渗透氢检测方法研究进展

Research Progress of Detection Techniques for Permeated Hydrogen

为实现“碳达峰、碳中和”战略目标,大力发展氢能产业至关重要。氢在制备、运输、储存和使用过程中,容易产生氢渗透,可造成金属材料发生氢损伤,不仅缩短了含氢管道和设备的服役寿命,还带来了严重的安全隐患。因此,推动渗透氢检测技术的发展具有十分重要的意义。渗透氢检测技术可分为室内渗透氢检测技术和现场渗透氢检测技术两大类。室内渗透氢检测方法主要有:电流法、熔融萃取法、热脱附法(TDS)、氢-微接触打印法(HMP)、二次离子质谱(SIMS)法、扫描开尔文探针-原子显微镜技术(SKPFM)法、原子探针技术(APT)和中子照相(NRG)法;现场渗透氢检测方法有:氢致变色识别法、氢通量法、氢探针法、氢传感器和现场开尔文探针(FKP)技术。在室内检测方面,本文总结了各方法的原理、适用范围和特点,重点综述了它们在氢检测领域中的应用。其中,电流法、熔融萃取法和TDS是检测试样表面的平均氢浓度,不具备局部分辨能力。HMP通过Ag^(+)和H的置换反应产生的银颗粒,反映氢的分布和扩散路径,但无法确定Fe有没有参与其中。SKPFM通过连续检测某一位置的电位,可以观察氢在特定位置的富集和扩散动力学过程,但材料外加电流/电位时,会干扰检测结果。SIMS和APT均采用质谱法检测,都具有局部分辨能力,但要充氘排除背景氢的影响。NRG通过检测氢强度和明亮区判断氢的浓度和分布,但空间分辨率只能达到微米级。在现场检测方面,本文调研了市面上几种检测设备的参数,总结了各方法的原理、使用范围和优缺点。最后,对未来渗透氢检测方法的发展提出了建议。

In order to achieve the goals of the“peak carbon dioxide emission and carbon neutrality”,it is essential to develop hydrogen energy.During the production,transportation,storage and use of hydrogen,hydrogen permeation is easy to occur and causes hydrogen damage to metal materials,which not only shortens the service life of pipelines and equipment,but also brings serious potential safety haz-ards.So it is of great significance to promote the development of permeated hydrogen detection tech-niques.Permeated hydrogen testing technology can be divided into indoor-and field-permeated hydro-gen testing techniques.The indoor permeated hydrogen testing techniques include current method,hot/melt extraction,thermal desorption spectroscopy(TDS),hydrogen micro-contact printing(HMP),scan-ning Kelvin probe force microscopy(SKPFM),secondary ion mass spectroscopy(SIMS),atom probe to-mography(APT)and neutron radiography(NRG).The field permeated hydrogen testing techniques in-clude hydrogenochromic method,hydrogen flux method,hydrogen probe method,hydrogen sensor,as well as field Kelvin probe(FKP)technique.For the indoor testing,the principles and characteristics of sev-eral detection techniques were summarized and applicable scope was also introduced.The current meth-od,hot/melt extraction and TDS are used to measure the average hydrogen concentration in materials,but none of the above methods have the ability of spatial resolution.The silver particles produced by the substitution reaction between Ag^(+)and H by HMP reflect the distribution and diffusion path of hydrogen,but it is not certain whether Fe participates in that.By continuously detecting the potential of a certain po-sition,SKPFM can reveal the hydrogen enrichment and the dynamic process of diffusion in a specific po-sition.However,when current/potential is applied on the sample surface,it will disturb the test results.Both SIMS and APT technology rely on mass spectrometry,and have spatial resolution but their measur-ing chamber need to be filled with deuterium to eliminate the influence of background hydrogen.NRG can judge the concentration and distribution of hydrogen by detecting the hydrogen intensity and bright area,but its spatial resolution can only reach micron level.For the field testing,the parameters of several testing equipment provided on the market are investigated in this article,while the principle,application scope,advantages and disadvantages of each method are also summarized.Finally,some suggestions are put forward for the future development of hydrogen permeation detection methods.