effective barrier against hydrogen. Compared to the bare N80 substrate, it reduced the effective diffusion coefficient by 83.68%, with hydrogen blocking efficiencies reaching as high as 99.23% (gas-phase) and 84.76% (liquid-phase).
    Conclusion A comprehensive evaluation confirms that all three nitride coatings provide good hydrogen resistance and other beneficial properties such as corrosion resistance and adhesion. The microstructural density of the coatings is the primary factor determining their hydrogen permeation resistance and mechanical properties, whereas corrosion resistance is principally governed by chemical composition. Future development of hydrogen barrier coatings for salt cavern hydrogen storage should prioritize process optimization to achieve low-defect, dense microstructures, followed by compositional optimization to enhance chemical stability and concurrently improve corrosion resistance and mechanical properties. This approach holds significant engineering guidance for ensuring the safe operation of salt cavern hydrogen storage infrastructure.

     

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