Article(id=1208051026331013698, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1208051024368083510, articleNumber=null, orderNo=null, doi=10.12404/j.issn.1671-1815.2404904, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1719763200000, receivedDateStr=2024-07-01, revisedDate=1742140800000, revisedDateStr=2025-03-17, acceptedDate=null, acceptedDateStr=null, onlineDate=1765951409179, onlineDateStr=2025-12-17, pubDate=1751040000000, pubDateStr=2025-06-28, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1765951409179, onlineIssueDateStr=2025-12-17, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1765951409179, creator=13701087609, updateTime=1765951409179, updator=13701087609, issue=Issue{id=1208051024368083510, tenantId=1146029695717560320, journalId=1146123166801305609, year='2025', volume='25', issue='18', pageStart='7455', pageEnd='7883', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1765951408712, creator=13701087609, updateTime=1765951896766, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1208053071507198943, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1208051024368083510, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1208053071507198944, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1208051024368083510, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=7455, endPage=7464, ext={EN=ArticleExt(id=1208051026993713744, articleId=1208051026331013698, tenantId=1146029695717560320, journalId=1146123166801305609, language=EN, title=A Review of Research Advance on Hydrogen Embrittlement of Metal Materials, columnId=1208051026863690315, journalTitle=Science Technology and Engineering, columnName=Surveies·Mining and Metallurgical Engineering, runingTitle=null, highlight=null, articleAbstract=

Hydrogen energy is a promising secondary low-carbon energy source in the 21st century of global energy transition. However, HE hydrogen embrittlement in metallic materials refers to the diffusion of hydrogen into the metal in different forms, either in solid solution or as hydrides, causing severe lattice distortion, reducing ductility and toughness, and leading to embrittlement and fracture. It has raised a number of safety issues and limited the service life of hydrogen storage systems due to its insidious nature, abruptness, and diverse failures. In recent years, scholars have been conducting extensive research on hydrogen embrittlement, benefiting from improved experimental tests and numerical simulation methods. A comprehensive review of the latest advancements in hydrogen embrittlement research was provided: elucidating the concept of hydrogen embrittlement and the prevailing mechanism, analyzing the characteristics and factors influencing hydrogen embrittlement in storage vessels, and summarizing the characteristics and primary application scopes of the existing macro to micro, static and dynamic experimental methods in the evaluation of material hydrogen embrittlement. Special attention is given to the research progress in combining these methods with numerical simulation analyses, including their applicability and limitations in practical engineering. Insights and references might be offered to the ongoing development of evaluation methodologies for the hydrogen embrittlement resistance of metal materials.

, correspAuthors=Jia-min ZHANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Lian-zhong SUN, Jia-min ZHANG, Bao-ping ZHANG, Xin-yi HU, Jiang HE, Cheng-cheng NIU), CN=ArticleExt(id=1208051029640319634, articleId=1208051026331013698, tenantId=1146029695717560320, journalId=1146123166801305609, language=CN, title=金属材料氢脆研究进展, columnId=1208051027090182742, journalTitle=科学技术与工程, columnName=综述·矿冶工程, runingTitle=null, highlight=null, articleAbstract=

氢能作为21世纪极具前景的一种低碳、高效的二次能源,是全球能源转型发展的重要载体之一。然而,金属材料的氢脆现象即:氢以不同形态扩散到金属中以固溶态存在或生成氢化物,致金属晶格高度变形,降低韧性及延性,引起脆化至断裂, 因其具有隐蔽性、突发性及失效形式多样性等特点,成为制约氢能储运系统服役寿命和安全性的关键因素。随着实验手段和数值模拟方法的不断完善,中外学者近年来针对氢脆问题进行了大量研究工作。综述了氢脆研究的最新进展:首先阐述了氢脆失效概念及氢脆发生机理,并分析了储氢压力容器的氢脆特征及不同影响因素,其次总结了现有评价材料氢脆敏感性的宏观至微观、静态和动态实验方法的特点及主要应用范围,着重讨论了与数值模拟分析方法结合的研究进展,包括其在实际工程应用中的适用性与局限性,以期为氢环境中金属材料抗氢脆性能评价方法的进一步发展提供借鉴和参考。

, correspAuthors=张佳敏, authorNote=null, correspAuthorsNote=
* 张佳敏(1995—),女,汉族,湖北广济人,博士,助理研究员。研究方向:地下空间储能研究。E-mail:
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孙连忠(1983—),男,汉族,山东肥城人,博士,副研究员。研究方向:钻井提速技术优化及地下储能工程技术。E-mail:

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孙连忠(1983—),男,汉族,山东肥城人,博士,副研究员。研究方向:钻井提速技术优化及地下储能工程技术。E-mail:

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孙连忠(1983—),男,汉族,山东肥城人,博士,副研究员。研究方向:钻井提速技术优化及地下储能工程技术。E-mail:

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金属材料氢脆研究进展
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孙连忠 , 张佳敏 * , 张保平 , 胡昕怡 , 何江 , 牛成成
科学技术与工程 | 综述·矿冶工程 2025,25(18): 7455-7464
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科学技术与工程 | 综述·矿冶工程 2025, 25(18): 7455-7464
金属材料氢脆研究进展
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孙连忠 , 张佳敏* , 张保平, 胡昕怡, 何江, 牛成成
作者信息
  • 中石化石油工程技术研究院有限公司, 北京 102206
  • 孙连忠(1983—),男,汉族,山东肥城人,博士,副研究员。研究方向:钻井提速技术优化及地下储能工程技术。E-mail:

通讯作者:

* 张佳敏(1995—),女,汉族,湖北广济人,博士,助理研究员。研究方向:地下空间储能研究。E-mail:
A Review of Research Advance on Hydrogen Embrittlement of Metal Materials
Lian-zhong SUN , Jia-min ZHANG* , Bao-ping ZHANG, Xin-yi HU, Jiang HE, Cheng-cheng NIU
Affiliations
  • Sinopec Research Institute of Petroleum Engineering Co., Ltd., Beijing 102206, China
出版时间: 2025-06-28 doi: 10.12404/j.issn.1671-1815.2404904
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氢能作为21世纪极具前景的一种低碳、高效的二次能源,是全球能源转型发展的重要载体之一。然而,金属材料的氢脆现象即:氢以不同形态扩散到金属中以固溶态存在或生成氢化物,致金属晶格高度变形,降低韧性及延性,引起脆化至断裂, 因其具有隐蔽性、突发性及失效形式多样性等特点,成为制约氢能储运系统服役寿命和安全性的关键因素。随着实验手段和数值模拟方法的不断完善,中外学者近年来针对氢脆问题进行了大量研究工作。综述了氢脆研究的最新进展:首先阐述了氢脆失效概念及氢脆发生机理,并分析了储氢压力容器的氢脆特征及不同影响因素,其次总结了现有评价材料氢脆敏感性的宏观至微观、静态和动态实验方法的特点及主要应用范围,着重讨论了与数值模拟分析方法结合的研究进展,包括其在实际工程应用中的适用性与局限性,以期为氢环境中金属材料抗氢脆性能评价方法的进一步发展提供借鉴和参考。

氢损伤  /  氢脆机理  /  金属材料  /  物理与数值模拟  /  研究进展

Hydrogen energy is a promising secondary low-carbon energy source in the 21st century of global energy transition. However, HE hydrogen embrittlement in metallic materials refers to the diffusion of hydrogen into the metal in different forms, either in solid solution or as hydrides, causing severe lattice distortion, reducing ductility and toughness, and leading to embrittlement and fracture. It has raised a number of safety issues and limited the service life of hydrogen storage systems due to its insidious nature, abruptness, and diverse failures. In recent years, scholars have been conducting extensive research on hydrogen embrittlement, benefiting from improved experimental tests and numerical simulation methods. A comprehensive review of the latest advancements in hydrogen embrittlement research was provided: elucidating the concept of hydrogen embrittlement and the prevailing mechanism, analyzing the characteristics and factors influencing hydrogen embrittlement in storage vessels, and summarizing the characteristics and primary application scopes of the existing macro to micro, static and dynamic experimental methods in the evaluation of material hydrogen embrittlement. Special attention is given to the research progress in combining these methods with numerical simulation analyses, including their applicability and limitations in practical engineering. Insights and references might be offered to the ongoing development of evaluation methodologies for the hydrogen embrittlement resistance of metal materials.

hydrogen damage  /  hydrogen embrittlement mechanism  /  physical and numerical simulation  /  metallic material  /  research and development progress
孙连忠, 张佳敏, 张保平, 胡昕怡, 何江, 牛成成. 金属材料氢脆研究进展. 科学技术与工程, 2025 , 25 (18) : 7455 -7464 . DOI: 10.12404/j.issn.1671-1815.2404904
Lian-zhong SUN, Jia-min ZHANG, Bao-ping ZHANG, Xin-yi HU, Jiang HE, Cheng-cheng NIU. A Review of Research Advance on Hydrogen Embrittlement of Metal Materials[J]. Science Technology and Engineering, 2025 , 25 (18) : 7455 -7464 . DOI: 10.12404/j.issn.1671-1815.2404904
氢能作为用能终端实现绿色低碳转型的重要载体之一,安全、高效、经济的储运技术是推动其快速实用化、产业化发展的关键[1]。国际氢能委员会报告《氢能规模化——全球能源转型的可持续途径》预测显示,至2050年,氢能有望占据全球终端能源消费的18%[2]。当下,世界重要经济体如美国、欧盟、日本,相继发布国家层面战略,以强化“碳中和”布局,抢占氢能产业发展制高点[3-4]。在“双碳”目标的引领下,中国对氢能这一战略性新兴产业的重视程度逐步提升,近年来相继出台了一系列政策措施与规划文件:特别是《氢能产业发展中长期规划(2021—2035年)》中明确了氢能在未来国家能源体系中的战略地位,为其长足发展提供了有力支持[5]。氢原子作为半径最小的原子,在储运过程中极易渗入材料内部,导致金属材料疲劳寿命降低、塑性强度减弱,结构或构件过早失效,甚至引发重大事故[6-7]。氢致金属材料损伤、断裂失效问题自1875年Johnson[8]发现材料氢脆现象以来就一直是一个世界性的复杂难题,至今也没有能够从根本上规避材料氢脆现象的措施。诸多学者提出了氢压、氢降低内聚力、氢促进局部塑性变形等不同理论模型来解释氢致损伤与破坏现象,但对于氢与材料微观结构相互作用导致脆化的机制仍存在争议[7]。为了表征已提出的氢脆机理,目前中外主要通过多尺度(宏观、微观、纳观)力学实验来验证,而数值模拟方法如分子动力学及有限元分析因其高实用性、工程可操作性和低成本优势,已成为研究微观氢脆过程与宏观现象关联的重要工具 [9-11]。然而,当前对储氢材料在氢气环境中损伤的研究相对匮乏,尤其缺乏对涵盖不同尺度的实验和数值模拟研究的全面对比分析,未能充分理解氢脆问题的多层次复杂性,使得材料寿命预测和安全评价受到制约[12-13]
因此,现对现有代表性的氢脆机理进行系统综述,分类讨论多尺度实验与数值模拟方法的研究进展,明确领域内亟需解决的技术难题,最后提出氢脆防控技术的发展路径,旨在为储氢材料的实际安全评估提供参考依据。
金属由于有氢存在或与氢反应引起的机械破坏称为氢损伤,其主要原因是氢的扩散和渗透[14]。这对金属性能的影响在任何情况下都是不利的。特别是氢脆问题,一般将氢致开裂与延迟断裂、氢鼓泡、以及由氢引起的力学性能变化等现象统称为氢脆,其具有隐蔽性、突发性且失效形式多样[15]
氢原子渗透到钢内部后,使钢的韧性降低,引发氢致开裂。其断口主要表现为脆性断裂,呈冰糖状,沿晶断裂,显示出大量微型、发育不完整的显微微坑,其纹路形似鸡爪,因此也被称为“鸡爪纹”,有时还会出现解理或准解理断裂,如图1所示。氢致滞后断裂作为氢致材质性能恶化的另一形式,描述了金属材料在受到氢脆作用后,在一段时间内需承受持续应力,最终发生突然断裂。这段时间被称为孕育期,在此期间,金属内部(尤其在拉应力区域)逐渐形成裂纹,在应力作用下逐渐扩展,直至达到临界裂纹长度,导致突然的脆性断裂。在高强度钢中发生的氢致延迟断裂与工作温度相关,主要发生在-100~150 ℃,在室温附近表现最为明显[8]。而氢鼓泡现象是指氢原子渗入金属的微缝隙或气孔中,聚集并形成分子氢,导致局部氢压急剧升高,进而在金属表面形成鼓泡或内部引起裂纹[16]
氢压理论 (hydrogen pressure, HP)由Zapffee等[18]于1941年提出,该理论认为金属中氢脆损伤主要是内部微孔隙中的高氢压引起的[19]。氢在金属中的溶解度随着温度降低而减小,导致大量氢原子析出。金属基体内的晶粒间缺陷形成氢陷阱,当表面的氢原子渗透到基体内部时,被氢陷阱捕获,并通过化合反应形成分子氢。氢从原子转变为分子时体积增大,在微孔隙中形成内应力[20]。随后氢原子在微孔隙中扩散与聚集,使得微孔隙内部的氢压不新增大。当压力到达临界强度时,会导致微孔隙周围金属裂纹的萌生、扩展和破坏[21]。HP理论不牵涉塑性变形,仅用于解释特定裂纹的形成,如白点、酸洗和电镀裂纹、以及无外应力电解充氢时产生的裂纹,但对于可逆的氢损伤,如氢致延迟新裂、氢致可逆塑性损失等,则无法提供合理的解释[22]
1926 年,Pfeil[23]首次提出了氢降低材料内部解理面结合能的概念,由此产生了氢降低内聚力理论 (hydrogen enhanced decohesion,HEDE)。Troiano[24]在研究钢中氢脆行为的基础上完善了该理论。随后Oriani等[25]也对机理的定量关系进行了一定补充和修正,在金属晶格中,原子间的吸引力来自正离子与自由电子之间的静电作用,而排斥力源自正离子间的相互作用和电子云的重叠。该理论的研究者认为,对大部分过渡金属来说,基体中原子的d层电子处于未填满状态,这为氢原子的1 s电子提供大量活动的空间。氢原子的电子活动会提高金属原子的活性,使电子密度增大,增加原子间斥力,从而降低金属键的强度。当氢压力大于基体的抗拉强度时,会形成裂纹导致氢脆。事实上,HEDE理论不能解释氢脆产生在非过渡族金属中的原因,并且由于现有科学研究手段无法测出原子间的结合力和氢原子运动轨迹,还没有实验能够直接证明HEDE机理。这一理论仍有待进一步研究、补充和完善。
1972年,Beachem[26]基于观察到的充氢金属拉伸断面上的众多撕裂脊和韧窝,提出了氢促进位错运动导致开裂的理论。随后,Birnbaum等[27]和Delafosse等[28]代表性研究团队接连对其进行了完善,最终形成了氢促进局部塑性变形理论 (hydrogen enhanced localized plasticity,HELP)。该理论认为氢原子会在材料中的裂纹尖端聚集,从而减少位错之间的相互作用力。因此,在外力作用下,这些位错更容易移动,使得材料在裂纹周围的塑性变形增加。随着位错的活动和运动,材料出现小孔洞,最终可能导致断裂[22,29]
氢致应变导致的空位聚集理论 (hydrogen enhanced strain induced vacancy,HESIV)由Nagumo等[30]在2000年提出。金属塑性变形时,应变累积会使材料内部形成空位或微小孔洞,氢原子的存在会加速这些孔洞的增长,使它们快速形成并扩展成裂纹,最终导致材料断裂[31]
2012年,Neeraj等[32]将HEDE、HELP和HESIV3种机理相结合,提出了纳米韧窝聚集导致氢脆机理 (nanovoid coalescence,NVC)。该理论的核心观点是:金属材料中一旦有裂纹形成,裂尖会集聚氢气,导致局部塑性变形,形成许多空位。氢在这些空位中聚集,使得局部应力超过了材料的强度极限,最终引发微小裂缝形成并使材料断裂[22]
上述氢脆机理的关键特征如图2所示。通常情况下,主要根据多种氢脆机理的协同作用来解释对应金属材料的氢脆现象,现有机理各自有片面性与浅层性,尚无完整的理论能够统一解释所有的氢脆现象[29-30]。目前,由于氢效应研究的范围涵盖了从微观晶格到宏观裂纹的不同尺度,跨尺度实验方法在揭示氢脆内在本质方面表现出显著优势并得到了广泛应用。
氢脆的力学实验评价方法从宏观尺度逐渐发展到微观,再到纳米和原子尺度。迄今为止,在宏观尺度已存在一套相对较为成熟的力学实验方法来评估材料的氢脆倾向性。根据外载荷加载方式的不同,又可被划分为静态实验和动态实验。
氢脆现象主要体现在I型拉应力条件下,即外加拉应力与裂纹面垂直。评估材料氢脆行为的宏观静态实验方法主要有慢应变速率拉伸实验和氢致开裂门槛应力强度因子实验等[33-34]。适用于研究恒定载荷下材料的氢气渗透和力学性能变化,尤其是对氢气储存罐和高压管道的长期服役评估[35]
慢应变速率拉伸实验 (slow strain rate tensile,SSRT)是检测氢对材料力学性能影响的最常用手段之一,具有设备成本低、操作方便且效率较高等优点。SSRT实验与常规拉伸实验的区别在于它的低应变速率,范围通常介于10-4 ~ 10-7 s-1。它通过与在惰性条件下进行的实验结果相对比,评估了材料在拉伸性能、断裂特征等方面的相对变化(如屈服强度、抗拉强度、断后延伸率、断面收缩率),从而反映氢对材料的真实影响[14]。其中,相对断面收缩率 (relative reduction of area,RRA) 是评价氢脆敏感性的主要参数:值范围为0~1,数值越小表示材料的氢脆程度越高。美国宇航局NASA据此制定了一种判断氢脆程度等级的划分方法:严重氢脆RRA<0.5;中度氢脆0.5<RRA<0.75;轻度氢脆0.75<RRA<0.9;无氢脆RRA>0.9[36]。国际和国内标准,包括ASTM G142、GB34542.2—2018和ANSI/CSA CHMC 1均明确规定了该方法用于评估材料的氢脆敏感性[37-39]
氢致开裂门槛应力强度因子实验 (hydrogen-induced cracking,HIC)是一种用于量化材料在高压氢环境下发生氢致滞后断裂敏感性的方法。主要测量材料在应力诱导下裂尖处的氢浓度,以确定裂纹开始扩展所需的最低应力强度因子,这也是临氢部件断裂力学疲劳分析中确定临界裂纹和构件疲劳寿命的一个重要参数。ANSI/CSA CHMC 1标准中规定了其测量方法[39]
此外,静态实验方法还包括应力控制线性加载实验 (linearly increasing stress test,LIST)和恒载荷实验 (constant load test,CLT)[40-41]。它们与SSRT的区别在于:SSRT采用应变控制加载,LIST采用应力控制的线性加载(可直接确定材料的氢脆临界应力),而CLT通过确定材料产生氢脆的临界应力或在特定加载条件下的临界氢含量来评估其耐氢脆性。目前,这两种方法还未广泛标准化,因此应用受到较大限制。
主要通过疲劳寿命和疲劳裂纹扩展速率等动态实验方法对储氢设备服役构件在长期压力波动环境下的氢脆行为进行宏观力学评价。从经济性考虑,只有当SSRT等静态实验结果表明材料氢脆现象不严重时,才继续开展疲劳寿命或疲劳裂纹扩展速率实验[42]
疲劳寿命实验通过比较试样在高压氢环境和惰性环境下的疲劳寿命来直接评估材料的氢脆敏感性,目的是得到S-N疲劳曲线。在S-N曲线中,S代表应力(stress),N代表循环次数(number of cycles),曲线上的每一个点表示在特定应力水平下材料可以承受多少循环载荷次数。由于高压氢气环境会显著增加材料氢脆敏感性而无需引入裂纹或缺陷,通常使用无裂纹光滑圆棒试样进行疲劳性能测试。高压氢环境主要影响材料的裂纹扩展过程,对疲劳寿命的影响取决于疲劳试验的频率和应力水平。SAE J2579、GB 34542.2—2018以及ANSI/CSA CHMC 1均规定了该方法用于评估高压氢环境对材料疲劳性能的影响[38-39,43]
疲劳裂纹扩展速率实验是一种评估含缺陷临氢部件寿命的方法。氢积聚在裂纹尖端增加了局部内能,致使近门槛值区域的疲劳裂纹扩展速率上升。实验过程中,裂纹扩展速率da/dN与应力强度因子ΔK显示3个阶段:①下门槛值ΔKKth,裂纹开始形成;②上门槛值ΔKthKKt,裂纹扩展速率加快,高压氢环境下速率明显高于空气环境;③裂纹达到断裂韧性ΔKtK,试样迅速断裂。在断裂力学疲劳分析中,高压氢环境下的疲劳裂纹扩展速率测试为提供了重要的设计参量,ANSI/CSA CHMC 1以及国家标准GB 34542.2—2018已将其列入基本试验类型[38-39]
随着制样技术的不断进步,微纳力学尺度实验为解析氢脆机理提供了关键的实验手段,这里主要介绍纳米压痕实验和环境TEM实验。
纳米压痕实验是一种用于反映材料微观力学响应的技术,通过载荷-压入深度位移曲线来实现。这种测试方法使用了非常小的压头(100 nm到几微米),可以测量材料微区对外力的抵抗能力,如纳米硬度和弹性模量[44]。引入的几何形状必需位错环和部分晶格旋转会导致压痕形成,反映材料内部位错的形成、增殖和运动情况。这种方法尤其适用于初始位错较少的材料,因为在压痕形成时,可以将压头和材料表面看作是完美贴合的(符合理想的弹性接触),但随着压力的增加,会出现弹性到塑性变形的位移突变[45]。纳米压痕技术比起宏观实验更容易看出材料的强度和缺陷之间的关系。目前,该技术主要用于奥氏体和经过退火处理的铁素体,如退火铁素体、奥氏体等初始位错较少的基体组织,但对于位错较多的材料,如马氏体,这个方法则难以直接得到材料的力学性能曲线[46]
当将压痕应力场转变为单向压缩或集中载荷的悬臂弯曲应力场时,就得到了微圆柱压缩和悬臂梁弯曲实验。它们为氢脆现象和其本质提供了互相补充的互相验证,即氢对位错移动的影响具有双重效应。微圆柱压缩实验中,试样内部受到单向均匀的压应力场影响,原子氢分布相对均匀,在有氢条件下,由于氢降低了位错形核的激活能,激活更多的滑移系,导致试样表现出较为均匀的变形[47]。而微悬臂弯曲实验中,由于存在预制的尖锐缺口,缺口前端会产生应力集中,含氢环境下,氢会减少位错形核的阻力,增加必需位错的形成。同时,氢限制了位错的移动,导致裂纹周围形成高密度的位错区域,随着应力增加,裂纹扩展加剧氢脆现象[47]
透射电子显微镜 (transmission electron microscope,TEM)是研究材料内部位错组态、数量以及位错运动的一种重要工具[48]。Robertson等[49]的研究表明,氢的存在会削弱位错之间的弹性相互作用,导致位错间距减小,从而加速位错移动并加剧氢脆现象。这一发现为氢导致材料性能下降提供了直接证据,深化了对HELP机制的理解。
综合来看,氢脆机理的多样性及分歧源于氢在材料中作用的复杂性,受材料结构、成分、应力状态等内在特性以及氢扩散、吸附和缺陷相互作用等多因素影响。这些跨尺度、多物理场耦合过程使氢致裂纹的萌生与扩展机制表现出显著的材料与环境依赖性。同时,实验技术受制于实时观测和微尺度分辨能力不足,难以全面捕捉关键动态过程,进一步加剧了理论解释的不统一。
为了在材料研发和实际工程设计中降低实验成本和研究复杂性,数值模拟方法被用来分析氢对晶体结构、位错分布及局部硬化行为的影响,能够为氢致金属损伤的微观机制提供直接证据[50-51]
现有微观数模方法旨在通过耦合氢气在晶格中的扩散模型和晶体塑性有限元模型,精确描述氢在材料内部的传输状态,了解氢在不同加载条件下对材料局部力学性能的影响,适用于复杂储氢工程结构的氢脆行为评估与设计优化 [52-53]
Miresmaili等[54]提出了一种耦合的晶体塑性-瞬态氢扩散模型用来研究微观结构对氢输运的影响,发现氢主要偏析在晶界处,并且晶粒尺寸对氢偏析量和浓度梯度的影响很大。Legrand等[55]通过数值分析研究了多晶聚合体中尺度效应和微观结构对氢扩散的影响。Ilin等[56]研究了不锈钢微观结构中的应力-应变不均性对扩散的影响。在比较多晶和等效均质材料中氢的运输时,Charles等[57]强调了不同尺度下合适的陷阱模型(陷阱密度函数)对真实模拟的重要性。此外,陈鹏程等[58]在相场氢脆断裂模型的基础上,引入应变能拉压分解并提供了模型的改进数值求解公式,推导了浓度场和位移场耦合项的刚度矩阵,并通过相场氢脆断裂计算程序模拟了两种不同模式的氢脆断裂过程。在断裂过程中,氢离子会向裂尖处扩散集中。氢浓度越高,临界破坏载荷越小,如图3所示。
在固体理论中,金属晶体被视作几乎不动的离子实嵌入了自由运动的电子海之中,即著名的自由电子气模型。为了描述这些自由电子带来的多体效应,DAW和BASKES提出了 (embedded atom method,EAM)方法,也被称为嵌入原子势方法[59-61]。EAM方法理论基础能较为准确的描述金属的结合能的形成,在研究氢脆方面也得到应用。Ramasubramaniam等[62]结合准静态和分子动力学计算方法,研发了一种EAM模型来模拟铁原子和氢原子的相互作用体系。在此基础上,Shishvan等[63]改进了该EAM方法并模拟预测了4340钢中铁原子与氢原子的相互作用力及缓慢加载条件下氢致裂纹的发展路径,如图4所示。但由于微观实验条件受限,对于该预测的有效性有待验证,其在氢环境下钢结构设计中的适用性还需要进一步研究。
数值模拟方法在研究氢对金属材料宏观结构的疲劳行为影响方面也得到应用。Arnaudov等[64]通过修正和扩展Manonukul等[65]提出的不考虑氢影响的金属疲劳寿命评估方法,建立了一种考虑金属组织内氢扩散的疲劳寿命计算模型框架。该模型综合了晶体塑性和氢扩散的方法,帮助理解材料内部微观结构、氢传输和材料的变形响应。考虑了材料中微观结构的特点、氢在材料中的传播以及材料的弹-塑性特性。同时,使用了一种修正的塑性滑移累积作为裂纹产生循环数的指标FIPH,以更好地估计局部氢浓度对裂纹形成的影响。
$\mathrm{FIP}_{H}\left(C_{\mathrm{T}}\right)=\bar{\varepsilon}^{\mathrm{p}}\left(C_{\mathrm{T}}\right)=\int_{0}^{t}\left(1+\frac{C_{\mathrm{T}} H_{\mathrm{T}}}{C_{0}}\right) \sqrt{\frac{2}{3} L^{\mathrm{P}}: L^{\mathrm{P}}} \mathrm{~d} t$
式(1)中: CT为晶格中被捕获的氢浓度; ε - p为累积的塑性应变; t为实验时间;C0为初始氢浓度;HT为特定参数,通过单个应变幅值下的疲劳实验寿命计算;LP为塑性变形速度梯度;为双点积符号,表示分解剪应力张量运算,用于描述塑性滑移系方向和滑移面。
图5所示,预测结果与实验数据显示出良好的一致性,而在低应变区域,由于微观力学模型高估了塑性应变,该方法在预测寿命时表现出一定的保守偏差。通过微观尺度模型的参数推导,建立宏观尺度上的氢脆规律模型,适用于跨尺度氢脆行为预测,特别是在储氢设备和运输管道的寿命预测中具有实际应用价值。
总体而言,氢致损伤数值模拟方法为研究氢对材料力学行为的影响提供了一种高效的手段。然而,氢扩散行为与应力场之间的耦合机制复杂,如何通过数值模型有效描述这种多物理场耦合作用仍未完全解决。跨尺度建模涉及从原子尺度的氢扩散行为到宏观结构的损伤演化过程,其计算成本较高且模型参数标定困难。可以直接指导储氢设备研制和氢储运工程设计的宏观氢致损伤模型,研究尚不充分。尚需进一步关注数值模拟方法在真实工程条件下的模拟效果,以探索不同材料体系的适用性,为探索开发新型耐氢脆材料以及氢气储运工程设计提供更深入的指导。
储氢作为氢能产业链“制、运、储、用”中的“储”关键一环,保障其安全、可靠、可持续发展是推动全球能源体系转型的关键。然而,储氢金属材料在高压氢气和多场耦合作用下易发生氢致损伤,严重限制了其性能和寿命。本文围绕这一工程难题,以氢脆现象为切入点,系统梳理了氢与材料微结构相互作用导致脆化的理论模型,分析了氢脆跨尺度力学实验性能评价方法和数值模拟的研究进展。
随着氢能需求的快速增长,储氢材料需在更严苛的环境下保持抗氢脆性能,但当前研究仍存在关键瓶颈。一方面,氢脆机理尚未形成统一理论,难以全面揭示氢与材料微观结构的复杂相互作用;另一方面,实验和数值模拟均面临技术限制:实验实时观测能力不足,高压、动态环境下难以精准捕捉裂纹萌生与扩展过程;数值模拟则难以精准处理多物理场耦合和跨尺度建模问题,预测精度有待提高。
未来,氢致损伤研究的重点在于揭示氢与材料微结构相互作用的本质及其多尺度力学行为的耦合机理。为深入解析微观机制,需结合同步辐射、三维原子探针等先进表征技术,利用分子动力学与第一性原理模拟,明确氢扩散与晶界、位错等缺陷的相互作用规律。宏观层面,应建立多场耦合实验体系,开发高精度、多场耦合实验技术,实时监测氢致损伤过程中的裂纹扩展与材料劣化行为,建立标准化的抗氢脆性能评价体系,为模型标定提供可靠数据支撑。
数值模拟技术亟需突破多物理场耦合建模的局限性,将氢扩散行为与温度、应力、湿度等多因素影响统一纳入预测框架,同时整合机器学习算法降低计算成本并提升精度,推动复杂环境下的快速多参数分析。在材料设计方面,需结合高通量计算和实验验证,筛选抗氢脆性能优异的材料成分和结构,优化表面涂层改性技术,聚焦纳米增强复合材料、梯度合金等具有优异抗氢脆性能的新型材料。
氢致损伤研究的难点在于储氢环境的复杂性和材料长期服役性能的不确定性。未来需要构建统一的理论框架,贯通实验、模拟与工程应用,实现从基础研究到工程实践的全链条技术整合,并制定系统化的设计标准,为储氢技术在复杂环境下的安全性和可靠性提供有力支撑。
总结而言,金属材料氢致损伤研究不仅承载着推动储氢技术突破的使命,也为绿色能源发展提供了重要机遇。通过基础理论创新与工程技术融合,未来可为氢能产业链的安全、高效运行奠定坚实的科学基础,助力全球能源体系的可持续转型。
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doi: 10.12404/j.issn.1671-1815.2404904
  • 接收时间:2024-07-01
  • 首发时间:2025-12-17
  • 出版时间:2025-06-28
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  • 收稿日期:2024-07-01
  • 修回日期:2025-03-17
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    中石化石油工程技术研究院有限公司, 北京 102206

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* 张佳敏(1995—),女,汉族,湖北广济人,博士,助理研究员。研究方向:地下空间储能研究。E-mail:
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Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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