常见聚合物在纯氢环境中的氢渗透行为

Hydrogen permeation behavior of common polymers in pure hydrogen environment

  • 摘要:
    目的 管道输氢是最为经济的长周期、大规模、长距离输氢方式,然而管线钢在氢气环境中会发生氢脆,以非金属聚合物来代替管线钢可以避免氢脆行为的发生。当前对于氢气在聚合物中的渗透行为研究较少,因此需要开展更为系统直观的研究。
    方法 选取6种管道输送系统中常见典型的聚合物,包括聚乙烯(PE)、聚酰胺(PA)、聚丙烯(PP)、聚醚醚酮(PEEK)、聚偏氟乙烯(PVDF)以及丁腈橡胶(NBR),观察低压(0.5 MPa)、不同温度下氢渗透后的微观形貌、化学组成与晶体结构的测试表征,计算不同温度下的氢渗透系数,结合表征测试结果与氢渗透系数分析氢渗透行为。
    结果 对于可能用作氢气管道管材的PE,PA与PP,在常温下截面未出现较大孔隙与裂纹,在较高温度(约为50 ℃)下,PE截面的孔隙与裂纹比PA和PP更轻微,3种非金属管材的结晶度轻微降低,化学组成与晶体结构未发生明显变化。对于可能用作氢气管道密封材料的PEEK,PVDF与NBR,在常温下截面未出现明显分层或损伤,在较高温度(约为50 ℃)下,PEEK断面出现轻微粗糙化,PVDF与NBR断面出现较为密集的孔隙,存在形成贯通式裂纹的风险,3种密封材料的化学组成与晶体结构未发生明显变化,结晶度也未降低。综合试验结果来看,PE与PEEK的微观形貌、化学组成及晶体结构受氢气渗透影响最小。
    结论 研究结果可用于指导城镇纯氢管网初步设计中的非金属管材与密封材料的选型工作,在未来的城镇低压纯氢/掺氢管道的非金属管材与密封材料选型上建议优先选用PE与PEEK。

     

    Abstract:
    Objective Pipeline hydrogen transportation is the most cost-effective solution for long-term, large-scale and long-distance hydrogen transport. However, pipeline steel is susceptible to hydrogen embrittlement in such environments. Replacing pipeline steel with non-metallic polymers can mitigate this issue. Currently, research on hydrogen permeation in polymers is limited, highlighting the need for a more systematic and intuitive study.
    Methods Six typical polymers used in pipeline systems—polyethylene (PE), polyamide (PA), polypropylene (PP), polyether ether ketone (PEEK), polyvinylidene fluoride (PVDF), and nitrile butadiene rubber (NBR)—were selected for study. Their microscopic morphology, chemical composition, and crystal structure were characterized after hydrogen permeation at low pressure (0.5 MPa) and various temperatures. Hydrogen permeation coefficients at different temperatures were calculated, and permeation behavior was analyzed based on the characterization results and coefficients.
    Results For PE, PA and PP—potential hydrogen pipe materials—no significant pores or cracks were observed on the cross-section at room temperature. At elevated temperatures (around 50 °C), PE exhibited less severe pores and cracks than PA and PP. All three materials showed a slight decrease in crystallinity, with no notable changes in chemical composition or crystal structure. For PEEK, PVDF and NBR—potential sealing materials—no obvious delamination or damage was detected at room temperature. At elevated temperatures (~50 °C), PEEK exhibited slight roughening, while PVDF and NBR exhibited relatively dense pore formation with a risk of through-cracks. The chemical composition and crystal structure of all three sealing materials remain largely unchanged, with no decrease in crystallinity. Overall, PE and PEEK demonstrated the greatest resistance to hydrogen permeation, with minimal changes in microscopic morphology, chemical composition, and crystal structure.
    Conclusion The research findings can inform the selection of non-metallic pipe and sealing materials in the preliminary design of urban pure hydrogen pipeline networks. It is recommended to prioritize PE and PEEK in choosing non-metallic materials for future urban low-pressure pure hydrogen or hydrogen-blended pipelines.

     

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