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Article(id=1276897232712503880, tenantId=1146029695717560320, journalId=1276577071032668183, issueId=1276897056350405403, articleNumber=null, orderNo=null, doi=10.3724/j.jiwhr.20250102, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1744905600000, receivedDateStr=2025-04-18, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1782365623881, onlineDateStr=2026-06-25, pubDate=1779897600000, pubDateStr=2026-05-28, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1782365623881, onlineIssueDateStr=2026-06-25, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1782365623881, creator=13701087609, updateTime=1782365623881, updator=13701087609, issue=Issue{id=1276897056350405403, tenantId=1146029695717560320, journalId=1276577071032668183, year='2026', volume='24', issue='3', pageStart='261', pageEnd='428', issueExtLink='null', onlineDate='null', pubDate='1779897600000', pubDateStr='2026-05-28', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1782365581834, creator='13701087609', updateTime=1782367082282, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1276903349781926250, tenantId=1146029695717560320, journalId=1276577071032668183, issueId=1276897056350405403, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1276903349781926251, tenantId=1146029695717560320, journalId=1276577071032668183, issueId=1276897056350405403, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=293, endPage=305, ext={EN=ArticleExt(id=1276897232951579210, articleId=1276897232712503880, tenantId=1146029695717560320, journalId=1276577071032668183, language=EN, title=Electrochemical experimental study on corrosion protection of PCCP prestressed steel wire coating, columnId=null, journalTitle=Journal of China Institute of Water Resources and Hydropower Research, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Corrosion-induced fracture of prestressed steel wires is one of the primary failure mechanisms in PCCP， with preventive measures and effectiveness evaluation being key focuses in durability research. To investigate the corrosion damage patterns of prestressed steel wires under stress-chloride coupling environments and identify effective anti-corrosion materials meeting durability requirements， this study examined the effects of applied stress on the corrosion behavior of bare wires in NaCl solutions at concentrations of 1%， 3.5%， 10%， and 20%， as well as single-component polyurea-coated wires in 3.5% NaCl solution， through open-circuit potential measurements， corrosion current density analysis， and electrochemical impedance spectroscopy， using stress-free conditions as the control group. For bare wires， chloride concentration predominantly governed corrosion progression， exhibiting the order： 3.5% NaCl > 1% NaCl > 10% NaCl > 20% NaCl. Stress only accelerated corrosion in low-concentration solutions. Regarding coated wires， applied stress accelerated coating resistance degradation， yet their corrosion current density remained five orders of magnitude lower than bare counterparts. After 25 days immersion under sustained load， the impedance modulus maintained 2.07×107 Ω·cm²， demonstrating that single-component polyurea coating significantly enhances corrosion resistance of prestressed wires in stress-chloride coupling environments.

, authors=null, authorsList=Sen YANG, Zhiheng SUN, Meng LI, Xiaonong DONG, authorCompany=null, correspAuthors=null, 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, fund=null), CN=ArticleExt(id=1276897236709675626, articleId=1276897232712503880, tenantId=1146029695717560320, journalId=1276577071032668183, language=CN, title=PCCP预应力钢丝涂层防腐电化学试验研究, columnId=0, journalTitle=中国水利水电科学研究院学报（中英文）, columnName=, runingTitle=null, highlight=null, articleAbstract=

预应力钢丝腐蚀断裂是预应力钢筒混凝土管（PCCP）破坏的主要原因之一，其预防措施及效果评价是耐久性研究关注的重点内容。为研究预应力钢丝在应力-氯盐耦合环境下腐蚀损伤规律及寻求该环境下满足钢丝耐久性要求的防腐材料，通过自腐蚀电位、腐蚀电流密度和电化学阻抗谱分析，以无应力状态为对照组，研究了应力对1%、3.5%、10%、20%浓度NaCl溶液中裸钢丝和3.5%NaCl溶液中钢丝涂刷单组分聚脲的腐蚀行为的影响。对于裸钢丝，氯盐浓度对钢丝腐蚀起主导作用，腐蚀快慢顺序为3.5%NaCl>1%NaCl>10%NaCl>20%NaCl；应力对腐蚀的加速作用仅体现在低浓度溶液。对于涂层钢丝，施加应力会加速降低涂层电阻，但其腐蚀电流密度仍较裸钢丝低5个数量级，70%极限应力下持载浸泡25 d后，阻抗模值仍高达2.07×107 Ω·cm2，表明单组分聚脲涂层有效提升了应力-氯盐耦合环境下预应力钢丝耐腐蚀性能。

, authors=

杨森（2003—），硕士生，主要从事水工混凝土建筑物的检测、评估与修补加固技术研究。 E-mail：

, authorsList=杨森, 孙志恒, 李萌, 董晓农, authorCompany=null, correspAuthors=null, authorNote=null, correspAuthorsNote=
孙志恒（1962—）， 教授级高级工程师， 主要从事水工混凝土建筑物的检测、评估与修补加固技术研究。 E-mail：
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杨森（2003—），硕士生，主要从事水工混凝土建筑物的检测、评估与修补加固技术研究。 E-mail：

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杨森（2003—），硕士生，主要从事水工混凝土建筑物的检测、评估与修补加固技术研究。 E-mail：

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prestressed steel wires under different chloride concentrations and stress levels, figureFileSmall=IEcAvI9O5nHiaW5dDY5iPw==, figureFileBig=gwuA78t2lp5p56CRVHnq+A==, tableContent=null), ArticleFig(id=1276897242296488596, tenantId=1146029695717560320, journalId=1276577071032668183, articleId=1276897232712503880, language=CN, label=图4, caption=不同氯盐浓度与应力下预应力钢丝的自腐蚀电位, figureFileSmall=IEcAvI9O5nHiaW5dDY5iPw==, figureFileBig=gwuA78t2lp5p56CRVHnq+A==, tableContent=null), ArticleFig(id=1276897242359403157, tenantId=1146029695717560320, journalId=1276577071032668183, articleId=1276897232712503880, language=EN, label=Fig.5, caption=Corrosion current density of prestressed steel wires under different chloride concentrations and stress levels, figureFileSmall=wUZVhvPkNNX61F7NacAKvw==, figureFileBig=4GEqL93izIt/Ic+kf26FSw==, tableContent=null), ArticleFig(id=1276897242430706326, tenantId=1146029695717560320, journalId=1276577071032668183, articleId=1276897232712503880, language=CN, label=图5, 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Composition of prestressed steel wire

, figureFileSmall=null, figureFileBig=null, tableContent=
元素CSiMnPSCrNiCu
wt.%0.70~0.750.10~0.300.60~0.90≤0.025≤0.025≤0.10≤0.10≤0.20
), ArticleFig(id=1276897244020347564, tenantId=1146029695717560320, journalId=1276577071032668183, articleId=1276897232712503880, language=CN, label=表1, caption=

预应力钢丝成分

, figureFileSmall=null, figureFileBig=null, tableContent=
元素CSiMnPSCrNiCu
wt.%0.70~0.750.10~0.300.60~0.90≤0.025≤0.025≤0.10≤0.10≤0.20
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Equivalent circuit fitting results of prestressed steel wires under different concentrations of NaCl solution and stress conditions

, figureFileSmall=null, figureFileBig=null, tableContent=
试验环境Rs/（Ω·cm2）Y0×10-3/（F·cm-2）nRct/（Ω·cm2）
0%-1%59.45604.84990.72691424.7
70%-1%49.75303.81750.73691266.6
0%-3.5%21.11804.95200.75071289.3
70%-3.5%14.10403.26330.74771133.8
0%-10%9.94883.39850.73941837.9
70%-10%8.99493.55600.75481598.0
0%-20%5.71443.49280.75803582.2
70%-20%6.01312.42440.77633644.1
), ArticleFig(id=1276897244150370990, tenantId=1146029695717560320, journalId=1276577071032668183, articleId=1276897232712503880, language=CN, label=表2, caption=

预应力钢丝在不同浓度NaCl溶液与应力条件下等效电路拟合结果

, figureFileSmall=null, figureFileBig=null, tableContent=
试验环境Rs/（Ω·cm2）Y0×10-3/（F·cm-2）nRct/（Ω·cm2）
0%-1%59.45604.84990.72691424.7
70%-1%49.75303.81750.73691266.6
0%-3.5%21.11804.95200.75071289.3
70%-3.5%14.10403.26330.74771133.8
0%-10%9.94883.39850.73941837.9
70%-10%8.99493.55600.75481598.0
0%-20%5.71443.49280.75803582.2
70%-20%6.01312.42440.77633644.1
), ArticleFig(id=1276897244221674159, tenantId=1146029695717560320, journalId=1276577071032668183, articleId=1276897232712503880, language=EN, label=Table 3, caption=

Equivalent circuit fitting results of polyurea coated steel wires in 3.5% NaCl solution under unstressed conditions

, figureFileSmall=null, figureFileBig=null, tableContent=
天数/dRs/（Ω·cm2）Y0×10-10/（F·cm-2）nRc×107/（Ω·cm2）
11955.72.93730.94165.0860
32005.22.85450.94613.3989
63257.52.57430.94923.9769
152973.22.17330.97284.4210
252598.42.54740.95553.9701
), ArticleFig(id=1276897244301365936, tenantId=1146029695717560320, journalId=1276577071032668183, articleId=1276897232712503880, language=CN, label=表3, caption=

涂刷聚脲的钢丝在3.5%NaCl溶液、无应力条件下等效电路拟合结果

, figureFileSmall=null, figureFileBig=null, tableContent=
天数/dRs/（Ω·cm2）Y0×10-10/（F·cm-2）nRc×107/（Ω·cm2）
11955.72.93730.94165.0860
32005.22.85450.94613.3989
63257.52.57430.94923.9769
152973.22.17330.97284.4210
252598.42.54740.95553.9701
), ArticleFig(id=1276897244368474801, tenantId=1146029695717560320, journalId=1276577071032668183, articleId=1276897232712503880, language=EN, label=Table 4, caption=

Equivalent circuit fitting results of polyurea coated steel wires in 3.5% NaCl solution with 70% ultimate stress conditions

, figureFileSmall=null, figureFileBig=null, tableContent=
天数/dRs/（Ω·cm2）Y0×10-10/（F·cm-2）nRc×107/（Ω·cm2）
11867.73.00920.94565.2064
32341.62.57310.94871.8673
62812.42.29850.94691.9234
153449.92.05430.96672.6575
252802.62.36990.95562.2801
), ArticleFig(id=1276897244439777970, tenantId=1146029695717560320, journalId=1276577071032668183, articleId=1276897232712503880, language=CN, label=表4, caption=

涂刷聚脲的钢丝在3.5%NaCl溶液、70%极限应力条件下等效电路拟合结果

, figureFileSmall=null, figureFileBig=null, tableContent=
天数/dRs/（Ω·cm2）Y0×10-10/（F·cm-2）nRc×107/（Ω·cm2）
11867.73.00920.94565.2064
32341.62.57310.94871.8673
62812.42.29850.94691.9234
153449.92.05430.96672.6575
252802.62.36990.95562.2801
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PCCP预应力钢丝涂层防腐电化学试验研究
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杨森 , 孙志恒 , 李萌 , 董晓农
中国水利水电科学研究院学报（中英文） | 2026,24(3): 293-305
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中国水利水电科学研究院学报（中英文） | 2026 , 24 (3) : 293 -305
PCCP预应力钢丝涂层防腐电化学试验研究
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杨森 , 孙志恒 , 李萌, 董晓农
作者信息
  • 流域水循环与水安全全国重点实验室 中国水利水电科学研究院，北京 100038
通讯作者:
孙志恒（1962—）， 教授级高级工程师， 主要从事水工混凝土建筑物的检测、评估与修补加固技术研究。 E-mail：
Electrochemical experimental study on corrosion protection of PCCP prestressed steel wire coating
Sen YANG , Zhiheng SUN , Meng LI, Xiaonong DONG
Affiliations
  • State Key Laboratory of Water Cycle and Water Security， China Institute of Water Resources and Hydropower Research， Beijing100038， China
出版时间: 2026-05-28 doi: 10.3724/j.jiwhr.20250102
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摘要
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预应力钢丝腐蚀断裂是预应力钢筒混凝土管（PCCP）破坏的主要原因之一，其预防措施及效果评价是耐久性研究关注的重点内容。为研究预应力钢丝在应力-氯盐耦合环境下腐蚀损伤规律及寻求该环境下满足钢丝耐久性要求的防腐材料，通过自腐蚀电位、腐蚀电流密度和电化学阻抗谱分析，以无应力状态为对照组，研究了应力对1%、3.5%、10%、20%浓度NaCl溶液中裸钢丝和3.5%NaCl溶液中钢丝涂刷单组分聚脲的腐蚀行为的影响。对于裸钢丝，氯盐浓度对钢丝腐蚀起主导作用，腐蚀快慢顺序为3.5%NaCl>1%NaCl>10%NaCl>20%NaCl；应力对腐蚀的加速作用仅体现在低浓度溶液。对于涂层钢丝，施加应力会加速降低涂层电阻，但其腐蚀电流密度仍较裸钢丝低5个数量级，70%极限应力下持载浸泡25 d后，阻抗模值仍高达2.07×107 Ω·cm2，表明单组分聚脲涂层有效提升了应力-氯盐耦合环境下预应力钢丝耐腐蚀性能。

PCCP  /  预应力钢丝  /  聚脲涂层  /  耐久性  /  电化学

Corrosion-induced fracture of prestressed steel wires is one of the primary failure mechanisms in PCCP， with preventive measures and effectiveness evaluation being key focuses in durability research. To investigate the corrosion damage patterns of prestressed steel wires under stress-chloride coupling environments and identify effective anti-corrosion materials meeting durability requirements， this study examined the effects of applied stress on the corrosion behavior of bare wires in NaCl solutions at concentrations of 1%， 3.5%， 10%， and 20%， as well as single-component polyurea-coated wires in 3.5% NaCl solution， through open-circuit potential measurements， corrosion current density analysis， and electrochemical impedance spectroscopy， using stress-free conditions as the control group. For bare wires， chloride concentration predominantly governed corrosion progression， exhibiting the order： 3.5% NaCl > 1% NaCl > 10% NaCl > 20% NaCl. Stress only accelerated corrosion in low-concentration solutions. Regarding coated wires， applied stress accelerated coating resistance degradation， yet their corrosion current density remained five orders of magnitude lower than bare counterparts. After 25 days immersion under sustained load， the impedance modulus maintained 2.07×107 Ω·cm²， demonstrating that single-component polyurea coating significantly enhances corrosion resistance of prestressed wires in stress-chloride coupling environments.

PCCP  /  prestressed steel wire  /  polyurea coating  /  durability  /  electrochemistry
杨森, 孙志恒, 李萌, 董晓农. PCCP预应力钢丝涂层防腐电化学试验研究. 中国水利水电科学研究院学报（中英文）, 2026 , 24 (3) : 293 -305 . DOI: 10.3724/j.jiwhr.20250102
Sen YANG, Zhiheng SUN, Meng LI, Xiaonong DONG. Electrochemical experimental study on corrosion protection of PCCP prestressed steel wire coating[J]. Journal of China Institute of Water Resources and Hydropower Research, 2026 , 24 (3) : 293 -305 . DOI: 10.3724/j.jiwhr.20250102
正文
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1　研究背景
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预应力钢筒混凝土管（Prestressed Concrete Cylinder Pipe，PCCP）是在带钢筒的管芯混凝土上螺旋缠绕预应力钢丝，并喷涂砂浆保护层和环氧煤沥青防腐涂层而制成的复合管材［1-2］，如图1所示。预应力钢筒混凝土管凭借其高工压承载能力和优异的抗渗性能［3］，广泛应用于各大输水工程［4-5］。伴随30多年的发展，我国PCCP存量规模显著增长［6］。在国家水网建设重大战略推进的背景下［7］，PCCP长期服役性能与复杂环境适应性问题日益受到学界关注。
预应力钢丝是PCCP结构和耐久性能的核心［8-9］，因此其断裂预防方法是研究重点内容。现有预防方法包括保护层外防腐涂层、砂浆/混凝土保护层和阴极保护。保护层外防腐涂层为PCCP提供致密屏障，阻止氯离子、氧气和水等有害介质侵入保护层；砂浆/混凝土保护层为钢丝提供碱性环境和握裹力，使钢丝处于钝化状态［10］，并阻止断丝大范围损失预应力；当有害介质侵蚀钢丝时，阴极保护为钢丝补充电子［11］，进一步延缓断丝。当前，大规模应用的环氧煤沥青涂层施工过程中易破损，在特定环境下易脆裂；砂浆保护层吸水率较高［3］，而混凝土保护层厚度较大（管重增加）；阴极保护运行维护难。
为此，本文考虑钢丝受载状态和侵蚀介质，探究荷载和氯盐浓度对钢丝腐蚀的影响；围绕预应力钢丝防腐问题，提出钢丝涂层电化学试验方法，探究涂层对氯离子的阻隔性能。本研究聚焦于钢丝腐蚀机理和涂层氯离子阻隔性能研究，可为钢丝表面直接涂敷涂层提供先导性探索，也可为保护层表面涂层抗侵蚀性能提供参考。
2　试验方法
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2.1　原材料
本试验采用的PCCP预应力钢丝化学组成如表1所示。
钢丝直径为6 mm，将钢丝切割成长度为230 mm的短钢丝段，用于制作涂层钢丝。首先使用200#、400#和800#砂纸逐级打磨钢丝至光亮状态，去除表面铁锈和氧化层，然后用酒精清洗表面油污，随后用去离子水冲洗干净，吹风机吹干备用，最后刷涂柔性涂层，涂层采用SK单组分聚脲，涂层厚度0.2 mm。
2.2　试验装置
PCCP预应力钢丝实际运行时的应力状态为极限应力状态（1570 MPa）的70%（1100 MPa），试件制作完毕后静置固化7 d，之后装配到钢丝拉伸装置上持载。水箱内径宽55 mm，工作电极面积为10.36 cm2，如图2—3所示。
2.3　试验环境
将试件分别置于1%、3.5%、10%、20%NaCl溶液、（23±2） ℃的环境中进行浸泡，以无应力钢丝为对照组，施加70%极限应力的钢丝为试验组，在1、3、6、15、25 d进行电化学测试，后续图中标记（70%-1%）为70%极限应力与1%NaCl溶液耦合环境，以此类推。
2.4　电化学测试
在本研究中，所采用的电化学工作站型号为CS310M，为武汉科思特仪器股份有限公司生产。电化学试验采用标准的三电极系统，包括以预应力钢丝作为工作电极，饱和甘汞电极（Saturated Calomel Electrode，SCE）作为参比电极，以及不锈钢片作为对电极。
在线性极化法（Linear Polarization Resistance，LPR）测试中，线性极化测试扫描电位为±0.01 V vs. OCP，扫描速率10 mV/min。在电化学阻抗谱（Electrochemical Impedance Spectroscopy，EIS）测试中，裸钢丝交流阻抗测试扰动电压为幅度10 mV的正弦电压信号，涂层钢丝交流阻抗测试扰动电压为幅度20 mV的正弦电压信号，扫描频率为10 mHz~100 kHz。
3　涂层防腐效果分析
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3.1　应力对自腐蚀电位Ecorr和腐蚀电流密度Icorr的影响
为明确应力对钢丝腐蚀行为的影响，通过分析不同持载状态下Ecorr和Icorr的演变特征，揭示应力对钢丝的腐蚀热力学与动力学参数的作用规律。
图4为不同氯盐浓度与应力下预应力钢丝的自腐蚀电位Ecorr，它反映了试件在溶液中发生腐蚀的难易程度。Ecorr越偏向负值，表明金属在环境中热力学稳定性越低，腐蚀倾向越大［12］。根据图4显示，随着浸泡时间的延续，所有裸钢丝自腐蚀电位均发生负移。不同氯盐浓度下的裸钢丝自腐蚀电位对应力的敏感性不同，在1%、3.5%、10%浓度的NaCl溶液中，与无载钢丝相比，持载钢丝自腐蚀电位都有不同程度的负移。在持载条件下第3 d的测试中负移现象最明显，1%、3.5%、10%浓度NaCl溶液中Ecorr分别负移了49.18、31.04、30.52 mV；在20%浓度的NaCl溶液中，与无载钢丝相比，持载钢丝自腐蚀电位变化并不显著。之后随着腐蚀产物逐渐积累在钢丝表面，裸钢丝Ecorr在浸泡25 d后稳定在-0.70~-0.68 V。由于力学因素的影响，预应力钢丝表面活性增强且腐蚀反应所需的活化能量减少，进而电化学-力学活性增强［13］。测量结果表明：应力对1%、3.5%、10%浓度的NaCl溶液中预应力钢丝具有腐蚀加剧的趋势。
尽管Ecorr演变能一定程度上反映钢丝的腐蚀倾向，但它不能直接指示腐蚀动力学，需要进一步检查极化行为［14］。图5—6为不同氯盐浓度与应力下预应力钢丝的腐蚀电流密度Icorr与极化电阻Rp。腐蚀电流密度Icorr与极化电阻Rp是反映金属腐蚀速率的动力学特征［15］，Icorr值越大，其腐蚀速率越快。Rp越大，腐蚀反应的阻力越大，腐蚀速率越慢。根据线性极化法（LPR）测试结果获得极化电阻Rp，可以通过Stern-Geary公式获得该状态下预应力钢丝的腐蚀电流密度Icorr：
Icorr=βaβc2.303(βa+βc)Rp=BRp
式中：Icorr为腐蚀电流密度；βa和βc分别为阳极极化曲线斜率和阴极极化曲线斜率；Rp为极化电阻；B为Stern-Geary常数，当其处于腐蚀状态时，取B=26 mV［16］。
根据图5显示，不同氯盐浓度下的裸钢丝腐蚀电流密度对应力的敏感性不同。在第3d的测试中，3.5%NaCl溶液与应力耦合条件下裸钢丝腐蚀电流密度最高，达到了25.48 μA/cm2，较无应力条件下提高了约10.54%；1%和10%浓度的NaCl溶液与应力耦合条件下裸钢丝腐蚀电流密度分别为22.57 μA/cm2和17.95 μA/cm2，较无应力条件下分别提高了约9.57%和19.19%，这是因为在应力作用下预应力钢丝表面产生微裂纹，溶液中的Cl-在微裂纹处吸附并加速腐蚀，形成腐蚀小孔［17］。而应力状态下20%NaCl溶液中的裸钢丝腐蚀电流密度变化并不显著，表明应力对腐蚀的加速作用仅体现在低浓度溶液。从图5中还可以看出，腐蚀电流密度并非与氯盐浓度成线性正相关，不同浓度NaCl溶液下的腐蚀快慢顺序为：3.5%NaCl>1%NaCl>10%NaCl>20%NaCl，应力状态下3.5%NaCl溶液中的裸钢丝腐蚀电流密度较1%NaCl、10%NaCl和20%NaCl溶液分别提高了约18.41%、38.43%和115.09%。裸钢丝腐蚀电流密度均远大于1 μA/cm2，处于高腐蚀状态，没有保护的预应力钢丝在NaCl溶液中很快发生腐蚀。之后腐蚀产物不断堆积在钢丝表面，可能会造成腐蚀电流密度轻微下降。
图7为涂刷单组分聚脲的钢丝在3.5%NaCl溶液与不同应力条件下的自腐蚀电位Ecorr，根据图7显示涂刷聚脲的钢丝的自腐蚀电位大约在-0.4 V，裸钢丝的自腐蚀电位大约在-0.68 V左右。涂刷聚脲的钢丝较裸钢丝的自腐蚀电位正移了约0.28 V，自腐蚀电位沿着正方向移动，表明在浸泡初期，涂层作为一种隔绝层，具有对侵蚀性介质屏蔽阻挡的能力，有效阻滞了溶液渗入至钢丝基体与涂层的界面，并大大减少了腐蚀反应（氧还原和金属溶解）的可用活性区域［18］。
图8—9为涂刷聚脲的钢丝在3.5%NaCl溶液与不同应力条件下的腐蚀电流密度Icorr与极化电阻Rp。根据图8—9显示，在第1 d的测试中，无应力状态与应力状态下的涂层钢丝腐蚀电流密度分别为3.8385×10-4 μA/cm2和3.6544×10-4 μA/cm2。在第3 d的测试中，无应力状态下的涂层钢丝Icorr升高至5.1076×10-4 μA/cm2，而应力状态下的涂层钢丝Icorr达到了1.0638×10-3 μA/cm2，较无应力状态提高了约108.28%。之后的每次测试均显示应力状态下的涂层钢丝腐蚀电流密度更高，这表明应力会提高涂层钢丝的腐蚀速率，但随着浸泡时间的延长，应力对涂层钢丝的影响逐渐稳定，腐蚀电流密度差距变小。在第25 d的测试中，无应力状态下的涂层钢丝Icorr升高至6.3923×10-4 μA/cm2，而应力状态下的涂层钢丝Icorr达到了7.5541×10-4 μA/cm2，较无应力状态提高了约18.17%；涂层钢丝的腐蚀电流密度变化趋势显示为先升高后降低再升高，这可能与涂层吸水性有关；在试验过程中，涂刷聚脲的钢丝的腐蚀电流密度处于10-4数量级，施加应力后会提高腐蚀电流密度，但仍比裸钢丝低约5个数量级，表明单组分聚脲涂层能有效提高预应力钢丝的耐腐蚀性能。
3.2　应力对电化学阻抗谱（EIS）的影响
根据3.1节中对腐蚀热力学和动力学参数分析可知，施加应力会提高钢丝腐蚀速率。然而单一的电化学测试手段可靠性比较低，其结果受到试件自身、测试方法、测试过程的影响。同时，各种电化学测试方法所获取的电化学参数不同，仅靠一种测试结果反映腐蚀情况不够准确。为进一步揭示界面反应机理，采用电化学阻抗谱对样品进行分析。在EIS分析中，Nyquist图以阻抗实部为横轴、负虚部为纵轴，表征不同电化学过程在复平面上的响应特征；Bode图分别绘制阻抗模值和相位角随频率的对数变化关系，用于表征阻抗的频率响应特性。前者可以直观地观察到不同反应区域，为分析体系中的主要反应控制机制提供初步判断，识别出体系的溶液电阻、电荷转移和扩散等过程；后者能够清晰地展示不同频率条件下体系的控制机理。
图10为预应力钢丝在不同浓度NaCl溶液与应力条件下的Nyquist图与Bode图。根据图10显示，预应力钢丝的Nyquist图呈现为一段单容抗弧，Bode相角图中含有一个波峰，意味着此时预应力钢丝表面电化学反应具有1个时间常数，采用图11所示的等效电路对EIS数据进行解析，其中Rs代表溶液电阻；Rct代表钢丝/溶液界面电荷转移电阻；考虑到试件表面的弥散效应，采用常相位角元件CPE代替钢丝/溶液界面的双电层电容，以获得更好的拟合效果，有
ZCPE=[Y0(jω)n]-1
式中：ZCPE和Y0分别为常相位角元件的阻抗和导纳；ω为激励信号的角频率；n为弥散指数，代表固体电极双电层偏离理想电容的程度，一般由于电极表面的粗糙度导致双电层电场的不均匀性，其取值范围为0<n<1，当n=0时，CPE等效为纯电阻，n=1时，CPE等效为理想电容［14］。预应力钢丝在不同浓度NaCl溶液与应力条件下等效电路拟合结果见表2。
电荷转移电阻Rct的值即为容抗弧的直径值，表示电极与溶液之间发生电荷转移的难度，Rct越大，试件的耐腐蚀性能越好［19］。根据图10显示，随着NaCl溶液浓度从1%增加至3.5%，容抗弧半径呈收缩趋势，说明预应力钢丝发生腐蚀的趋势增强；增加至10%，容抗弧半径反而呈增大趋势，继续增加至20%，容抗弧半径继续扩大，说明预应力钢丝在极高浓度氯盐中发生腐蚀的趋势下降，以上现象表明容抗弧半径并非与氯盐浓度成线性关系。在应力状态下，除了20%NaCl溶液，1%、3.5%、10%NaCl溶液中的裸钢丝阻抗谱半径均产生不同程度的缩小，表明应力会促进裸钢丝腐蚀且不同氯盐浓度下的裸钢丝对应力的敏感性不同。
根据表2的拟合结果可以看出，随着氯盐浓度的增大，溶液电阻Rs呈不断缩小的趋势，而电荷转移电阻Rct却并非随着氯盐浓度的增大而呈线性减小，其中3.5%NaCl溶液与应力耦合条件下的裸钢丝Rct最小，为1289.3 Ω·cm2。应力状态下1%、3.5%、10%NaCl溶液中的裸钢丝电荷转移电阻Rct较无应力状态发生不同程度的降低。
图12—13分别为无应力与70%极限应力条件下的涂刷聚脲的钢丝浸泡在3.5%NaCl溶液中随时间变化的Nyquist图与Bode图。根据图12—13显示，涂刷聚脲的钢丝的Nyquist图呈现为一段单容抗弧，高频区为一段压扁的圆弧，采用图14所示的等效电路对EIS数据进行解析，其中Rs代表溶液电阻；Rc代表涂层电阻；CPE为常相位角元件，拟合结果见表3—4。
根据图12—13显示，无论是否施加应力，涂层钢丝Nyquist图中高频区容抗弧半径在浸没初期都快速缩小，这主要是由于水分通过涂层孔隙不断扩散以及氧的吸收，导致防腐涂层防护性能退化。随着浸没时间的延长，水分和氧的吸收达到相对平衡状态，对防腐涂层阻滞性能的影响减小，容抗弧半径后续测试下降缓慢。有研究表明当有机涂层低频区域的阻抗模值小于106 Ω·cm2以后，其对金属基体不再产生有效的腐蚀防护作用［20］。根据Bode图显示，随着浸泡时间的延长，阻抗模值在不断降低，但阻抗模值仍处于107数量级，相角图呈现一个时间常数特征，说明涂层还未失效，对于预应力钢丝仍有较好的保护。值得注意的是，在应力状态下的容抗弧半径缩小程度明显大于无应力状态，低频区阻抗模值下降更明显。25 d后，无应力状态下，涂层钢丝低频区的阻抗模值|Z0.01Hz|从6.7827×107 Ω·cm2下降至3.8392×107 Ω·cm2，降低了约43%，应力状态下涂层钢丝低频区的阻抗模值|Z0.01Hz|从7.0954×107 Ω·cm2下降至2.0687×107 Ω·cm2，降低了约71%。以上结果表明，应力能够加速防腐涂层的阻滞性能的退化。
涂层抵抗电解质溶液渗入的能力取决于涂层的吸水率，与涂层电容的大小Y0有密切联系，涂层电容越小，说明渗透到涂层内部的电解质溶液就越少，吸水率也越低。因此，涂层电容的大小可反映涂层抗渗性能的好坏［21］。根据表3—4的拟合结果显示，涂层的电容Y0无明显变化规律，说明其抗渗性能在试验周期内始终维持在一个较良好的状态。而随着在3.5%NaCl溶液中浸泡时间的延长，涂层电阻Rc整体呈微弱递减的规律。表明随着试验进行，防腐涂层出现微弱的老化，其原因可能是由于电解质溶液通过涂层微孔或涂层缺陷向涂层内部不断渗透，导致涂层阻滞性能逐渐降低，涂层电阻逐渐减小，但在整个试验周期内其值始终大于107 Ω·cm2，说明其能对钢丝提供有效保护。无应力状态下涂层钢丝的Rc从5.0860×107 Ω·cm2降低至3.9701×107 Ω·cm2，应力状态下涂层钢丝的Rc从5.2064×107 Ω·cm2降低至2.2801×107 Ω·cm2，表明施加应力会加速涂层防护效果的下降，与线性极化法结论保持一致。
3.3　腐蚀机理分析
图15为预应力钢丝在3.5%NaCl溶液与应力耦合条件下宏观腐蚀形貌演变。根据图15显示，试验开始后，样品较快失去原有的金属光泽，3 d时钢丝表面已基本被锈蚀层覆盖，6 d时钢丝表面已形成致密锈层，样品随着浸泡时间的延长，腐蚀产物不断堆积在钢丝表面，外层产物为Fe2O3（红锈），内层产物是氧化不完全产生的Fe3O4（黑锈）。
事实上，钢丝腐蚀通常是一个电化学腐蚀过程，阳极和阴极的反应分别为：
Fe-2e⁻=Fe²⁺
O₂+2H₂O+4e⁻=4OH⁻
Fe2+从钢丝表面进入溶液中与水解产生的OH-进一步反应生成Fe（OH）2：
Fe2++2OH-=Fe(OH)2
该化合物被溶解氧化后生成氢氧化铁Fe（OH）3，并进一步生成Fe2O3，一部分氧化不完全的变成Fe3O4：
4Fe(OH)2+2H₂O+O₂=4Fe(OH)3
2Fe(OH)3=Fe2O3+3H₂O
6Fe(OH)2+O₂=2Fe3O4+6H₂O
裸钢丝的腐蚀电流密度之所以没有随着NaCl浓度升高而一直升高，是因为在较高浓度NaCl溶液中的溶解氧含量反而较低，抑制了阴极反应，此时溶解氧含量占反应进程的主导地位，且应力叠加效应不显著，表明钢丝腐蚀电流密度并非与氯盐浓度成线性正相关。
4　结论
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（1）不同氯盐浓度下的预应力钢丝腐蚀电流密度对应力的敏感性不同。70%极限应力状态下1%、3.5%和10%浓度的NaCl溶液中裸钢丝腐蚀电流密度较无应力状态分别提高了9.57%、10.54%和19.19%，而20%NaCl溶液中的裸钢丝腐蚀电流密度变化不明显。
（2）外部因素对预应力钢丝腐蚀速率的影响：氯盐浓度>应力。无论是否施加应力，不同浓度NaCl溶液下裸钢丝的腐蚀快慢顺序为：3.5%NaCl>1%NaCl>10%NaCl>20%NaCl。提高Cl-浓度可以加速预应力钢丝的腐蚀，但是过高的离子浓度反而降低了溶液中的溶解氧含量，抑制了电化学腐蚀的阴极反应，导致腐蚀速率下降。
（3）在应力-氯盐耦合环境下，涂刷0.2 mm厚单组分聚脲的钢丝表现出显著防腐效果：70%极限应力下持载浸泡25 d后，其腐蚀电流密度为7.5541×10-4 μA/cm2，较同条件下的裸钢丝腐蚀电流密度25.48 μA/cm2低5个数量级；低频区阻抗谱模值仍高达2.07×107 Ω·cm2，较初值降低了约71%。

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doi: 10.3724/j.jiwhr.20250102
  • 接收时间：2025-04-18
  • 首发时间：2026-06-25
  • 出版时间：2026-05-28
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  • 收稿日期：2025-04-18
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    流域水循环与水安全全国重点实验室 中国水利水电科学研究院，北京 100038

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孙志恒（1962—）， 教授级高级工程师， 主要从事水工混凝土建筑物的检测、评估与修补加固技术研究。 E-mail：
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2种不同金属材料的力学参数
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Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
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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