Article(id=1208361642132357652, tenantId=1146029695717560320, journalId=1146031591421210625, issueId=1208361635656352181, articleNumber=null, orderNo=19, doi=10.3981/j.issn.1000-7857.2024.12.01751, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1734278400000, receivedDateStr=2024-12-16, revisedDate=1749052800000, revisedDateStr=2025-06-05, acceptedDate=1756396800000, acceptedDateStr=2025-08-29, onlineDate=1766025465757, onlineDateStr=2025-12-18, pubDate=1757692800000, pubDateStr=2025-09-13, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1762358400000, onlineIssueDateStr=2025-11-06, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766025465757, creator=13701087609, updateTime=1774079939416, updator=sys-migrate, issue=Issue{id=1208361635656352181, tenantId=1146029695717560320, journalId=1146031591421210625, year='2025', volume='43', issue='17', pageStart='1', pageEnd='144', issueExtLink='null', onlineDate='null', pubDate='1757692800000', pubDateStr='2025-09-13', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766025464214, creator='13701087609', updateTime=1774330860874, updator='13041195026', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1243196994169189037, tenantId=1146029695717560320, journalId=1146031591421210625, issueId=1208361635656352181, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1243196994169189038, tenantId=1146029695717560320, journalId=1146031591421210625, issueId=1208361635656352181, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=77, endPage=84, ext={EN=ArticleExt(id=1208361643004772897, articleId=1208361642132357652, tenantId=1146029695717560320, journalId=1146031591421210625, language=EN, title=Review on corrosion of titanium alloys in extreme deep−sea environments, columnId=1150494642224591153, journalTitle=Science & Technology Review, columnName=Exclusive, runingTitle=null, highlight=null, articleAbstract=

Engineering equipments serving in extremely harsh deep−sea environments will withstand complex environmental factors such as low temperature, low dissolved oxygen, low pH, pollutants, and microorganisms, as well as the effects of hydrothermal, ocean currents, hydrostatic pressure, and complex loads, which pose serious threats to the safety of these equipments in service. Titanium alloy, as a highly corrosion−resistant marine structural material, plays a crucial role in the manufacturing of deep−sea engineering equipments. However, the service behavior and failure mechanism of titanium alloy in extreme deep−sea environments are still unclear, leading to a lack of scientific basis for the selection, design, and protection of titanium alloy structures in deep−sea equipment. This paper analyzes the corrosion resistance and basic corrosion electrochemical characteristics of titanium alloys, systematically reviews the problems of microbial corrosion, crevice corrosion, galvanic corrosion, hydrogen embrittlement and stress corrosion, corrosion fatigue, and multi−factor coupled corrosion damage faced by titanium alloy materials in extreme deep−sea environments, and proposes the research focus and development direction of titanium alloy corrosion in deep−sea environments.

, authors=null, authorsList=Junsheng WU, Kefeng HU, Chaofang DONG, Lingyue HU, Bowei ZHANG, Lin FAN, Kui XIAO, Mingxian SUN, Xingyue YONG, Xiaogang LI, authorCompany=null, correspAuthors=null, authorNote=null, correspAuthorsNote=null, copyrightStatement=All rights reserved. Unauthorized reproduction is prohibited., 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, fund=null), CN=ArticleExt(id=1208361643344511531, articleId=1208361642132357652, tenantId=1146029695717560320, journalId=1146031591421210625, language=CN, title=深海极端环境下钛合金腐蚀科学问题评述, columnId=1150494642375586098, journalTitle=科技导报, columnName=特色专题, runingTitle=null, highlight=null, articleAbstract=

工程装备在极端苛刻的深海环境中服役,将承受低温、低溶解氧、低pH值、污染物和微生物等复杂环境因素以及热液、洋流、高压和复杂工况载荷的作用,对深海装备的服役安全造成严重威胁。钛合金作为高耐蚀海洋结构材料,在深海工程装备制造中具有举足轻重的地位,但目前仍对钛合金在深海极端环境下的服役行为和失效机制认识不清,导致深海装备钛合金结构选材、设计和防护缺乏科学依据。通过对钛合金的耐蚀性及基本腐蚀电化学特征分析,梳理评述了钛合金材料在深海极端环境下所面临的微生物腐蚀、缝隙腐蚀、电偶腐蚀、氢脆及应力腐蚀、腐蚀疲劳以及多因素耦合腐蚀损伤问题,并提出了深海环境下钛合金腐蚀研究重点和发展方向。

, authors=

吴俊升,教授,研究方向为材料海洋腐蚀与防护,电子信箱:

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吴俊升,教授,研究方向为材料海洋腐蚀与防护,电子信箱:

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吴俊升,教授,研究方向为材料海洋腐蚀与防护,电子信箱:

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深海极端环境下钛合金腐蚀科学问题评述
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吴俊升 1 , 胡科峰 2 , 董超芳 1 , 胡凌越 2 , 张博威 1 , 范林 3 , 肖葵 1 , 孙明先 3 , 雍兴跃 4 , 李晓刚 1
科技导报 | 特色专题 2025,43(17): 77-84
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科技导报 |特色专题 2025 , 43 (17) : 77 -84
深海极端环境下钛合金腐蚀科学问题评述
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吴俊升1 , 胡科峰2, 董超芳1, 胡凌越2, 张博威1, 范林3, 肖葵1, 孙明先3, 雍兴跃4, 李晓刚1
作者信息
  • 1. 北京科技大学新材料技术研究院,北京 100083
  • 2. 武汉第二船舶设计研究所,武汉 430064
  • 3. 中国船舶集团有限公司第七二五研究所海洋腐蚀与防护全国重点实验室,青岛 266237
  • 4. 北京化工大学有机无机复合材料国家重点实验室,北京 100029
Review on corrosion of titanium alloys in extreme deep−sea environments
Junsheng WU1 , Kefeng HU2, Chaofang DONG1, Lingyue HU2, Bowei ZHANG1, Lin FAN3, Kui XIAO1, Mingxian SUN3, Xingyue YONG4, Xiaogang LI1
Affiliations
  • 1. Institute of Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China
  • 2. Wuhan Second Ship Design Institute, Wuhan 430064, China
  • 3. National Key Laboratory of Marine Corrosion and Protection, Luoyang Ship Material Research Institute (LSRMI), Qingdao 266237, China
  • 4. State Key Laboratory of Organic−Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
出版时间: 2025-09-13 doi: 10.3981/j.issn.1000-7857.2024.12.01751
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工程装备在极端苛刻的深海环境中服役,将承受低温、低溶解氧、低pH值、污染物和微生物等复杂环境因素以及热液、洋流、高压和复杂工况载荷的作用,对深海装备的服役安全造成严重威胁。钛合金作为高耐蚀海洋结构材料,在深海工程装备制造中具有举足轻重的地位,但目前仍对钛合金在深海极端环境下的服役行为和失效机制认识不清,导致深海装备钛合金结构选材、设计和防护缺乏科学依据。通过对钛合金的耐蚀性及基本腐蚀电化学特征分析,梳理评述了钛合金材料在深海极端环境下所面临的微生物腐蚀、缝隙腐蚀、电偶腐蚀、氢脆及应力腐蚀、腐蚀疲劳以及多因素耦合腐蚀损伤问题,并提出了深海环境下钛合金腐蚀研究重点和发展方向。

深海极端环境  /  钛合金  /  工程装备  /  腐蚀  /  失效

Engineering equipments serving in extremely harsh deep−sea environments will withstand complex environmental factors such as low temperature, low dissolved oxygen, low pH, pollutants, and microorganisms, as well as the effects of hydrothermal, ocean currents, hydrostatic pressure, and complex loads, which pose serious threats to the safety of these equipments in service. Titanium alloy, as a highly corrosion−resistant marine structural material, plays a crucial role in the manufacturing of deep−sea engineering equipments. However, the service behavior and failure mechanism of titanium alloy in extreme deep−sea environments are still unclear, leading to a lack of scientific basis for the selection, design, and protection of titanium alloy structures in deep−sea equipment. This paper analyzes the corrosion resistance and basic corrosion electrochemical characteristics of titanium alloys, systematically reviews the problems of microbial corrosion, crevice corrosion, galvanic corrosion, hydrogen embrittlement and stress corrosion, corrosion fatigue, and multi−factor coupled corrosion damage faced by titanium alloy materials in extreme deep−sea environments, and proposes the research focus and development direction of titanium alloy corrosion in deep−sea environments.

extreme deep−sea environment  /  titanium alloy  /  engineering equipment  /  corrosion  /  failure
吴俊升, 胡科峰, 董超芳, 胡凌越, 张博威, 范林, 肖葵, 孙明先, 雍兴跃, 李晓刚. 深海极端环境下钛合金腐蚀科学问题评述. 科技导报, 2025 , 43 (17) : 77 -84 . DOI: 10.3981/j.issn.1000-7857.2024.12.01751
Junsheng WU, Kefeng HU, Chaofang DONG, Lingyue HU, Bowei ZHANG, Lin FAN, Kui XIAO, Mingxian SUN, Xingyue YONG, Xiaogang LI. Review on corrosion of titanium alloys in extreme deep−sea environments[J]. Science & Technology Review, 2025 , 43 (17) : 77 -84 . DOI: 10.3981/j.issn.1000-7857.2024.12.01751
随着科技的进步和陆地资源的日益枯竭,深海资源的开发利用已成为各国争夺的焦点,深海装备制造和深海材料研发必将成为各国研究和竞争的前沿热点。工程装备在极端苛刻的深海环境中服役,将承受低温、低溶解氧、低pH值、污染物和微生物等复杂环境因素以及热液、洋流、高压和复杂工况载荷的耦合作用。材料在深海环境下的腐蚀行为与浅层海水中表现迥异,有些规律甚至截然相反,这会对深海装备的安全服役造成严重威胁[12]。材料的腐蚀损伤已成为制约中国开发利用深海资源所需装备材料研发的关键瓶颈问题。
大量的研究表明,随着海水深度加大,金属材料总体上呈现均匀腐蚀速率降低、局部腐蚀加剧的趋势[35]。温度、溶解氧、静水压是影响深海海水腐蚀最重要的3个环境要素,也是导致深海腐蚀与浅海腐蚀行为迥异的主要影响因素。随着水深温度的降低,金属材料无论是均匀腐蚀还是局部腐蚀都呈降低趋势;溶解氧对深海腐蚀影响巨大,随着水深增加氧含量降低,促使阴极去极化反应由吸氧反应向析氢反应转变,对于碳钢等活性金属,均匀腐蚀速率大都随氧含量呈非线性正相关[6];而对于钛合金、不锈钢等钝性金属尚有分歧,通常都认为阴极析氢降低了钝化膜的稳定性,导致腐蚀电位、点蚀电位负移,在一定程度上促进了钝性金属的局部腐蚀[7];静水压力是深海区别于浅海最重要的特征环境因素[89],通常认为静水压力加速了金属腐蚀溶解动力学过程,促进了氯离子的吸附,改变了腐蚀产物或钝化膜的组成,并促进了氢渗透过程,提高了应力腐蚀敏感性。大量的研究和工程实践表明,深海环境下金属的均匀腐蚀有所减轻,而点蚀、缝隙腐蚀、氢脆和应力腐蚀等复杂局部腐蚀成为工程装备深海安全服役的最大威胁。
因此,传统海洋工程基于腐蚀减薄余量的寿命设计思路应用于深海环境就会存在很大的风险,尤其对于钛合金、不锈钢等钝性金属,必须系统研究包括点蚀、缝隙腐蚀、电偶腐蚀、应力腐蚀、腐蚀疲劳等局部腐蚀及耦合腐蚀问题,获取详实的深海腐蚀数据,建立可靠的腐蚀损伤预测模型,才能为工程装备选材设计及寿命评估提供方法和依据。钛合金作为一种最耐蚀的海洋结构材料,在深海工程装备制造中具有举足轻重的地位,但目前关于钛合金在深海极端环境中的腐蚀研究较少,对钛合金在深海水环境下的服役行为和失效机制认识不清,导致深海装备钛合金结构选材、设计和防护缺乏科学依据。本文主要针对钛合金材料在深海极端环境下所面临的腐蚀问题进行分析评述,并提出了深海环境下钛合金腐蚀研究重点和发展方向建议。
钛合金由于其优良的耐腐蚀性,被公认为“海洋金属”,也是理想的船舶用材料。大量的海洋工程实践和科学试验都表明,钛合金在纯净的海水中具有优良的耐蚀性,均匀腐蚀几乎不会发生,耐点蚀和缝隙腐蚀性能也十分优异。中国在南海、东海、黄海3个海域16年的实海试验表明,钛合金材料在全浸、潮差、飞溅区海水中几乎没有发生明显的腐蚀现象。在南海800~1000 m深海环境下3年的实海暴露试验也证实,钛合金在深海环境下具有优良的耐均匀腐蚀性能。
钛合金材料在海水环境中所表现出来的优良耐蚀性,主要归结于以下5个方面原因:(1) 金属钛与氧的相对反应性极快,超过了铝、镍和不锈钢,这就决定了钛合金表面很难以金属态存在于有氧环境中;(2) 钛合金在大气或水环境中都能自发形成致密氧化膜,无疏松氢氧化物层的存在,其氧化膜的屏蔽阻挡性能极好;(3) 金属钛表面形成的氧化物TiO、TiO2和Ti2O3等都非常稳定,抗氯离子侵蚀性能优异;(4) 钛表面氧化膜形成为外延生长机制,界面结合力强,体积比为1.76,为压应力状态,膜层缺陷少;(5) 钛表面氧化膜具有极好的自修复特性,在受到环境介质侵蚀或外力破坏后,会快速再钝化进入稳定状态。这些优良特性,决定了钛合金是天然的耐腐蚀金属材料。因此,通常都认为采用钛合金制造的工程装备,可以避免腐蚀问题,这就导致在海洋工程设计中很少考虑钛合金结构的腐蚀及防护问题,这种一贯的思维会带来严重的工程安全隐患,尤其对于长期在深海等极端环境中使用的装备,其服役安全问题不可忽视。
事实上,尽管钛合金材料耐蚀性优良,但在深海极端环境因素、力学载荷,以及微生物群落的耦合作用下,钛合金结构在深海环境中仍会面临性能退化及腐蚀失效等环境损伤问题。例如,北京科技大学研究发现[10],当海水pH<2时,钛合金钝化膜的稳定性大幅降低,耐蚀性显著下降;硫离子和氟离子对钛合金的稳定性有较大影响,尤其是当氟离子浓度超过0.005 mol/L,钛合金会发生严重的腐蚀问题。美国海军在太平洋700~2000 m的实海暴露试验发现,13V−11Cr−3Al高强度钛合金发生了应力腐蚀开裂,且焊缝和热影响区应力腐蚀敏感性要高于母材金属[11]。国内哈尔滨工程大学、中国科学院金属研究所和东北大学等单位研究发现,随着深海静水压力的增加,钛合金的应力腐蚀敏感性增加,TC4钛合金在20 MPa静水压力下的应力腐蚀呈氢致开裂形式,随着强度的提升,钛合金应力腐蚀敏感性呈增加趋势[12]。此外,在海洋装备工程结构中,不可避免存在电偶、缝隙、焊接等复杂结构,更加剧了钛合金局部腐蚀损伤的复杂性和破坏性。
金属钛的标准电极电位为−1.63 V(vs SHE),从理论上来说钛属于电化学活性极高的金属。但由于其易钝化的特性,使得其在实际环境中的电化学反应并不容易进行。在实际表层海水中监测到钛合金的腐蚀电位在−200~+200 mV(vs Ag/AgCl),比大部分金属材料的腐蚀电位都要正很多。这也是在海水中钛合金不易发生腐蚀的主要电化学热力学依据。通过电化学极化曲线测试,也能够从动力学上证明钛合金在海水中具有极低的维钝电流密度和很宽的钝化电位区。钛合金的基本电化学热力学和动力学特征都可以证明其在海水环境中具有优良的电化学稳定性。
但在深海环境中,低溶氧浓度、低pH值、污染物和高静水压力等极端环境因素对钛合金的电化学活性有较大的影响。主要表现在:(1) 深海水中溶解氧含量的降低,不利于钛合金钝化膜的形成,尤其是对于外力损伤破坏造成的钝化膜缺陷,在低氧海水中的修复速率会大大降低,进而影响钛合金钝化膜的完整性和稳定性;(2) 局部闭塞环境或其他原因导致海水pH<2的极端情况,钛合金的阳极溶解电流急剧增加,钛合金钝化膜的稳定性大幅降低;(3) 深海环境因海底喷发和环境污染存在的硫离子和氟离子对钛合金的稳定性有较大影响,尤其是氟离子对钛合金阳极电化学过程影响显著,极大地降低了点蚀电位,增大阳极维钝电流密度,促进钝化膜的溶解;(4) 深海高静水压力会提高氯离子的活性,促进其渗入金属表面钝化膜,造成钝化膜的破坏进而诱发点蚀[13];(5) 高静水压力会影响金属电极过程动力学,Liu等[8]认为静水压力可以减小双电层中外Helmholtz层到金属电极表面的距离,通过压缩双电层来实现对金属阳极电极反应的促进作用。对于钛合金来讲,在钝化膜生长的过程中双电层只存在于钝化膜/溶液和金属基体/溶液界面,因此静水压力同时促进了钛合金溶解和钝化膜的溶解过程,致使钝化膜一直处于“钝化膜破裂−再钝化”的状态,是静水压力下钝化膜耐蚀性变差的主要原因。
因此,尽管钛合金在海水中呈现了优良的电化学稳定性和耐蚀性,但在深海极端环境下,尤其是在高静水压力、局部酸化、低溶氧量、污染物(硫化氢、氟离子等)等环境工况下,钛合金的电化学反应特征与浅海环境完全不同,其钝化膜的稳定性也会变差,如果再叠加材料组织结构劣化、结构载荷、特殊构型等复杂工况条件,钛合金的电化学腐蚀风险仍然存在,必须引起高度重视。
通常认为,深海环境由于无光、低氧、高压、寡营养等特征,导致随着海水深度的增加海洋宏观生物和微生物群落数量急剧减少,因而目前关于深海生物污损腐蚀方面的研究几乎空白。根据中国船舶集团有限公司第七二五研究所(七二五所)和北京科技大学等单位在中国南海开展的不同深度海水实海试验结果来看,确实在水深超过800 m后,几乎没有大型宏观海生物的附着,也未发现明显的生物污损腐蚀迹象。那么在深海环境中,海洋微生物是否会对金属材料的腐蚀产生影响呢?随着海洋生物学的发展,科学家逐渐发现深海是最大的微生物生态系统,具有丰富的生物多样性,尽管深海微生物种群跟表层海水相比有明显的差异,但大量的研究报道都表明,包括硫酸盐还原菌(SRB)、硝酸盐还原菌(NRB)等与腐蚀相关的微生物种群广泛存在于深海海水和沉积物中[1415]。事实上,在深海少氧环境下,更有利于硫酸盐还原菌等厌氧菌的生存和生长,其对金属腐蚀的影响不可忽视,尤其在深海高压、低氧、低温、低pH等特殊环境下,SRB等典型蚀损微生物在金属表面的分布及其对钛合金等钝性金属局部腐蚀损伤影响是深海腐蚀研究的重要前沿科学问题。
关于深海极端环境中微生物对钛合金的腐蚀影响报道很少,但从钛合金本身所具有的生物相容性特点来看,在深海中广泛存在的SRB、NRB等菌种会优先附着在钛合金表面。深海微生物的附着,是否会导致钛合金发生腐蚀失效无法预知。但微生物的大量附着,其生命活动过程对钛合金表面氧化膜结构、局部腐蚀微环境等的影响是可以肯定的,另外,SRB等微生物的生物代谢过程产生硫化氢等,会引起局部环境酸化,促进阴极析氢,这同样对钛合金的氢脆和应力腐蚀具有促进作用。同时,由于深海装备在服役过程中会频繁上浮下潜,浅海区的污损生物附着十分普遍,在浅海和深海交替服役环境下微生物的附着状态和生命活动过程将更加复杂多变,其对钛合金腐蚀的影响也十分复杂。
金属的缝隙腐蚀是海洋工程实践中导致突发性事故主要的局部腐蚀破坏形式之一,其腐蚀过程具有影响因素复杂、隐蔽性强、监测困难等特点,一直是海洋腐蚀研究的难点。在深海装备工程结构中,金属连接、密封、紧固等结构件总是不可避免地存在缝隙结构,缝隙腐蚀几乎无法避免,尤其是钛合金等钝性金属,尽管具有较好的耐海水氯离子点蚀性能,但由于闭塞区的存在,缝隙腐蚀比点蚀更容易发生。
试验研究表明,钛合金在常温海水中通常都表现出了良好的耐缝隙腐蚀性能[16],但在高温、酸性缝隙环境下,钛合金也会发生严重的缝隙腐蚀[17]。目前关于深海环境中钛合金结构是否会发生缝隙腐蚀,缺乏理论和试验依据。如果按照Pickering[18]提出的基于缝隙闭塞区欧姆电势差理论的临界欧姆电势差模型(IR降理论),对于深海环境,尽管低氧含量降低了缝隙腐蚀发生的原始驱动力,但在高静水压力的作用下,一方面,会增加介质渗透性,促进氯离子等侵蚀性阴离子向缝隙内部的扩散迁移速率,这会导致缝隙内电流密度增大进而增加IR降,使得缝隙内金属进入活化溶解电位区;另一方面,高静水压力会导致金属腐蚀产物更加致密化并多以氧化物存在,这也会造成缝隙口和缝隙内部腐蚀产物电阻增加,进而增大IR降。此外,静水压力会抑制缝隙内氢气等气体的析出逃逸,缝隙内气泡的聚集也是产生IR降的原因之一。试验研究方面,七二五所等单位通过在南海深海中的腐蚀暴露试验发现,包括316L不锈钢、N6和Monel400等镍基合金在深海环境中都发生了严重的缝隙腐蚀,微观分析表明缝隙腐蚀导致的局部腐蚀损伤远比点蚀严重,且不锈钢在深海中的缝隙腐蚀程度明显高于浅海环境。这些初步的实海腐蚀试验现象表明,深海中钝性金属发生缝隙腐蚀的概率要高于浅海环境,应该引起足够的重视。
对于钛合金等钝性金属而言,钝化膜的完整性和稳定性是决定其耐蚀性的前提,在深海环境中,工程结构往往存在包括异种金属接触的缝隙结构,由于电偶腐蚀等原因导致闭塞微环境的酸化问题,常常会出现pH值低于2的极端情况,容易诱发钛合金缝隙腐蚀;另外,深海工程缝隙连接结构,在静水压力和交变载荷的作用下,往往还会叠加微动磨损问题,磨损使钛合金表面钝化膜破坏,不断裸露出新鲜的金属表面,缝隙接触面钛合金表面呈现活化状态,这种情况可能会诱发严重的缝隙局部腐蚀问题。
钝性金属钛合金在海水中的开路电位在−200~+200 mV(vs Ag/AgCl)之间,比大部分金属材料的开路电位都要正。因此,在海洋工程结构中,绝大部分金属材料与钛合金偶接后,其他金属充当阳极,腐蚀加剧,而钛合金一般都为阴极,腐蚀受到抑制。从理论上讲,海洋工程钛合金结构设计中,不太需要考虑钛合金自身的电偶腐蚀问题。
在深海环境中,尽管钛合金电偶腐蚀一般不会发生,但其与其他电位更负的活泼金属偶接后,会产生其他方面的问题:其一,当钛合金与其他活泼金属偶接形成缝隙结构时,由于钛合金与其他金属之间的电位差较大,负电位金属发生电偶加速腐蚀,导致在缝隙闭塞环境内部溶液介质的自催化酸化加剧,钛合金表面由于充当阴极析氢,有可能会使钛合金表面钝化膜溶解破坏,进而引起氢脆等问题;其二,当钛合金与其他金属偶接后,无论是否形成缝隙结构,都可能会引起钛合金的阴极析氢问题。有研究[1920]表明,在电偶作用下,充当阴极的钛合金表面存在氢吸附行为,其钝化膜内的二氧化钛逐渐向低价态的钛氧化物和钛的氢化物转变,导致钛钝化膜缺陷密度增加,钝化膜稳定性降低,而阴极析氢同样会引起氢脆等问题。
因此,在深海环境中,钛合金的电偶腐蚀问题并不是要单纯关注钛合金本身的电偶腐蚀,而更多的是需要考虑与其偶接的负电位金属由于电偶效应,导致缝隙微环境酸化、促进钛合金阴极析氢,进而引起氢脆和应力腐蚀等问题,这对深海装备钛合金结构的腐蚀损伤尤为重要。
氢脆和应力腐蚀是海洋工程装备用钛合金面临的主要威胁之一,据统计,钛合金结构有40%以上的事故与锻造、加工、焊接、热处理等过程中引入的残余应力所造成的应力腐蚀开裂有关,大量的试验研究都证明了钛合金尤其是高强度钛合金在海水环境中具有应力腐蚀敏感性。
深海环境的高静水压和低氧浓度,使得大部分金属材料都呈现了比表层海水环境更高的应力腐蚀敏感性。美国海军在太平洋700~2000 m的实海暴露试验发现,13V−11Cr−3Al高强度钛合金发生了应力腐蚀开裂,且焊缝和热影响区应力腐蚀敏感性要高于母材金属。Liu等[21]通过模拟深海试验发现Ti−6Al−4V钛合金在20 MPa静水压力下浸泡300 d后,U型弯试样顶端发现了宏观应力腐蚀裂纹,研究认为静水压力促进了钛合金钝化膜的活化溶解,导致表面微环境酸化,进而促进了氢的吸附和渗透,从而促进钛合金的应力腐蚀,在压力下,氢气进入钛中,然后通过加速位错运动促进裂纹形核和扩展。杨小佳等[22]在实验室模拟深海环境中研究发现,硫化物的加入会降低TA2钛合金钝化膜稳定性,并对阴极析氢反应有较明显的促进作用,进而促进了钛合金在深海环境中的应力腐蚀敏感性。越来越多的室内模拟试验结果证实钛合金在深海环境下会发生应力腐蚀开裂,是深海极端环境下钛合金结构腐蚀损伤失效的主要形式。
高强金属材料的应力腐蚀开裂机理包括阳极溶解机制、氢致开裂机制及其混合机制。但对于钛合金材料来说,发生应力腐蚀的理论依据仍然存在较大的争议,尤其在深海环境中,钛合金环境是否会发生应力腐蚀以及应力腐蚀发生的机理还很不清晰。一方面,对于阳极溶解机制来说,钛合金优良的钝化特性使其无论是按照膜破裂机制还是点蚀形核机制,其发生阳极溶解型应力腐蚀的电化学条件并不充分。大量的实验研究发现,采用标准光滑钛合金试样在海水环境下应力腐蚀敏感性并不高。但对于深海环境,如前所述,高静水压力、低氧含量、局部环境酸化、污染物因素都会造成钛合金钝化膜活化甚至破坏,因此,在深海极端环境条件下,具备钛合金发生阳极溶解型应力腐蚀的电化学条件。另一方面,假设钛合金在深海环境中可以保持良好的钝化状态,即不会发生钛合金腐蚀所导致的阴极析氢过程,是否意味着就不具备发生氢脆的条件呢?在这种情况下,氢从何而来,这也是很多人认为钛合金在深海中不会发生氢脆的主要依据。事实上,深海中钛合金发生氢脆的氢来源存在多种可能途径:(1) 在复杂应力载荷作用下钛合金发生局部塑性变形,导致局部钝化膜破裂,暴露的新鲜金属会瞬间溶解,然后再次钝化,在应力作用下钝化膜再次破裂,该过程往复发生会不断产生析氢反应,最终导致应力腐蚀裂纹的形核或者扩展;(2) 如存在缝隙结构,缝隙闭塞微环境的自催化酸化效应,会导致缝隙内部钛合金钝化膜破坏并发生析氢反应;(3) 异种金属偶接情况下,负电位金属电偶加速腐蚀导致的钛合金阴极析氢过程加剧;(4) 焊缝、加工残余应力等形成的微裂纹,在裂纹尖端可以形成低pH(< 2)微环境,具备了析氢反应的条件;(5) 深海中微生物的代谢活动,尤其是SRB的代谢产物中会产生浓度较大的H2S、HS和S2−等,它们既促进H的生成,降低H的复合速率,又促进H渗透扩散至高应力区,诱发裂纹萌生,加速裂纹扩展;(6) 在深海工程装备中,如采用阴极保护措施不当,也会导致钛合金发生析氢反应,造成钛合金的氢损伤问题;(7) 当然,钛合金材料在制造和加工过程中也会有氢的吸附、扩散和滞留氢陷阱导致的氢脆问题。
因此,无论是从已有的为数不多的试验研究报道,还是理论分析,都表明在深海极端环境下钛合金结构发生阳极溶解应力腐蚀的电化学条件以及氢脆发生的条件都有依据。从已公开的几起深海装备应力腐蚀开裂事故也可以证明,氢脆和应力腐蚀是钛合金在深海中所面对的最主要的风险之一,深入全面了解钛合金在深海极端环境中的应力腐蚀机理以及影响应力腐蚀主要因素,对钛合金在深海中全面应用和长期安全服役有着重要的意义。
钛合金的疲劳损伤失效在航空领域获得广泛关注,通常都认为钛合金优良的耐蚀性使其对腐蚀环境敏感性较低,一些研究结果表明,钛合金在海水和空气中的疲劳极限差别很小。赵晴[23]研究结果表明,腐蚀环境对 TC4−DT 光滑试件的高周腐蚀疲劳寿命影响较小,在3.5% NaCl 溶液腐蚀介质中,TC4−DT的高周疲劳寿命只比空气环境下降低了5%左右。钛合金具有较大的缺口敏感性,因此腐蚀环境对TC4−DT缺口试件的疲劳寿命影响更小。通常认为,钛合金在高循环载荷作用下受到的疲劳损伤,以及在低循环载荷作用下受到的腐蚀损伤是关键因素[24]。一些研究结果也证明,在高应力水平下腐蚀介质对疲劳寿命影响不大,而低应力水平下腐蚀疲劳寿命则大大低于单纯的疲劳寿命。
现有文献中对钛合金在海水环境中的腐蚀疲劳研究很少,而深海环境中钛合金的腐蚀疲劳的研究几乎处于空白。赵宇翔[25]对深海用TC4ELI钛合金的腐蚀−疲劳裂纹扩展行为进行了加速试验研究,发现TC4ELI钛合金在腐蚀−疲劳裂纹扩展中会出现先减速后加速的特殊现象,研究认为是腐蚀导致的裂尖钝化与材料性能降低之间的竞争作用,初步揭示了在海水环境中高强度钛合金具有腐蚀疲劳敏感性,但该研究并未关注深海高静水压力这一关键的极端环境条件。
由于深海装备在服役期间经常性地上浮和下潜,钛合金耐压壳结构需承受深海超高静水压力的交变循环作用,在高应力水平作用下局部区域接近屈服极限,应力集中位置易产生明显的塑性损伤,因此深海装备钛合金耐压壳结构的疲劳问题为典型的低周疲劳范畴[26]。同时由于耐压壳体是复杂焊接结构,受焊接工艺条件的影响,不可避免地存在焊接缺陷以及焊接残余应力等,这些部位由于应力集中容易萌生疲劳裂纹,在循环载荷作用下裂纹发生扩展进而引起结构破坏,因此耐压壳结构的低周疲劳问题不容忽视。
如前所述,深海装备服役过程中,除了承受上浮下潜的交变应力载荷,还面临着高静水压力、低氧含量、局部环境酸化以及污染物和微生物等极端环境的影响,钛合金结构在深海环境中是否会发生腐蚀促进低周疲劳损伤问题,目前还没有定论。但从钛合金低周疲劳和深海环境基本特征推测,这种可能性是存在的:首先,钛合金结构在服役时需承受高应力水平作用,某些局部应力集中区域,会出现超过特定微观范围的高塑性应变,使得钝化膜发生破裂,裸露的金属表面会发生快速腐蚀溶解,并导致阴极析氢,这会加速钛合金结构疲劳破坏过程,进而缩短疲劳寿命;其次,深海高静水压力和低氧浓度,都会促进钝化膜的失稳破坏,并抑制塑性变形和疲劳裂纹的自修复再钝化过程,进而促进疲劳裂纹的萌生和扩展;最后,深海中微生物作用、电偶腐蚀、缝隙腐蚀等都会导致钛合金结构局部微环境的酸化析氢等问题,加速金属阳极溶解和氢吸附和渗透过程,这也会促进腐蚀疲劳的发生。因此,深海高静水压力作用下的钛合金低周腐蚀疲劳也是深海装备服役安全必须要关注的科学问题。
钛合金材料本身所表现出的优良耐蚀性能,使得人们普遍认为采用钛合金制造海洋工程装备可以避免腐蚀失效问题。因此,相对于其他海洋工程材料,钛合金的海洋腐蚀研究较少,尤其是在深海环境中,目前开展的研究还很不系统。从已有的报道来看,在极端深海环境下,钛合金无论是电化学特征、微生物腐蚀,还是电偶腐蚀、缝隙腐蚀、应力腐蚀、腐蚀疲劳等都与浅海环境有较大差异,总体上都比浅海环境有所加剧。尽管已经开展并获得了一些进展,但目前对钛合金结构在深海环境中的腐蚀损伤行为还缺乏认识,尤其是实验室标准材料试验所得出的评价和预测结果,往往跟工程实际中钛合金结构在深海工况下发生的多起腐蚀损伤失效安全事故情况严重背离。其中重要的原因就是实际工程装备钛合金结构所处工况条件非常复杂,往往是极端环境因素、材料因素、载荷因素、复杂结构等多因素耦合构成的复杂体系,伴随着电化学−微生物−应力载荷−缝隙−电偶等耦合腐蚀作用,极大地提高了深海装备钛合金结构的腐蚀损伤风险,也给钛合金结构深海腐蚀研究带来了极大的挑战。
实验室的深海腐蚀研究,往往都是针对单一的腐蚀过程或形式进行,所获得的结果很难获得对实际深海工程结构腐蚀损伤预测评估的有效支撑。例如,深海中服役的工程装备除了受到高静水压力的作用外,由于结构载荷、海流作用、残余应力等普遍存在局部拉应力,尤其是深海装备中广泛采用的管道接头、紧固件、法兰等受力连接件和密封结构,极易引发应力−缝隙的耦合腐蚀,以及异种金属接触而导致的电偶−缝隙−应力耦合腐蚀,在上浮下潜过程中,还会出现多种腐蚀形式与疲劳损伤的耦合问题。关于多因素、多形式的耦合腐蚀问题,已经逐渐成为了腐蚀领域的研究热点。例如,Li等[27]和Zhu等[28]研究发现拉应力能够大幅降低304、13Cr不锈钢的临界缝隙腐蚀电位,尤其是施加较大的塑性应力可以促进缝隙内部亚稳态点蚀向稳态点蚀的转变,极大地提高了不锈钢缝隙腐蚀敏感性;另一方面,当存在缝隙时,N80钢的屈服强度、拉伸强度、断裂伸长率均降低,应力腐蚀敏感性显著增加[29],揭示了应力和缝隙对金属的腐蚀具有协同促进效应。钟显康等[30]研究表明,应力的施加会加剧N80钢的缝隙腐蚀,使缝隙口处蚀坑加深,这反过来又会导致应力的进一步集中,增加应力腐蚀敏感性,证明了缝隙和应力对腐蚀具有协同作用。实验研究和工程实践都表明,在深海复杂环境下同时存在缝隙和应力的情况下,应力与缝隙的耦合协同腐蚀损伤是深海装备服役安全的最大隐患,必须给予重视。
因此,在深海极端环境中,深海装备钛合金结构的耦合腐蚀损伤是深海装备安全服役中最值得关注的关键科学问题。必须充分考虑深海复杂环境因素、微生物因素、力学载荷、偶接结构等复杂系统问题,重点关注包括电偶−缝隙耦合腐蚀、缝隙−微动磨损腐蚀、缝隙−应力腐蚀、电偶−应力腐蚀、电偶−缝隙−应力腐蚀、电偶−缝隙−疲劳耦合腐蚀、微生物−缝隙−应力腐蚀、微生物−缝隙−疲劳等多种可能的耦合腐蚀损伤情况,方可能得出更符合深海海洋工程实际钛合金结构腐蚀损伤行为和机理的科学结论,进而为深海装备的设计制造和安全服役评估提供可靠的理论支撑。
相对于大气和浅海水等常规腐蚀环境,钛合金在深海环境中的腐蚀研究还很不系统,基于传统对“海洋金属”钛合金耐蚀性的固有认识,导致深海工程装备尤其是复杂钛合金结构的设计和选用存在很高的风险,需要系统开展深海极端环境钛合金材料及结构的腐蚀损伤研究。
1) 实海试验是评价材料在深海环境中腐蚀行为和规律的最直接有效的方法。但由于深海试验难度极大,试验周期很长,钛合金的深海腐蚀数据非常缺乏,需要通过长期的深海实海试验和工程实践,系统收集获取钛合金材料尤其是典型钛合金结构在深海极端环境下的腐蚀数据,研究钛合金及结构在复杂深海环境中的基本腐蚀行为与规律。
2) 基于实际服役深海环境因素及实海试验结果,研究发展室内加速模拟深海腐蚀评价技术尤为重要,通过对静水压力、温度、溶解氧、污染物等深海环境特征因素的有效模拟调控,结合电化学测试等技术手段,可原位监测研究深海腐蚀的电化学过程和机理,通过力学载荷的原位加载来研究应力腐蚀和腐蚀疲劳,系统阐明深海极端环境中钛合金的腐蚀损伤规律和机理。
3) 对于深海环境下的钛合金材料腐蚀研究,无论是实海试验还是室内模拟试验研究,开展起来都十分困难,而且由于深海高静水压极端环境特征,可用于深海研究的实验方法和原位监测技术手段都十分有限,很难在有限时间内获得详实全面的科学实验结果和有效数据。因此,迫切需要将基于材料基因工程理念的腐蚀计算模拟研究手段引入深海腐蚀研究中来,通过将跨尺度腐蚀计算与室内模拟试验验证相结合,可以使钛合金的深海腐蚀研究更加高效,且能从理论和实验2个层面更加深入地认识和了解深海环境下钛合金结构的腐蚀损伤行为和机理。
4) 结合深海装备工程实践和服役环境特征,需要重点关注深海极端环境因素、微生物因素、材料及工艺因素、载荷因素等多因素耦合集成构成的复杂体系,系统研究深海环境下钛合金材料的电化学−微生物−应力载荷−微动磨损−缝隙−电偶等耦合腐蚀行为与机理,阐明深海极端环境下钛合金复杂结构的腐蚀电化学特征,缝隙腐蚀、电偶腐蚀、氢脆及应力腐蚀、腐蚀疲劳及其多因素耦合等腐蚀损伤失效特征与规律,为深海装备的安全服役与寿命评估提供理论基础。
  • 国家自然科学基金项目(52371051,51931008)
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2025年第43卷第17期
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doi: 10.3981/j.issn.1000-7857.2024.12.01751
  • 接收时间:2024-12-16
  • 首发时间:2025-12-18
  • 出版时间:2025-09-13
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  • 收稿日期:2024-12-16
  • 修回日期:2025-06-05
  • 录用日期:2025-08-29
基金
国家自然科学基金项目(52371051,51931008)
作者信息
    1. 北京科技大学新材料技术研究院,北京 100083
    2. 武汉第二船舶设计研究所,武汉 430064
    3. 中国船舶集团有限公司第七二五研究所海洋腐蚀与防护全国重点实验室,青岛 266237
    4. 北京化工大学有机无机复合材料国家重点实验室,北京 100029
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
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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