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基于扫描微探针技术的现代腐蚀电化学研究进展

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曹发和 ¹ , 李鑫冉 ¹ , 黄秋雨 ¹ , 肖煜华 ¹ , 张勤号 ²

科技导报 | 特色专题 2025,43(17): 49-61

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科技导报 |特色专题 2025 , 43 (17) : 49 -61

基于扫描微探针技术的现代腐蚀电化学研究进展

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曹发和¹, 李鑫冉¹, 黄秋雨¹, 肖煜华¹, 张勤号²

作者信息

1. 中山大学材料学院，深圳 518107

2. 宁波大学机械工程与力学学院，宁波 315211

Research progress in modern corrosion electrochemistry based on scanning probe techniques

Fahe CAO¹, Xinran LI¹, Qiuyu HUANG¹, Yuhua XIAO¹, Qinhao ZHANG²

Affiliations

1. School of Material, Sun Yat−sen University, Shenzhen 518107, China

2. Faculty of Mechanical Engineering and Mechanics, Ningbo University, Ningbo 315211, China

出版时间: 2025-09-13 doi: 10.3981/j.issn.1000-7857.2024.12.01748

文章导航

摘要

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基于混合电位理论的经典腐蚀电化学对于腐蚀与防护的研究具有重要的促进作用，但也必须认识到腐蚀反应的多反应耦合非平衡不可逆的特征，并由此导致的Butler−Volmer和Nernst−Planck方程的过度简化，以及对构成腐蚀的电极反应研究的弱化。从腐蚀方程出发，指出腐蚀电化学的内涵，综述了扫描电化学显微镜（SECM）、扫描振动电极（SVET）、局部电化学阻抗（LEUS）和扫描电化学池显微镜（SECCM）4种典型扫描探针技术在腐蚀反应动力学、空间物种监测、腐蚀活性分布等方面应用的优势与进展，发现高分辨扫描探针技术可识别低至几个纳米腐蚀点与皮安级腐蚀电流，实现了腐蚀发生发展过程反应活性空间差异与动力学的原位监测，进一步结合计算模拟可量化比较分析腐蚀数据。最后展望了现代腐蚀电化学的发展趋势，可继续从多反应耦合的非平衡不可逆腐蚀反应的本质出发，深度融合跨尺度表征，建立宏观−微观的辩证统一关系。

关键词

腐蚀电化学 / 多反应 / 非平衡 / 扫描探针技术 / 腐蚀反应动力学

Abstract

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Classical corrosion electrochemistry based on mixed potential theory has played an important role in advancing research on corrosion and protection. However, it is also essential to recognize the multi−reaction coupling, non−equilibrium, and irreversible nature of corrosion processes, which often leads to excessive simplifications in the Butler–Volmer and Nernst–Planck equations and a weakened focus on the individual electrode reactions that constitute corrosion. Starting from the fundamental corrosion equation, this work clarifies the connotation of corrosion electrochemistry and reviews the advantages and recent progress of four representative scanning probe techniques—scanning electrochemical microscopy (SECM), scanning vibrating electrode technique (SVET), localized electrochemical impedance spectroscopy (LEIS), and scanning electrochemical cell microscopy (SECCM)—in probing corrosion reaction kinetics, monitoring spatially distributed species, and mapping corrosion activity. High−resolution scanning probe methods have been shown to detect corrosion sites as small as a few nanometers and corrosion currents at the picoampere level, enabling in−situ monitoring of the spatial heterogeneity and kinetics of corrosion processes. When further combined with computational modeling, these techniques allow for quantitative comparative analysis of corrosion data. Finally, the paper summarizes and discusses future trends in modern corrosion electrochemistry, suggesting that further research should be rooted in the intrinsic nature of multi−reaction−coupled, non−equilibrium, irreversible corrosion processes, deeply integrating multi−scale characterization, and establishing a dialectical unity between macroscopic and microscopic perspectives.

Key words

corrosion electrochemistry / multi−reaction / non−equilibrium / scanning probe technology / corrosion reaction kinetic

引用本文

曹发和, 李鑫冉, 黄秋雨, 肖煜华, 张勤号. 基于扫描微探针技术的现代腐蚀电化学研究进展. 科技导报, 2025 , 43 (17) : 49 -61 . DOI: 10.3981/j.issn.1000-7857.2024.12.01748

Fahe CAO, Xinran LI, Qiuyu HUANG, Yuhua XIAO, Qinhao ZHANG. Research progress in modern corrosion electrochemistry based on scanning probe techniques[J]. Science & Technology Review, 2025 , 43 (17) : 49 -61 . DOI: 10.3981/j.issn.1000-7857.2024.12.01748

正文

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金属材料在服役过程中通常由于环境的作用，发生电化学/化学反应导致性能衰变的过程称之为腐蚀^[1−2]。多数金属腐蚀现象都具有电化学特征，即金属及其合金在发生腐蚀时至少有2类反应：一类是金属阳极溶解形成离子并释放电子；另一类是阴极去极化反应获得电子过程，如析氢反应和/或吸氧反应^[3]。在过去的40多年里，包括电化学阻抗谱、极化曲线和电化学噪声在内的多种电化学方法得到快速发展，为腐蚀检测、速率评价、寿命评估和腐蚀机制研究提供了大量且重要的信息。需要指出的是，传统腐蚀电化学的研究对象是平板电极（planar electrode，以一维线性传质模型为基础，一般腐蚀研究电极面积约1.0 cm²），所获得的电化学信息是整个电极的平均信息，特别是极化曲线技术，且极化曲线难以获得构成腐蚀的电极反应动力学信息。电化学阻抗谱虽有较宽的频率范围（通常为10⁵~10⁻² Hz），具有一定程度的时间尺度分辨，但是所获得的界面行为和电荷转移电阻等仍是以整个电极平均信息为基础的结果。电化学噪声方法虽能较好地检测局部腐蚀的发生发展，其不足之处主要是复杂的数据处理和分析方法，以及噪声信号特征与腐蚀信息之间对应关系的建立，一般需要辅以形貌观察等离线物理表征^[4−6]。必须指出的是：腐蚀电化学过程包含至少2个电化学反应耦合的非平衡电化学过程，并通常伴随化学反应^[7]，即腐蚀反应具有非平衡不可逆多反应耦合的特点，较大程度上限制了电化学测试技术的应用，也限制了腐蚀电化学的研究与发展。

目前对于腐蚀电化学的核心基础理论框架仍是基于混合电位理论（mixed potential theory），获得如下腐蚀方程

(1)

$ i=i_{\mathrm{corr}}(e^{-\frac{\eta}{\beta\mathrm{_c}}}-e^{\frac{\eta}{\beta\mathrm{_a}}}) $

腐蚀电化学的数据分析基本都是建立在该方程的基础上，获得诸如极化电阻（R_p）、阴阳极Tafel斜率（β_a和β_c）、自腐蚀电流（i_corr）、自腐蚀电位（E_corr）、电荷转移电阻（R_ct）、双电层电容（C_dl）、膜电阻（R_film）和扩散阻抗（W）等系列电化学特征参数，这些参数与腐蚀速率及腐蚀机制等存在或紧密或松散的联系。腐蚀电化学方法可通过精准解析界面过程（EIS）、快速量化腐蚀速率（极化曲线）和动态捕捉局部失效（电化学噪声），为工程材料防护、寿命预测及失效分析提供核心技术支持。其优势在于高灵敏度、多尺度覆盖（微观−宏观）及实时监测能力，是工业防腐优化与智能运维的关键工具。很多研究工作围绕不同环境体系、不同金属/涂镀层下实现电化学测试，并试图建立相关电化学特征参数与腐蚀行为之间的联系^[8−10]。然而，当前腐蚀电化学常常会遇到困难，如Tafel极化线性区不明显，导致线性拟合时偶然性和误差较大；弱极化区阴极和阳极反应的耦合电流难以分离，很难获得具体腐蚀阴阳极反应动力学数据；EIS分析过度依赖等效电路，但是等效电路自身的物理化学图像不够清晰；对于部分腐蚀体系（如高阻体系、易钝化体系），极化曲线和电化学阻抗谱重复性欠佳等。这些问题的存在易导致对腐蚀电化学数据分析流于形式，使得腐蚀电化学变成测试工具，限制腐蚀电化学的发展。产生这些问题的根源有2点。（1）金属腐蚀多以局部腐蚀形式发生发展（微纳尺度），特别是在腐蚀初期。而电化学阻抗谱和极化曲线测试与分析是以整个测试电极（厘米尺度）的信息为基础，不具备空间分辨。这也是一定程度上腐蚀电化学测试结果重现性欠佳，以及测试结果与电极面积有关的原因。（2）腐蚀电化学分析基础是基于混合电位理论的腐蚀基本方程，不是各自电化学反应本身，即反应信息不够明确。腐蚀基本方程是对腐蚀电化学阴阳极反应的多步假设和简化而得，而现状是直接应用腐蚀基本方程去分析腐蚀电化学数据，获得相关特征参数，鲜有探讨是否可行及其合理性的工作报道。因此，有必要基于现代电化学和仪器科学的发展，深入微纳尺度，原位实时研究腐蚀基本过程和行为特征，发展现代腐蚀电化学，这将是腐蚀方法研究第2次重大机遇与挑战。目前，国内外已开展基于扫描微探针技术的腐蚀行为与动力学研究，并取得了进展。

1 基于扫描探针技术的腐蚀电化学进展

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1.1 扫描电化学显微镜（SECM）

1989年，Bard等^[11−12]引入SECM扫描探针技术，并对其操作原理与应用发展做出系列开创性工作。SECM典型测试原理见图1，通常具有高传质速率的微/纳米探针在腐蚀金属上方几纳米至几十微米区间三维扫描，使得探针和基底样品电极扩散层相互作用，进而实时收集反应产物或监测局域化学环境变化。依据操作模式与目的不同，双恒电位仪可独立对探针和基底电极施加外部极化，实现对液相体系中腐蚀样品的原位电化学/化学成像，具有微/纳级高空间分辨率、化学灵敏性高与非侵入性特点。SECM空间分辨率高度依赖于探针几何尺寸和探针/基底电极距离，其中几何尺寸包括电极大小和电极半径与绝缘包裹层半径比值（RG值）。一般来说，电极尺寸和RG值越小，探针可以逼近到基底上方更近距离，分辨率越高。然而，纳米探针制备重复性差，存在热漂移、电化学与静电损伤、精确针尖定位和针尖污染等因素，限制了纳米级高分辨成像^[12−13]，因此，SECM应用的常见空间尺寸在微米量级。据报道，SECM探针直径也可低至约6 nm，实现10 nm Au颗粒上皮安级反应电流的超高分辨成像^[14]。

金属微区腐蚀研究常采用的SECM操作模式如图2所示。该领域往往基于直流SECM（DC−SECM）的反馈模式（图2（a））、产生−收集模式（图2（b））和氧化还原竞争模式（图2（c）），评估腐蚀样品局域电子转移特性^[15−17]，收集阴阳极反应腐蚀产物（如Fe²⁺、O₂、H₂）^[18−21]，或反应中间物种（如Mg⁺、Cu⁺、Ti^x≤3+、H₂O₂）^[22−26]等。还可通过电位模式（图2（d）），利用离子选择性探针在无电流扰动下实时监测金属离子（如Al³⁺、Mg²⁺、Zn²⁺、Na⁺、Cl⁻）与pH演变^[27−33]等。亦可采用交流SECM（AC−SECM，图2（e））通过向探针施加定频正弦波扰动，在低电导率或无氧化还原媒介液相中，可视化腐蚀样品局域双电层电容与电荷转移电阻等阻抗参数^[34−35]。经过30余年的发展，SECM已被广泛应用于裸金属与覆膜金属^[13,36−37]、合金与电偶对^[35,38]，及涂层与缓蚀剂保护下金属^[39−40]的局部腐蚀行为与动力学研究。特别是结合COMSOL多物理场模拟可进一步获取腐蚀物种空间浓度分布、腐蚀速率、腐蚀反应本征动力学参数，以及绘制腐蚀区域几何形貌等定量腐蚀信息^[41−45]。

局部腐蚀活性可视化与腐蚀机理分析为SECM腐蚀应用的热点研究领域。Li等^[46]采用SECM基底产生−探针收集模式，以I³⁻/I⁻为氧化还原媒介研究了组分及其占比对马氏体不锈钢腐蚀行为的影响，证明了点蚀的萌生与扩展发生在富含MnS和TiN夹杂相的特定区域。Wang等^[29]成功制备了5 μm直径的长效、高选择性Pt/RuO_x全固态微型pH传感器，在模拟海水中监测了X80管线钢预制切口处pH随腐蚀进程的演变，发现切口附近首先出现显著pH碱化之后逐渐酸化，结合其他物性表征提出了切口处Fe溶出Fe²⁺后逐渐转换为稳定α−FeOOH的反应机制。在异种金属电偶研究中，Alvarez−Pampliega等^[30]采用钨pH电极研究了Fe/Cu电偶腐蚀过程局域pH分布，结果表明Fe上酸性与碱性位点共存，揭示了电偶效应驱动下Fe表面仅有部分充当阳极。Sundaresan等^[13]基于反馈模式监测了酸性氟化物溶液中钛/不锈钢（TA1/304SS）电偶腐蚀活性位点，证明了电偶对随时间演变的阴阳极极性反转现象。此外，Yanagisawa等^[47]利用SECM进行了同种金属异质性微电偶，监测到双相钢马氏体相钝化膜比铁素体相钝化膜具有更好的电子导电性和弱钝化性。在防腐涂层/缓蚀剂评价中，Feng等^[48]在纯锌上制备了三价铬转化膜，通过反馈模式原位研究了转化膜初期局部腐蚀与自愈行为，表明浸泡24 h后转化膜开裂发生局部腐蚀，添加聚苯胺可抑制氧还原反应阻碍腐蚀过程，提高转化膜自愈能力。Wang等^[49]基于AC−SECM通过监测阻抗|Z|和相位角变化，分析了含单宁酸的氧化石墨烯−介孔二氧化硅涂层的自愈过程，结果表明AC−SECM高度依赖于测试频率，高频（60000 Hz）测试下清晰显示96 h后涂层发生愈合。对于应力场作用下的腐蚀行为研究，SECM也可以用提供局部活性以及腐蚀类型演化等信息。Nazarov等^[50]采用SECM方法研究了拉伸应力对AISI 304不锈钢钝化击穿的影响，结果表明，由于具有破裂钝化膜的阳极性较强的区域与邻近的阴极表面之间的电偶联，应力部位将发生腐蚀。Chen等^[51]通过SECM研究结果表明：随着应变水平的增加，304L不锈钢的表面反应活性显著增强，且应变诱导的α׳马氏体和剪切带区域具有比基体更高的表面反应活性，更容易发生腐蚀，微观电偶腐蚀的激活导致局部腐蚀速率提高。Huang等^[52]使用SECM分析不同弹性应力对TA2阳极行为的影响，探讨了应力水平、钝化膜以及晶粒结构等对腐蚀行为的影响。以上典型应用仍是把SECM作为腐蚀活性/化学环境成像工具，对腐蚀反应过程物种演变与动力学信息研究仍不足。

基于腐蚀电化学反应的中间物种鉴别与反应动力学分析，是深入理解金属腐蚀行为的基础，也是SECM重要腐蚀应用。Li等^{[20, 53]}采用改进的探针产生−基底收集模式，通过定量收集高纯Fe、Cu、Ti阴极氧还原（ORR）过程中H₂O₂，考察了pH、极化电位、电解质阴离子或氧化膜状态对氧还原活性与选择性的影响。结果表明，不同金属表面ORR均非简单4e⁻还原过程，高pH值和强阴极极化促进4e⁻选择性，覆膜金属Ti表明ORR活性往往小于裸金属且高度依赖表面膜活化程度及阴离子介质。对于阳极溶解过程，Bard等^[11]还提出了进一步改进的探针产生−基底收集模式，量化了变价金属Ti在酸性氟化物溶液中表观溶解价态随电位依赖性关系，提出Ti在钝化电位之下表观溶解价态低于三价，即使在强阴极极化区间仍存在钛离子溶出。此外，基底产生−探针收集模式成功用于金属Mg溶解过程Mg⁺的监测，为Mg溶解的负差数效应提供了直接电化学证据^[22]。关于腐蚀反应动力学研究，其往往基于反馈模式，在含有氧化还原媒介的溶液中测试探针对样品表面逼近曲线，通过理论逼近电流公式拟合测试值已获媒介在金属表面有效再生速率常数，以量化金属腐蚀活性。代表性研究如Asserghine等^[54]采用FcMeOH作为媒介研究了其在Ti4G表面的钝化膜再生速率，证明钝化膜浸泡时间延长生成速率减慢，20 min时达到稳定最小值，Ti4G发生完全钝化。然而简化模型可能造成理论量化结果与实际结果偏差。

COMSOL多物理场模拟使SECM数据进入量化新阶段，其不但可以定量氧化还原媒介再生速率^[55]，还可定量具体腐蚀本征动力学参数^[56]，或模拟腐蚀物种的三维空间分布与腐蚀几何维度成像^[40,43]。Zhang等^[57]首次将改性的探针产生−基底收集模拟应用于腐蚀领域，活性金属Fe探针上同时发生析氢与溶解反应，基底电极通过定量高效率（91%）收集探针H₂，成功从Fe表观腐蚀电流中分离出净析氢电流，进一步构建COMSOL二维轴对称模型，基于Butler−Volmer方程和Fick定律模拟出酸性高氯酸钠溶液中Fe表面析氢反应本征速率常数为2.5×10⁻⁶ cm/s，传递系数为0.7。Clark等^[43]将半径700 nm次微米Pt电极用于316L不锈钢点蚀高分辨成像，之后将SECM电化学数据结合三维COMSOL多物理模拟，量化相距1 μm点蚀坑的空间几何维度并报道点蚀动态演化过程。

发展至今，SECM已开发出多种功能型探针，并常采用多模式结合，或与其他扫描探针技术、谱学技术及理论计算结合，在更全面分析和深入认识金属局部腐蚀行为中展现出巨大应用潜力^[18,58−60]。典型工作如Zhu等^[61]开发了一种全固态Pt−Pt/IrO_x超微电极，用于316L不锈钢在6.0%氯化铁溶液中开路电位下的电化学/化学可视化研究，同时监测局部阳极溶出的Fe²⁺与局部阴极质子消耗引起的pH变化。扫描清楚地显示了局部阳极电流和阴极pH峰位置之间的表观距离约为84 μm，高度为15 μm。为最小化电场失真，Xavier等^[26]开发了三壁超微电极探针，通过引入内置参比电极使参比电极尽可能接近离子选择性电极，实现了AZ63镁合金上方Mg²⁺、pH的同时监测。Zhang等^[57]采用反馈模式、基底产生−探针收集模式，及电位模式SECM，对Ni²⁺、H⁺、H₂监测研究了镍钛诺在NaCl溶液中异质活性与局域pH环境变化，观察到Ni²⁺溶出阳极区域的局部酸化与阴极区域的碱化。Bastos等^[18]和Chen等^[51]结合SECM与原位表面增强拉曼光谱、COMSOL模拟、第一性原理计算及分子动力学模拟，深入分析了氧化膜特性对高纯钛析氢及吸氧反应行为与动力学影响。综上，多功能、多模式、多技术结合已然成为SECM在腐蚀领域研究的重要发展方向，但目前仍缺乏从电化学反应角度深入研究腐蚀反应相关研究。

1.2 扫描振动电极（SVET）

20世纪80年代，Jadhav等^[62]首次将SVET应用于腐蚀研究。其基本测试原理见图3，其中定频正弦振动的探针（通常垂直振动）位于被测金属上方，样品处于自由腐蚀或极化状态。金属腐蚀诱发局部阴阳极离子流动，形成局部电场，振动探针通过测试样品表面振动幅度内电位差△V，进而基于欧姆定律i= −k△V/△d（k为溶液电导率，d为2个振动点间距）获取样品上方局部电流密度演变的电化学图像，电流正负可反映局域阴阳极特性。该技术通常采用10~30 μm沉积铂黑的Pt振动电极作为探针，且探针−基底间隔一般大于4倍探针振幅，以防撞击基底、避免探头屏蔽效应或高估真实电流。当探针−基底间距为典型值100 μm时，SVET空间分辨率约为200 μm。SVET对腐蚀点源电压与电流信号的检测还受溶液电导率等影响，在0.005~0.5 mol/L NaCl溶液中其可识别约200 nV电压差和低至几个纳安的腐蚀电流^[63]。

SVET可方便识别腐蚀局部阴阳极位置或相对活性，在局部腐蚀（尤其是电偶腐蚀、焊缝腐蚀和应力腐蚀等）^[64−67]，或防腐涂层与缓蚀剂评价中具有广泛应用^[68−72]。Nguyen等^[73]通过SVET研究了铈盐对锌基牺牲涂层钢切割边缘的影响，表明铈盐加速了锌基牺牲层的电偶腐蚀，硝酸铈存在下加速尤为严重。此外，铝、镁合金元素的加入促进了局部腐蚀，影响了腐蚀产物的形成和分布。Zhou等^[74]研究了搅拌摩擦焊（FSW）工艺中转速对AZ31镁合金焊接接头腐蚀性能的影响，SVET结果显示在1800 r/min下形成的镁合金焊接接头表面电流最小，电流差值约为0.86 mA/cm²，远小于其他转速下电流差值（可高达约12 mA/cm²）。该结果与接头显微组织及宏观电化学良好吻合，进一步证明了优化旋转速度有助于焊接过程中的高效热机械处理，细化晶粒，从而提高耐腐蚀性。Yang等^[75]成功将SVET技术应用于超强不锈钢应力腐蚀研究，考察了不同拉应力和时间周期下裂纹尖端和基体处的电流密度分布，结果显示裂纹尖端的腐蚀电化学活性更高，且电流密度随施加应力与时间增加而增大。在1500 MPa应力下浸泡96 h裂纹尖端电流密度急速增加至10.4 μA/cm²，约为无应力时电流的3倍。相似地，Sun等^[76]采用SVET研究了预裂纹超高强度不锈钢Cr₁₂Ni₅MoCo₁₄在酸性和应力环境下的电化学行为，探讨了活性差异及其可能的原因。Ge等^[77]通过喷涂在Q235碳钢表面合成了具有不同孔隙率的Co₂₁Fe₁₄Ni₈Cr₁₆Mo₁₆C₁₅B₁₀高熵金属玻璃涂层，之后利用SVET评估系列涂层保护下Q235碳钢在氯化钠溶液中局部腐蚀活性演变。扫描结果显示低孔隙率涂层表面平均电位差小于10 μV，具有优异耐腐蚀性；而高孔隙率涂层表面电位差高达几十毫伏并随时间增加而增大，展示出更高腐蚀反应活性，这对应于高孔隙涂层中存在的大量缺陷。Guo等^[66]首次将丹参提取物用作Q235钢在1 mol/L HCl溶液中的新型缓蚀剂，SVET监测表明缓蚀剂加入显著延缓了阳极溶解，浸泡24 h后最大缓蚀效率达到91.3%，并在72 h内保持在90.4%。

相较SECM，SVET提供振动平面内所有离子电流信息而非与腐蚀过程直接相关的物种浓度，缺乏对离子种类的化学鉴别，与腐蚀反应自身相关性弱；探针的振动及其造成的物种扩散与屏蔽效应，导致样品−探针较大间隔（通常为100~200 μm），分辨率通常低于SECM；此外，溶液电导率k默认为定值可能对剧烈腐蚀样品产生较大误差^[78]。因此，SVET往往被视为半定量的腐蚀可视化技术，而难以真正确定腐蚀反应及评估腐蚀速率。

基于COSMOL模拟，SVET结果定量及其离子电流测试结果与反应物种的关联成为可能^[79−82]。例如，Kozlica等^[64]利用SVET测试了AZ31−AA5083镁铝合金板电偶腐蚀离子通量分布，通过考虑金属Mg和Al阴阳极腐蚀反应及其后水解过程，建立了基于AZ31镁和AA5083铝的铆接板腐蚀演化的COMSOL数值模型，成功模拟了电偶腐蚀产物空间分布及其演变，该模型与SVET实验阴极阳电流密度分布良好匹配，证明了镁铝双层氢氧化物沉积行为。然而，采用COMSOL模拟SVET数据需假设可能发生的各类腐蚀反应，以构建合理的腐蚀物理模型，操作的复杂与不确定性使SVET定量分析仍较为困难，迄今为止，SVET腐蚀应用仍集中于局部腐蚀半定量成像研究，难以实现对构成腐蚀的电化学反应和化学反应的定量定性研究。

1.3 局部电化学阻抗谱（LEIS）

20世纪90年代，Lillard等^[83]和Chang等^[84]提出了另一种扫描探针技术LEIS，其测试基本原理见图4。测试过程样品整体被施加定频正弦电压扰动，通过测试探针中双微电极间电压差△V与微电极间隔求得局部电流，进而结合局部电流与施加扰动电位获取局部阻抗，该阻抗值代表探针/溶液/样品3组分界面及其区间内总阻抗^[85]。LEIS测试不依赖于溶液中氧化还原物种的存在，其空间分辨率通常由双微电极探针尺寸（通常为Pt电极）、2个微电极丝间隔以及探针−基底距离决定。由于探针结构复杂，该技术高空间分辨率有限，最佳分辨率可达约10 μm^[84]。通过与更高分辨的探针装置耦接（如AFM−LEIS^[86]、SECCM−LEIS^[87]），可显著提高其分辨率。据报道，采用SECCM的准参比电极向基底样品施加交流偏压，SECCM−LEIS的分辨率可高达180 nm^[88]。

基于此，LEIS与AC−SECM均通过正弦扰动测试界面与溶液区阻抗，可在低电导率溶液中进行，便于对腐蚀初期与末期的缓慢反应阶段获得理想电化学成像质量，适用于腐蚀发生发展的完整过程监测与定量分析。相较而言，LEIS探针双微电极配置导致其空间分辨率通常低于AC−SECM^[89]。目前，LEIS已被报道用于缓蚀剂、涂层、电偶对与应力作用等腐蚀体系的无损检测^[90−94]。Liu等^[92]采用LEIS在10 Hz下评价了苯并三唑缓蚀剂复合涂层对Q235碳钢表面划痕的腐蚀自愈能力。LEIS结果显示划痕处的阻抗低于周围区域，从腐蚀初期2 h至末期36 h划痕处局部阻抗增加了3.1×10⁴ Ω，而在无缓蚀剂保护下阻抗值降低了3.1×10⁴ Ω，有力证明了新型缓蚀剂的高效腐蚀抑制效果。Liu等^[93]利用LEIS监测了Ti6Al4V/AA6061异种金属焊接头在质量百分比为3.5% NaCl溶液中长达16 d的电偶腐蚀行为，结果显示腐蚀初期接头处腐蚀阻抗最小，随浸泡周期延长腐蚀逐渐扩展到Al基体，证明了腐蚀主要发生在铝基体和焊缝处金属，导致点蚀和腐蚀产物的大量积累。Li等^[95]通过LEIS技术研究了拉伸应力和压缩应力及力的大小对X70管道钢腐蚀的影响。Tang等^[96]则通过LEIS清晰地揭示了应力对X70管道钢在近中性pH条件下阳极溶解行为的影响，并表征了应力、裂纹尖端应力集中效应以及时间因素对局部溶解速率的贡献。Nazarov等^[97]使用LEIS研究机械应力对碳钢（SAE 1008）和奥氏体不锈钢（301LN）表面钝化膜的影响，以及这些区域在应力存在下重新钝化的能力。

通常LEIS与AC−SECM均在固定频率下测试，具有高度频率依赖性，阻抗原始数据解析困难，两者腐蚀应用远低于直流/电位SECM与SEVT技术。多频响应采集AC−SECM（4D AC−SECM）的发展弥补了LEIS对频率依赖性的不足^[33,98]。代表性工作如，Zhu等^[33]采用4D AC−SECM，对涂漆覆锡低碳钢在8000~270 Hz的频率范围内全频阻抗谱进行了自动成像，通过等效电路有效地将整体交流响应分解为与微电极、样品界面电容以及表面局部法拉第过程相关的元件，这些参数具有更清晰的物理意义，而经典LEIS技术难以实现。然而全频阻抗谱需要更长测试时间，可能使实时成像结果失真。与SVET技术相似，LEIS也很难建立电化学信息与腐蚀反应之间的直接关联关系，难以据此发展定量的现代腐蚀电化学。

1.4 扫描电化学池显微镜（SECCM）

扫描电化学池显微镜（SECCM）是从微毛细管池技术（microcapillary cell）发展而来，最早的工作可以追溯到Williams等^[99]在2009年提出的利用直径约1 μm玻璃管探测电极表面氧化还原活性的扫描微管接触方法（scanning micropipet contact method, SMCM）。2010年，为了测试局部电化学性质，同时实现表面形貌信息收集，Ebejer等^[100]研究了一种双管SECCM方法，该方法通过流经2个准参比对电极（QRCE）之间的离子电导电流的交流部分（i_AC）作为控制探针−基底距离的反馈信号，基本原理如图5所示。经过不断发展，SECCM逐渐成为对各种材料进行微/纳米电化学测量的通用方法，可同时收集电化学和形貌信息数据，更好地理解微观结构与电化学活性之间的关系。微液滴电解池避免了对邻近区域干扰，借助三维移动装置可获得不同测试条件下的高通量数据。此外，相较其他几项扫描探针技术，SECCM探针一般为装有测试溶液的纳米级玻璃开口毛细管，其实际分辨率等同于液滴与基底之间的接触尺寸，约为探针直径的1~1.5倍，因此SECCM具有更高空间分辨率。其分辨率通常为几十纳米，检测电流信号可达皮安级^[101]。

由于该方法可以在具有多相结构的材料表面实现原位电化学信息的高分辨成像，自2019年起，该方法用于腐蚀研究开始逐渐增多。Yule等^[102−103]利用低碳钢作为研究对象，在低碳钢表面利用SECCM技术开展了阴极析氢反应（HER）纳米活性位点分布和晶面对阳极溶剂反应活性差异成像研究。结果表明，酸性溶液内，对于低指数晶面，铁溶解反应以及析氢反应活性均为（100）>（111）>（101），中性溶液内阳极电流则在（101）晶面最大，说明不同晶面的电化学活性存在差异，同时不同溶液条件下晶面的电化学活性差异顺序也会改变。Jayamaha等^[104]则利用oil−SECCM技术（在测试基底表面覆盖一层油膜以提高测试液滴稳定性），在Zn−Al合金表面实现了高通量微区电化学测试，获得了6个具有不同微观结构特征区域的电化学差异。实验结果表明，Zn−Al合金表面α相容易出现早期金属溶解以及氧还原反应，还有金属离子的重新沉积。EDS结果分析表明这是由于该相处存在高Al含量（30%~50%），导致出现Al溶解的同时局部pH在发生氧还原反应期间升高。截至2023年，利用SECCM技术研究的金属腐蚀对象包括Ag^[105]、Zn^[106]、Cu^[107]、Al合金^[108−109]、316L不锈钢^[110]，以及Mg合金/单晶Mg^[111−112]等。结合其他的形貌表征技术，如背散射电子衍射（EBSD）以及原子力显微镜（AFM），SECCM技术被广泛地运用于分析阴极和阳极过程的动力学、表面氧化物点蚀以及微结构/组成相关的电化学活性差异。除了电化学活性差异方面的研究，该技术也被用于研究不同晶面取向对缓蚀剂作用效果的影响^[113−114]。如Ebejer等^[100]利用oil−SECCM技术发现Cu缓蚀剂（BTA−R）在不同晶面上的缓蚀效果存在差距，具体表现在对于ORR（阴极反应）或者Cu溶解反应（阳极反应）抑制效果的差别。

SECCM在腐蚀研究中具有优越时空分辨率与高通量表征的重要优势，能够在纳米尺度提供腐蚀微区原位的电化学和形貌信息。但其也存在微液滴与QRCE稳定性问题，且批量数据处理解读困难，在腐蚀电化学反应机制研究上仍有很大空间。

2 总结与展望

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目前，传统以极化曲线和电化学阻抗谱为代表的腐蚀电化学技术，以及与之对应的以腐蚀速率评价与监测为主要目标的腐蚀电化学应用，未能与现代电化学的发展同步。扫描探针技术在腐蚀与防护领域已经开展不少研究，但仍过多关注微区活性，空间分布等作为“显微镜”功能而使用，缺乏从电化学−化学反应角度发展非平衡不可逆的腐蚀电化学。结合课题组的研究以及相关的报道，现代腐蚀电化学可以从以下3个方面开展工作。

1）深刻认识多反应耦合的非平衡不可逆腐蚀反应的本质内涵，发展与之适应的电化学测试技术与解析方法，定性定量描述腐蚀反应的构成及其控制因素，发展基于电化学−化学反应的腐蚀电化学。例如，针对不同腐蚀体系特征，联合应用多种扫描探针技术优势，结合COMSOL等有限元模拟数据解析方法，建立时空间分辨的“电化学−化学腐蚀”耦合模型，从腐蚀反应出发深入理解腐蚀行为。

2）深度融合原位谱学和量化计算，获得腐蚀反应的物种分子/原子/电子层面信息，深入揭示金属/溶液界面行为，明确腐蚀反应路径与动力学特征，实现多尺度腐蚀行为与机制研究。例如，融合微区实验、分子模拟计算与原位组成表征，探究金属/涂层/溶液界面腐蚀产物与行为演变，指导环境友好型防护技术开发。

3）建立宏观−微观的辩证统一关系，既要发展基于现代扫描微探针的微区技术，实现高时空分辨的腐蚀萌生诱导的研究及其动力学，也要理解宏观尺度下腐蚀发生发展以及腐蚀产物对腐蚀行为影响，且微观要服务于宏观，最终实现腐蚀可控。例如，开展从微观缺陷演化到宏观失效行为的跨尺度研究，结合SECCM等高通量测试微区技术与宏观组成、结构及电化学等表征，分析预测不同服役环境金属腐蚀差异，指导高性能合金设计应用。

基金

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国家自然科学基金项目（52371088，52071347，51771174，51171172，52201096，52401132）；广东省基础与应用基础研究基金项目（2025A1515012093）

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2025年第43卷第17期

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doi: 10.3981/j.issn.1000-7857.2024.12.01748

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：2025-05-06
录用日期：2025-08-21

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国家自然科学基金项目（52371088，52071347，51771174，51171172，52201096，52401132）；广东省基础与应用基础研究基金项目（2025A1515012093）

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1. 中山大学材料学院，深圳 518107

2. 宁波大学机械工程与力学学院，宁波 315211

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2种不同金属材料的力学参数

科 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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