在各种不同腐蚀类型中，大气腐蚀是存在最广泛的一种腐蚀，它造成的损失约占腐蚀总损失的50%以上[4]。防护大气腐蚀最有效的方法是将金属从腐蚀环境中分离出来。目前，可以通过永久防护和临时防护两种方法实现对金属的保护。永久防护包括使用合金、金属涂层、电镀、阴极保护和阳极保护；临时防护包括涂蜡、油脂、气相缓蚀剂和干燥剂[5]。因气相缓蚀剂的生产成本低、防腐蚀效率出色、使用操作简便，所以在保护金属、合金等方面的应用越来越受欢迎[6~8]。同时，以气相缓蚀剂为基础的气相防锈技术也得到了更多的应用，这些技术提高了工作效率和金属的使用寿命，降低了石油和天然气、军事、汽车、电子、电气和其他工业部门的腐蚀防护总成本[9, 10]。
随着气相缓蚀剂广泛的应用，其性能评价和分析方法受到极大的重视。对于气相缓蚀剂性能的评价，目前建立了多种方法，但在实际评价和分析过程中，仍应结合气相缓蚀剂不同类型和不同结构、实际使用环境的条件，探究气相缓蚀剂不同方面的性能和经济效益等方面，选择最合适的方法。
1 气相缓蚀剂的特点及性能
气相缓蚀剂 (VPI)，又叫挥发性缓蚀剂 (VCI)，能在常温下自动挥发出特殊气体，依靠其挥发的缓蚀剂分子或基团在金属表面形成氧化膜、沉淀膜或分子及离子的吸附，从而抑制金属腐蚀过程的电化学反应，减小腐蚀电流，达到缓蚀的目的[5]。
1.1 特点
与其它防腐蚀方法相比，气相缓蚀剂具有以下优点[11, 12]：(1) 挥发的气相缓蚀剂气体充满整个密闭空间，可以到达防锈材料不易涂覆处 (金属的内腔、缝隙、小孔等)，使用气相缓蚀剂无需考虑金属的形状和结构，这是目前任何一种方法都不能实现的，也是气相缓蚀剂最大的特点。(2) 气相缓蚀剂防护技术操作简单，性价比最高，可用于大大小小的金属零件和设备。(3) 气相缓蚀剂在金属表面会形成极薄的膜，启用金属包装时，金属表面的气相缓蚀剂会快速挥发，无需擦除或清洗就可立刻投入使用。(4) 气相缓蚀剂和其他防护技术 (如阴极保护等) 相兼容，两者结合使用时，不仅会降低金属的腐蚀速率；也降低了阴极保护所需的电力需求。
但是，气相缓蚀剂的使用期限较难预测，无法精确计算剩余的防护时间，导致存在浪费或防护不到位的问题。
1.2 挥发性
气相缓蚀剂应用于密闭或半密闭空间，需在一定温度、持续时间内确保空间中气相缓蚀剂维持一定浓度，能够挥发吸附至金属表面起缓蚀作用。因此VCI应具有一定饱和蒸汽压，其挥发性也由饱和蒸汽压衡量。饱和蒸汽压低的VCI，有效作用距离短、挥发速率慢、诱导期长，会使金属表面的VCI未达所需浓度前就被腐蚀，但具有更持久的防锈能力；饱和蒸汽压大的VCI，有效作用距离长、挥发速率快、诱导期短，能快速挥发至金属表面抑制早期腐蚀过程，但因其挥发速率过快，耗量大，持久性能大大降低[14]。故气相缓蚀剂要有合适的饱和蒸汽压才能达到最佳防护效果。
不同气相缓蚀剂的蒸汽压差别较大，如何根据气相缓蚀剂的饱和蒸汽压和使用要求，调控其挥发性，是一个重要的环节，常用的方法有：(1) 将具有不同挥发性的气相缓蚀剂进行复配从而改变其挥发性；(2) 将气相缓蚀剂吸附在无机多孔载体上。
1.3 溶解度
气相缓蚀剂的溶解度对其应用性能也有重要的影响。气相缓蚀剂在溶液中需要有一定的溶解性，这样才能快速饱和已吸湿的金属表面。若溶解度过大，吸附在金属表面的缓蚀剂分子会发生脱附现象，不能形成有效的吸附膜；若溶解度过小，金属表面的水介质中能溶解的缓蚀剂过少，在金属表面不能形成有效、完整的吸附膜，有时不但达不到缓蚀的目的，反而会加速金属腐蚀[15]。
气相缓蚀剂还可配成气相缓蚀溶液使用，所以在溶剂中需要一定的溶解性，来满足其使用需求。气相缓蚀剂在有机溶剂中的溶解度，关系到其生产过程和使用过程，在生产过程中为提高气相缓蚀剂的产率，要选择对气相缓蚀剂溶解性小的溶剂。
1.4 吸附性
VCI分子可以通过物理吸附或化学吸附或两者兼有的方式吸附在金属表面[16]。物理吸附过程是带电的金属表面与VCI分子间发生静电相互作用。化学吸附过程是通过VCI分子结构中P、N、O、S等原子的孤对电子与金属表面进行配位完成的[17]。金属表面与VCI分子间相互作用的性质可以利用各种吸附等温线模型进行讨论，吸附等温线在理解VCI分子吸附过程可以提供一些关键信息，可用于确定吸附自由能标准值及其与表面覆盖率的关系[18]。目前，主要用于气相缓蚀剂吸附研究的平衡吸附等温线有Langmuir、Freundlich、Temkin、Floy-Huggins等。其中Langmuir吸附等温线和Freundlich吸附等温线应用较广泛，前者适用于均匀吸附过程，后者适用于非均相体系，特别是有机缓蚀剂。
1.5 缓蚀性
气相缓蚀剂分子中应该含有一个或一个以上的缓蚀基团，以使气相缓蚀剂具备一定的缓蚀性能。气相缓蚀剂的缓蚀效果与其分子结构密切相关，主要是受到缓蚀基团的影响。气相缓蚀剂挥发后遇水解离出保护基团，其未配对电子或孤对电子可以使VCI分子很好地吸附在金属表面，发生钝化阻止金属的腐蚀；VCI分子在金属表面形成单分子层，排斥水分子防止金属腐蚀。起决定性作用的是缓蚀基团，其影响主要表现在以下几方面[22]：(1) 极性强、能与金属配位的缓蚀基团吸附性强，缓蚀性能高。(2) 缓蚀基团具有选择性，如F对Al和Mg有保护作用，却会加速钢和Cu的腐蚀。(3) 复配时缓蚀基团之间的相互作用也会影响缓蚀效果。
2 气相缓蚀剂的分类
2.1 按化学组成分类
无机缓蚀剂是最为常用的VCI防腐蚀技术，在许多应用中得到广泛的研究。无机缓蚀剂一般用于酸性气体或氯离子含量高的环境中。无机缓蚀剂分子是通过吸附在金属表面，抑制腐蚀介质对金属材料的腐蚀，来达到缓蚀的目的。铬酸盐类无机缓蚀剂在VCI中表现非常出色，但六价铬酸盐会产生许多环境问题，Cr6+在人体和动物体内积累，会导致癌变，因此铬酸盐类缓蚀剂的使用已大大减少。
聚合物缓蚀剂是在金属表面形成保护层来防止腐蚀。聚合物缓蚀剂具有优良的缓蚀效果和绿色环保等优点，是近年来的主要研究目标。典型的聚合物缓蚀剂主要是有机膦酸、聚乙烯、聚天冬氨酸和一些天然高分子物质[25]。
2.2 按电化学腐蚀类型分类
气相缓蚀剂按电化学腐蚀类型可分为阳极缓蚀剂、阴极缓蚀剂和混合型缓蚀剂。阳极缓蚀剂也称为钝化缓蚀剂，通过抑制金属腐蚀的阳极反应进行防护。VCI分子的阴离子和金属表面的金属阳离子发生钝化，钝化过程VCI分子通过吸附及在金属表面被动形成氧化层，发生较大的阳极位移来延缓金属腐蚀。铬酸盐、亚硝酸盐和硝酸盐等阳极缓蚀剂可以在无氧环境下在金属表面形成氧化膜[28]；钼酸盐、钨酸盐和磷酸盐等阳极缓蚀剂只能在含氧环境中形成氧化膜。但阳极缓蚀剂主要缺点在于，缓蚀剂浓度略下降时，金属的腐蚀速率会大大上升。
阴极缓蚀剂是通过抑制金属腐蚀的阴极反应进行防护。VCI分子通过阳离子迁移到阴极区，与阴离子反应形成沉淀吸附在金属表面，减少活性阴极面积，使金属表面的阻抗增加，降低了导致腐蚀的化学物质的扩散速率，以防止金属进一步腐蚀。肼和亚硫酸钠等阴极缓蚀剂通过与周围氧分子发生化学反应消耗氧分子，从而减缓阴极反应[29]。阴极缓蚀剂一般用于碱性介质中，锑、砷和锌等阻碍了阴极析氢反应中氢离子的结合，易与氢氧根离子沉淀。
混合型缓蚀剂是典型的成膜化合物，可以同时抑制阳极反应和阴极反应过程。混合型缓蚀剂大多是具有高电负性的有机化合物，如氮、硫或乙炔醇等在金属表面形成一层保护膜，延缓金属腐蚀过程。
3 气相缓蚀剂的挥发性测试
气相缓蚀剂的挥发性一般用饱和蒸汽压来衡量。但气相缓蚀剂的常温蒸汽压通常都很小，使用一般的仪器不宜测量，误差较大，其测量方法也多种多样。
对于初始状态为液态的气相缓蚀剂，先将待测气相缓蚀剂放入恒温容器内保存，再向容器内充入惰性气体，测量所用气体的体积，即可获得待测液态气相缓蚀剂的气体含量或惰性气体的损失量。若容器中引入的惰性气体是饱和的，则可计算出液态气相缓蚀剂的饱和蒸汽压[30]。
对于初始状态为固态的气相缓蚀剂，目前发展出多种测试方法，这些方法分为动态法、静态法、表面蒸发法、沸点法[13]。
式中，M为VCI的相对分子量；R为气体通用常数；T为气体所处的温度；m为VCI在单位时间经小孔逸出的质量；S为小孔面积。根据上式可以测定VCI在不同温度下的饱和蒸汽压，通过调节小孔面积的大小，可以应用于不同蒸汽压范围的测定。
(3) 流失筒法 (Torsion effusion)：使气相缓蚀剂在一个小的玻璃的“流失筒”内在一定温度下挥发，是基于VCI分子在饱和蒸汽压下从小孔进入真空时产生的作用力进行测试。“流失筒”内有两个轻玻璃球，球体上各有一个小孔，位于对称、相反方向上。先将测量室抽真空，当气相缓蚀剂挥发时，其蒸汽自小孔喷出产生反作用力，又因两孔方向相反，对纤维丝产生旋转力矩。转动角度的大小与蒸汽压成一定的比例关系，可通过下式求出气相缓蚀剂的蒸汽压[33]：
式中，
上述测试方法(1)~(3)用来测试气相缓蚀剂蒸汽压较为复杂，且需要特殊的仪器设备。而密闭空间挥发减量法因操作简便，无需特定的仪器设备，成为常用方法。Andreev和Kuznetsov[36]提出了一种可以初步评估气相缓蚀剂的蒸汽压的方法，虽然该方法的准确度不高，但是可以避免费力的测量。
4 气相缓蚀剂的缓蚀性测试
4.1 腐蚀失重法
4.1.1 分类及特点
腐蚀失重法可分为大气环境实验和实验室加速实验两种。大气环境实验最接近气相缓蚀剂的实际使用环境，实验结果真实可靠，具有说服力；但大气环境实验周期过长，跟不上现代气相缓蚀剂研制的快节奏，会出现测试与研发脱节的问题。
实验室加速实验是通过测量金属在一定温度的腐蚀介质中放置一定时间后所损失的重量进而求出金属的腐蚀速率，能反映出在加速时间内试样的腐蚀情况。腐蚀失重法虽较为原始，但它可以模拟大气腐蚀状态下气相缓蚀剂的作用过程，具有简便、易操作、测试条件稳定、无需借助特殊仪器、结果直观等优点。但其局限性是只能测得金属表面腐蚀速率平均值，无法反映金属表面的局部腐蚀或点蚀。腐蚀失重法除被广泛应用于筛选气相缓蚀剂外，还能验证其他测试方法的准确性。
4.1.2 实验装置的改进
Skinner[37]针对当时出现的结果重现性差、实验加速性差等问题进行了一系列改进。改进后的方法使用低成本的一次性组件解决了气相缓蚀剂在测试时对实验装置的污染，提高了重现性，还可以得到定量的结果。Wan等[38]研究Skinner的实验装置后发现，由于其实验装置为半开放体系，导致饱和蒸汽压较传统VCI降低了10%~20%，不适用于新型气相缓蚀剂。进一步优化后，将传统垂直挂片改为在顶部水平安放，使水蒸气均匀冷凝在试片表面，减少试片锈蚀的偶然因素；将加热方式由整体加热改为底部加热，使顶部的试片与电解质溶液处温差变大，使加热挥发的水蒸气更易冷凝在试片表面。该方法重现性和加速性更好，试样腐蚀形貌特征更明显。
目前，以腐蚀失重法为基础建立了静态缓蚀实验，目的是评价气相缓蚀剂在常温、凝露条件下的气相防锈能力；动态缓蚀实验，目的是评价气相缓蚀剂在空气流通且温度变化的实验条件下的气相防锈能力。
4.1.3 实验条件的优化
进行腐蚀失重法测试时，气相缓蚀剂的预膜时间、温度以及试片的位置等都会对测定结果产生影响。翁永基[39]以MR-POM为例，研究了缓蚀剂预挥发和预膜时间对缓蚀效率的影响。魏刚等[40]研究了预挥发和预膜对DICHAN缓蚀性能的影响，结果表明，在进行预挥发和预膜后，防锈效果随预挥发和预膜时间的延长而显著提高。刘淑坤等[41]考察温度对气相缓蚀剂缓蚀效果的影响，对不同金属材料和气相缓蚀剂体系的影响各不相同。李海清等[42]综合国内外气相缓蚀剂缓蚀性能评价方法，对实验条件进行优化，得到最佳实验条件为：实验温度60 ℃；循环周期为加热8 h静置16 h，24 h为一个循环；实验周期为1 d；溶液为含NaHCO3、Na2SO4、NaCl的质量浓度分别为1 g/L的电解质溶液60 mL。
4.1.4 腐蚀失重法为基础的相关标准
早在20世纪50年代初美国和日本就颁布了气相缓蚀剂的测试标准。我国于20世纪80年代初才参照国外先进标准制定和颁布相关部门的行业标准。目前以腐蚀失重法为基础评价气相缓蚀剂性能的标准有很多，如联邦标准FED-STD-101中的4031项、美军标准Mil-85062、日本工业标准JISZ-1519-2019、国内机械行业标准GB/T 35491-2017。上述各标准的测试流程相似，按以下步骤进行：金属试样抛光清洗、测试溶液配制、实验装置选择、温度和相对湿度调控、预膜时长选定、金属试样腐蚀等级评定[43]。
国内GB/T 35491-2017介绍了如何加速消耗粉末状和液状气相缓蚀剂，挂片法和压片法两种气相缓蚀能力检测方法，再结合相容性实验和接触腐蚀性实验较全面的对气相缓蚀剂性能进行评价。但是腐蚀失重法评价气相缓蚀剂性能的测试仪器和方法，多年未有太大变化，测试周期也相对较长。
4.2 电化学分析法
金属的大气腐蚀是金属表面在薄层电解质液膜下的一种特殊形式的电化学腐蚀过程。因此，电化学测量技术和数据处理方法都可以使用。但由于液膜非常薄，传统的电化学研究方法很难对这种微量电解质体系准确地测量。因为当液膜极薄时，靠近被测金属电极表面的鲁金毛细管的参比电极会发生短路。所以，传统电化学方法需要根据薄液层体系的特点改进。对于气相缓蚀剂机理的电化学研究手段可以分为模拟大气腐蚀水全浸法和薄层电解质液法。
电化学测试法通过表征气相缓蚀剂与金属界面作用过程中产生的电化学信号，来研究缓蚀效率和缓蚀机理。电化学测试法具有快速简单、信息丰富以及原位测量等优点，现已成为研究气相缓蚀剂的主要手段。
4.2.1 模拟大气腐蚀水全浸法
4.2.2 薄层电解质液测试法
(1) 电阻探针
(2) 气相缓蚀剂监测器
气相缓蚀剂监测器 (VCIM) 是在电化学探测电池 (ACM) 的基础上优化改进得到的一种技术。利用ACM可以进行薄液层下的电化学研究，目前ACM技术因其简单、快速和准确等优点，广泛应用于金属大气腐蚀行为研究[54]。VCIM在ACM基础上改进，由多个大小相同的软钢板组成的，每个软钢板间通过聚酯薄膜绝缘，在环氧树脂内嵌入电池装置，形成的单金属双电极的气相缓蚀剂监测装置。
除上述两种方法外，近年科研人员对气相缓蚀剂在薄层液膜下的腐蚀分析提出多种思路。Zhang等[56]为在薄层液膜下三电极系统进行电化学测试，首先对钢样表面预膜，再将滤纸放置在钢样 (即工作电极) 上，在滤纸上滴加1 mL电解液，模拟薄层液膜，进行电化学测试。Wang等[57]为用电化学方法研究薄层液膜下气相缓蚀机理，建立了一套实验装置。该装置先将金属试样在NaCl溶液中浸泡3 min，待表面形成薄层液膜后，悬挂在含气相缓蚀剂和无气相缓蚀剂的密闭容器内，测试后进行对比。Ren等[58]为模拟气相缓蚀剂在海洋大气环境中对E36钢的缓蚀，搭建了一个电化学实验箱。该实验箱可模拟设定温度下的海洋大气，气相缓蚀剂均匀充满整个实验箱。采用三电极体系在电极上形成的薄层液膜进行开路电位、极化曲线和电化学阻抗等电化学测试。
4.2.3 极化曲线法
极化曲线法可直接获得Tafel斜率、腐蚀电流密度、腐蚀电位等参数，根据有无气相缓蚀剂的腐蚀电流密度计算可求出缓蚀率，还可以研究缓蚀剂对腐蚀电位、腐蚀速率、bA和bk等动力学参数的影响，因此该方法在判断缓蚀机理和评价缓蚀剂方面广泛应用。
极化曲线法常用于测定酸性介质中缓蚀剂对金属腐蚀速率的影响。该方法的缺点是：由强极化区的极化曲线外推到自腐蚀电位下得到的腐蚀速率有较大偏差；极化到Tafel直线段所需电流较大，易引起电极表面状态、真实表面积和周围介质的显著变化；另外，测定完整的极化曲线所需时间较长。冯礼奎等[59]采用极化曲线法研究了两种碳钢用气相缓蚀剂的缓蚀行为，结果表明这两种气相缓蚀剂都为阳极型，同腐蚀失重法测得的结果一致。
4.2.4 线性极化法
线性极化法 (LPR) 对工作电极外加电流极化，测得极化电阻，配合Tafel常数计算腐蚀电流和腐蚀速率[22]。该方法对腐蚀体系的干扰小、测量时间短、重现性好，对腐蚀变化响应快，能测得瞬时腐蚀速率，可快速连续测定金属腐蚀速率。
4.2.5 电化学阻抗谱技术
4.2.6 电化学噪声技术
4.2.7 电化学频率调制技术
4.2.8 扫描振动参比电极
扫描振动参比电极技术 (SVET) 可在探针不接触样品表面的情况下，测量局部电流、电位随远离被测电极表面位置的变化及样品在液下局部腐蚀电位[79]。SVET技术具有较好的空间分辨率，可观察材料表面发生氧化还原反应的区域，检测腐蚀处电流波动[80]。用于分析缓蚀剂于金属表面和腐蚀介质在微米甚至纳米尺度上的相互作用[81]。SVET的主要优点在于测试时间短、灵敏度高、无破坏性、可进行电化学活性测量，电化学活性谱图可以评价缓蚀剂分子在金属试样上离子电流分布的影响，进而了解金属和缓蚀剂相互作用期间的电化学过程[81, 82]。但腐蚀产物形成时，会导致SVET测量的电流变低，出现较大误差。虽然SVET可获得一些定量信息，但该技术不能取代评价缓蚀效率的传统方法，可以作为辅助手段使用[83]。
4.2.9 电化学石英晶体微天平
5 气相缓蚀剂膜形态和结构分析
腐蚀失重法和电化学方法可以有效评价气相缓蚀剂的缓蚀效率，但缺少金属表面损伤的形态信息[93]。气相缓蚀剂通常是在腐蚀电解液下的金属表面生成一层保护膜，其保护作用取决于表面膜结构和缓蚀剂对表面膜缺陷的修护能力，因此缓蚀膜的形态与结构分析是探明缓蚀机理和进一步评价缓蚀作用效果的基本研究内容。显微学法可以提供样品表面的微观形貌和腐蚀特征；光谱法和表面分析技术可以研究金属表面的缓蚀膜，表征缓蚀剂和金属表面的相互作用。
5.1 扫描电镜及能谱分析仪
Belarbi等[98]利用SEM和EDS技术对碳钢表面进行了表征，结果与电化学测试和腐蚀失重法得到的数据一致，发现癸硫醇有非常好的缓蚀性能和较高的持久性。
5.2 原子力显微镜
5.3 X射线光电子能谱
5.4 Fourier红外光谱技术
5.5 表面增强Raman散射光谱
6 气相缓蚀剂构效关系计算
气相缓蚀剂的构效关系是指研究化学物质与描述参数间数学关系，不仅能对气相缓蚀剂进行筛选，还可使缓蚀机理更明确，是分析气相缓蚀剂的重要手段[25]。过去气相缓蚀剂的选择标准主要是建立在实验室和现场测试的基础上，而现在量子化学计算 (QC) 和分子动力学模拟 (MD) 可以从理论上预测并计算气相缓蚀剂在特定环境中的缓蚀性能，有助于从理论上研究缓蚀性能和缓蚀机理与其分子结构、官能团电子分布及环境间的关系，在理论上指导高性能的缓蚀剂的设计、合成；也有助于从分子水平上探究缓蚀机理，发生化学变化时分子能量和几何形状的变化。
6.1 量子化学计算法
量子化学计算以量子力学为基础，包含Abinitio法、半经验分子轨道 (MNDO) 和密度泛函理论 (DFT)，旨在研究原子和分子的电子结构及电子间的相关作用[120]。
6.2 分子动力学模拟法
量子化学计算和分子动力模拟都可以研究缓蚀剂分子在金属表面的吸附过程及能量变化。但是QC只适用于几百个原子的体系，研究电子转移、原子变价的化学过程；MD适用于多达数百万个原子的体系，研究动力学过程、温度变化的体系。
7 展望
未来气相缓蚀剂分析方法的研究主要集中在以下几个方面：
(1) 针对应用于各种不同环境下的气相缓蚀剂，再对腐蚀失重法的测试条件进行定向优化改进，最大程度上还原气相缓蚀剂使用时的环境。
(2) 在结合薄层液膜的基础上，发展气相缓蚀机理研究的新型测试技术，同时使更多电化学测试技术能在薄层液膜上进行。借鉴薄层液膜条件下金属腐蚀行为的测试技术，对气相缓蚀剂在金属界面的缓蚀行为进行研究，进一步探索气相缓蚀剂的电化学缓蚀机理。
(3) 丝束电极是一种集成微电极阵列，该方法得到的数据重现性较好，可以用来测量薄液膜下金属的腐蚀电位。微液滴电极是使用微观尺寸的辅助电极和参比电极组成三电极体系，用于测量金属在电解质液滴下的局部腐蚀。这两种技术可用于金属表面薄层液膜的腐蚀分析，日后或可用于气相缓蚀剂在薄层液膜的缓蚀机理分析。
(4) 扫描电化学显微镜 (SECM) 可以提供研究样品的表面几何形貌，还可分辨不均匀电极表面的电化学活性，研究微区电化学动力学过程等。据文献可知，SECM已用于液相缓蚀剂体系中，未来在气相缓蚀剂领域的腐蚀分析亦有较大的前景。
(5) 电化学原子力显微镜(ECAFM)作为最重要的电化学扫描探针显微技术之一，可用于观察表面吸附物种的形态和结构、金属电极的氧化还原过程和金属表面电化学腐蚀过程。但该技术还未应用于气相缓蚀剂，在以后的气相缓蚀剂研究中可以尝试使用。
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[J].在湛江高湿热、高盐度、强辐照的热带海洋大气环境下，分别对有氧化皮与无氧化皮的SPHC热轧钢板进行了15，30，90和180 d暴晒实验，研究了氧化皮对SPHC热轧钢板的初期腐蚀行为的影响。采用X射线衍射仪分析了氧化皮与锈层的组成成分，采用扫描电镜观察了腐蚀产物表面和截面的微观形貌，采用X射线能谱仪分析了锈层的元素分布，同时对暴晒后的试样进行极化曲线测试。结果表明，氧化皮的主要组成成分为Fe<sub>3</sub>O<sub>4</sub>，可以明显减缓钢的早期腐蚀速率。随着腐蚀的进行，氧化皮逐渐转化为锈层，腐蚀产物不断生成，有氧化皮试样与无氧化皮试样的腐蚀行为逐渐趋于一致，腐蚀速率差别较小。氧化皮通过屏蔽作用减缓了钢的早期腐蚀速率，并没有改变腐蚀产物的成分。
Mechanism of galvanic corrosion of coupled 2024 Al-alloy and 316L stainless steel beneath a thin electrolyte film studied by real-time monitoring technologies
[J].
实时监测技术研究薄液膜下电偶腐蚀的机理
[J].采用大气腐蚀检测技术 (ACM)、零电阻电流技术 (ZRA) 以及电化学阻抗谱技术 (EIS) 对2024铝合金与316L不锈钢在薄液膜下的电偶腐蚀行为进行了实时监测。结果表明,电偶腐蚀的过程可分为诱导期、加速期和减速期3个阶段。随着两电极之间距离的减小,电偶腐蚀会快速诱发,且腐蚀速率迅速增加,但电偶腐蚀的加速期变短。
Application of micro-electrochemical technologies in atmospheric corrosion of thin electrolyte layer
[J].
微区电化学技术在薄液膜大气腐蚀中的应用
[J].
Electrochemical principle analysis of scanning kelvin probe
[J].
扫描Kelvin探针的电化学原理分析
[J].
Research progress of galvanic corrosion in marine environment
[J].
海洋环境中金属电偶腐蚀研究进展
[J].
Applications of kelvin probe technique in the studies of atmospheric corrosion
[J].
Kelvin探头参比电极技术在大气腐蚀研究中的应用
[J].Kelvin探头参比电极技术是近年来大气腐蚀领域中最为活跃的研究方向之一。它能够不接触、无破坏的检测薄液膜甚至涂层下金属表面的腐蚀电位分布。文中介绍了该技术的发展历史、技术要点，着重讨论了该技术在研究金属表面有机涂层的剥离和薄液层下金属的腐蚀两方面的应用。
Evaluation of environmental factors related with atmosphere corrosivity in hunan provice by atmospheric corrosion monitoring technique
[J].
湖南地区大气腐蚀严酷性的环境因素与大气腐蚀监测仪评定
[J].
Comparison study of volatile corrosion inhibitors in steam And Cl2 gas environment on mild steel
[J].
Technical note: cyclohexylamine carbonate as vapor phase inhibitor for Nd-Fe-B magnet
[J].
Protective behavior of volatile corrosion inhibitor on atmospheric corrosion process of carbon steel under thin electrolyte liquid film of chloride solutions
[J].The corrosion process of carbon steel and corrosion resistance behavior of volatile corrosion inhibitor (VCI) under thin electrolyte liquid film containing chloride was investigated by electrochemical measurements and surface characterization. Results indicated that composite VCI was\n composed of sodium molybdate and sodium benzoate, and exhibited higher corrosion resistance in 3.5% NaCl solution compared with absence of VCI. The corrosion current density obviously decreased with presence of VCI, and the synergies between binary components increased the corrosion inhibiting\n rate on carbon steel to up to 90%. The corrosion current density of carbon steel increased with increased temperature after volatilization of VCI. A closed container was carried out to mimic atmospheric corrosion condition, and its vapor corrosion inhibition property was evaluated in this\n closed container. Results showed that the VCI acted as an inhibitor by suppressing anodic dissolution and metallic ion transfer through the formation of protective film. It was also observed that the variation of carbon steel surface with volatilization of VCI was assessed by atomic force\n microscope (AFM) and scanning electron microscope (SEM). The anodic process for carbon steel without VCI affected the corrosion rate due to accumulation of corrosion products, while the morphology of carbon steel was hardly changed with volatilization of VCI. The results showed that the VCI\n volatilized to the surface and form to protect film. VCI was automatically volatilized into gas, which protected steel from corrosion. This composite VCI can then be applied as a significant corrosion inhibition method.
Study on vapor phase corrosion inhibitor for E36 ship steel in marine atmospheric environment
[J].This study aims to investigate the effect of vapor phase corrosion inhibitor (VCI) imidazoline, quinoline and urea on E36 ship steel in simulated marine atmospheric environment.
Corrosion inhibition behavior of salt-type vapor phase corrosion inhibitor for carbon steel
[J].
碳钢用盐型气相缓蚀剂的缓蚀行为
[J].
Current status and trend of corrosion monitoring techniques
[J].
腐蚀监测技术现状及发展趋势
[J].
Screening the corrosion inhibitor by linear polarization resistance technology
[J].
应用线性极化电阻法现场筛选缓蚀剂
[J].
A method to measure corrosion rate by combination of ac impedance and weak polarization
[J].
一种交流阻抗和弱极化相结合的腐蚀速度测量方法
[J].
Review of mechanistic analysis by electrochemical impedance spectroscopy
[J].
A concise review on corrosion inhibitors: types, mechanisms and electrochemical evaluation studies
[J].
Surface modification for Al alloy by volatile corrosion inhibitors from cyclohexylamine, octanoic acid, and their reaction product
[J].
Noise-analysis applied to electrochemical systems
[J].
Electrochemical emission spectroscopy for monitoring uniform and localized corrosion
[J].
Corrosion monitoring system based on measurement and analysis of electrochemical noise
[J].
Electrochemical noise analysis of polyurethane-coated steel subjected to erosion-corrosion
[J].
Analysis and application of electrochemical noose I. Theory of electrochemical noise analysis
[J].
电化学噪声的分析与应用——Ⅰ.电化学噪声的分析原理
[J].
Electrochemical noise (EN) technique: review of recent practical applications to corrosion electrochemistry research
[J].The ability to analyze different electrochemical corrosion phenomena, in-situ, without requiring any form of electrode perturbation has strongly attracted the attention of corrosion researchers towards the application of electrochemical noise (EN) analysis method. With the ability to analyze stochastic and chaotic electrode potential and current fluctuations at E-OCP, the EN analysis method is capable of providing information about the kinetics and mechanism of metallic corrosion with accuracy that can match conventional electrochemical techniques. Herein, we review the recent applications of EN analysis method to electrochemical corrosion research. We discuss briefly the theory behind the measurement of EN, and then highlight some of its application in the evaluation of corrosion inhibitors, pitting corrosion, coatings on metals, microbiologically-induced corrosion, as well as CO2-corrosion. The drawbacks of the EN analysis method have also been highlighted and future considerations on the use of this important electrochemical technique have also been proposed.
Corrosion of pure magnesium under thin electrolyte films Ⅱ-influence of thin electrolyte films on anodic process of pure magnesium corrosion
[J].
利用电化学方法研究纯镁在薄液膜下的腐蚀行为Ⅱ-薄液膜对纯镁腐蚀阳极过程的影响
[J].
Monitoring of crevice corrosion with the electrochemical frequency modulation technique
[J].
Synthesis and characterization of novel fatty alcohol ethoxylate surfactants for corrosion inhibition of mild steel
[J].
Sodium alginate: a promising biopolymer for corrosion protection of API X60 high strength carbon steel in saline medium
[J].
Application of electrochemical measurement technology in the inhibition behavior research of corrosion inhibitors
[J].
电化学测试技术在缓蚀剂缓蚀行为研究中的应用
[J].
A new 1,2,4-triazole derivative as an excellent corrosion inhibitor: electrochemical experiments with theoretical validation
[J].
Novel gossypol–indole modification as a green corrosion inhibitor for low–carbon steel in aggressive alkaline–saline solution
[J].
Application of micro-area electrochemical method in the field of galvanic corrosion
[J].
微区电化学方法在电偶腐蚀领域的应用
[J].
Review on corrosion test methods and evaluation techniques for materials in atmospheric environment
[J].
材料大气环境腐蚀实验方法与评价技术进展
[J].从大气腐蚀加速试验方法、大气腐蚀电化学方法及大气腐蚀监检测技术对大气腐蚀试验方法进行了综述。大气腐蚀加速试验中，多因子循环复合腐蚀试验已经成为模拟大气腐蚀加速试验的主要发展方向；同时，随着电化学方法空间分辨率的提升，大气腐蚀电化学方法也从宏观电化学技术向微区电化学技术延伸；另外，随着物联网及计算机技术的发展，基于数据挖掘及机器学习等现代化的数据处理技术也在大气腐蚀监检测技术中得到了应用。
SVET study of the interaction of 2-mercaptobenzothiazole corrosion inhibitor with Au, Cu and Au-Cu galvanic pair
[J].
Review of corrosive environments for copper and its corrosion inhibitors
[J].
Concerning the efficiency of corrosion inhibitors as given by SVET
[J].
Corrosion inhibition of galvanized steel in NaCl solution by tolytriazole
[J].
Localized corrosion behavior studies by SVET of 1010 steel in different concentrations of sodium chloride containing [m-2HEA][Ol] ionic liquid as corrosion inhibitor
[J].
Application of electrochemical quartz crystal microbalance
[J].Electrochemical Quartz Crystal Microbalance (EQCM) is a testing technique that combines quartz crystal microbalance (QCM) and electrochemical detection. EQCM is one of effective methods to study the surface reaction due to its simplicity, rapidness, and the ability to dynamically detect the deposition, adsorption, or dissolution of an active material on a quartz crystal at nanogram level. At the same time, because the EQCM testing technology is an in-situ testing method, online real-time monitoring can be realized. With its high precision and high sensitivity, it is possible to further analyze the reaction process and deep-level mechanism at the surface interface. This paper summarizes the application of EQCM in the fields of electrochemical, biomedical and oil field chemistry, as well as research mechanism and dynamics, and puts forward the new research direction of EQCM and the problems in its development.<br>Contents<br>1 Introduction<br>2 Application of EQCM in electrochemistry<br>2.1 Application of EQCM in electro-synthesis<br>2.2 Application of EQCM in electrode-position and dissolution<br>2.3 Application of EQCM in adsorption and desorption<br>2.4 Application of EQCM in polymer modified electrode<br>2.5 Membrane ionic, charge conduction movement and determination<br>2.6 EQCM in energy conversion and storage applications<br>3 Application of EQCM in biomedical and oilfield chemistry<br>4 Application of EQCM in other areas<br>4.1 Gas detection<br>4.2 Structural characterization<br>5 Application of EQCM in study of the reaction process of kinetics and mechanism<br>5.1 Study of reaction mechanism by EQCM<br>5.2 Study on thermodynamics and kinetics of reaction process by EQCM<br>6 Conclusion
电化学石英晶体微天平的应用
[J].电化学石英晶体微天平（EQCM）即石英晶体微天平（QCM）与电化学检测相结合的测试技术。电化学石英晶体微天平以其简单、快速，可以在纳克级水平上对活性物质在石英晶振片上发生的沉积、吸附或溶解等过程进行动态检测等优势而成为表界面反应研究的有效手段之一。由于EQCM测试技术为原位测试方法，可以实现在线实时监测，利用其高精度和高灵敏度可以进一步对表界面上发生反应的过程及深层次的机理进行分析。本文就EQCM在电化学、生物医学及油田化学等领域以及研究机理及动力学等方面的应用进行了总结阐述，提出了EQCM的研究新方向以及发展中面临的问题。
A systematic investigation of current efficiency during brass deposition from a pyrophosphate electrolyte using RDE, RCE, and QCM
[J].
Anodic behavior of copper in acetonitrile: the influence of carbon dioxide and dimethylamine
[J].
Review on the application of quartz crystal microbalance in the research of metal corrosion
[J].
石英晶体微天平在金属腐蚀研究中的应用
[J].
Application of the quartz crystal microbalance technique in corrosion studies. A review
[J].
A comparative electrochemical and quantum chemical calculation study of BTAH and BTAOH as copper corrosion inhibitors in near neutral chloride solution
[J].
A study on the filming kinetics of corrosion inhibitors in Fe/Na2SO4 system using EQCM
[J].
Electrochemical characterization and surface morphology techniques for corrosion inhibition—a review
[J].
A combined electrochemical and theoretical analysis of environmentally benign polymer for corrosion protection of N80 steel in sweet corrosive environment
[J].
Analysis the theory and application of SEM and EDS analytical method
[J].
解析SEM&EDS分析原理及应用
[J].
Development of modern SEM and its application in material science
[J].
现代扫描电镜的发展及其在材料科学中的应用
[J].
Application of SEM with EDX in material analysis
[J].
带能谱分析的扫描电子显微镜在材料分析中的应用
[J].
Thiols as volatile corrosion inhibitors for top-of-the-line corrosion
[J].
How the atomic force microscope works?
[A]. BragaPC, RicciD. Atomic Force Microscopy in Biomedical Research [M].
AFM in liquid and on-spot study of metal corrosion
[J].
液相型AFM的研制与金属腐蚀原位研究
[J]. 光电子·激光,
A review of the application of atomic force microscopy in wood science research
[J].
原子力显微镜在木材科学研究中的应用
[J].
Film formation mechanism of carboxylic acid-based volatile corrosion inhibitors on 45 steel surface
[J].
45钢表面羧酸类气相缓蚀剂的成膜机理
[J].
Application of X-ray photoelectron spectroscopy in material surface research
[J].
X射线光电子能谱在材料表面研究中的应用
[J].
Enhanced photocatalytic activity in Ag-nanoparticle-dispersed BaTiO3 composite thin films: role of charge transfer
[J].
Copper-nanoparticle-dispersed amorphous BaTiO3 thin films as hole-trapping centers: enhanced photocatalytic activity and stability
[J].
SPR enhanced photocatalytic properties of Au-dispersed amorphous BaTiO3 nanocomposite thin films
[J].
Application of X-ray photoelectron spectroscopy in material surface analysis
[J].
X射线光电子能谱技术在材料表面分析中的应用
[J].
Comparative study of bis-piperidiniummethyl-urea and mono-piperidiniummethyl-urea as volatile corrosion inhibitors for mild steel
[J].
Thermal analysis and FTIR studies of volatile corrosion inhibitor model systems
[J].
Traditional Chinese medicine extracts as novel corrosion inhibitors for AZ91 magnesium alloy in saline environment
[J].Zingiber officinale Roscoe extract, Raphanus sativus L. extract, Rheum palmatum extract, Coptis chinensis extract, Glycyrrhiza uralensis extract (GUE), Potentilla discolor extract (PDE) and Taraxacum officinale extract (TOE) were screened for the green corrosion inhibitors of AZ91 alloy in saline environment. The experiment results demonstrated that GUE, PDE and TOE can significantly enhance the corrosion resistance of AZ91 alloy by 73.4, 87.6 and 84.6%, respectively. Surface characterization using FTIR, UV-Vis and XPS revealed that the organic compounds of GUE, PDE and TOE can interact with the alloy surface to form a protective physisorbed film, effectively mitigating the corrosion process of AZ91 alloy. The present results may be helpful to discover the new green inhibitors with high inhibition efficiency for AZ91 alloy.© 2022. The Author(s).
Surface-enhanced Raman spectroscopy (SERS): progress and trends
[J].Surface-enhanced Raman spectroscopy (SERS) combines molecular fingerprint specificity with potential single-molecule sensitivity. Therefore, the SERS technique is an attractive tool for sensing molecules in trace amounts within the field of chemical and biochemical analytics. Since SERS is an ongoing topic, which can be illustrated by the increased annual number of publications within the last few years, this review reflects the progress and trends in SERS research in approximately the last three years. The main reason why the SERS technique has not been established as a routine analytic technique, despite its high specificity and sensitivity, is due to the low reproducibility of the SERS signal. Thus, this review is dominated by the discussion of the various concepts for generating powerful, reproducible, SERS-active surfaces. Furthermore, the limit of sensitivity in SERS is introduced in the context of single-molecule spectroscopy and the calculation of the 'real' enhancement factor. In order to shed more light onto the underlying molecular processes of SERS, the theoretical description of SERS spectra is also a growing research field and will be summarized here. In addition, the recording of SERS spectra is affected by a number of parameters, such as laser power, integration time, and analyte concentration. To benefit from synergies, SERS is combined with other methods, such as scanning probe microscopy and microfluidics, which illustrates the broad applications of this powerful technique.
Surface-enhanced spectroscopy: toward practical analysis probe
[J].Surface-enhanced spectroscopy (SES) is a consequence of extreme electromagnetic fields and chemical interactions near a surface. SES is highly sensitive and selective and has been exploited in chemistry, physics, biology, and medicine. It is a rapidly developing technique and is expected to become an important analysis tool. This review introduces theories and concepts of SES techniques including surface-enhanced (SE) Raman scattering, SE infrared absorption, SE chiroptical spectroscopy, and SE fluorescence. Then recent research and applications are discussed to indicate current challenges and future directions.
Application of laser raman spectroscopy to the research of metal corrosion
[J].
激光拉曼光谱在金属腐蚀研究中的应用
[J].
Periodic trends in electrode-chemisorbate bonding: benzonitrile on platinum-group and other noble metals as probed by surface-enhanced Raman spectroscopy combined with density functional theory
[J].Detailed intramolecular vibrational spectra obtained by means of surface-enhanced Raman scattering (SERS) for benzonitrile adsorbed on seven electrode surfaces-four Pt-group metals (platinum, palladium, rhodium, and iridium) and the Group IB metals (copper, silver, and gold)-are reported with the aim of exploring the metal-dependent nature of surface-chemisorbate interactions. The Pt-group surfaces were prepared as ultrathin electrodeposited films on gold, enabling the SERS activity inherent to the substrate to be imparted to the overlayer material. Benzonitrile was selected as a "model" organic adsorbate since it displays a rich array of coupled aromatic ring as well as substituent modes which collectively can provide insight into the various molecular perturbations induced by surface coordination via the nitrile substituent. The experimental spectra are compared with ab initio calculations of vibrational frequencies, bond geometries, and charge distributions obtained by means of Density Functional Theory (DFT), which yields valuable insight into the underlying structural reasons for the sensitivity of the experimental coordination-induced frequency shifts to the nature of the intramolecular mode and the metal surface. The DFT results also form an invaluable aid in making SER spectral assignments, along with providing detailed information on the coupled atomic displacements involved in each vibrational mode. Benzonitrile surface coordination was modeled in the DFT calculations by binding the nitrile group to metal atoms and small metal clusters. While the majority of the aromatic-ring SER frequencies are altered only slightly (approximately < 5 cm(-1)) upon surface coordination, several modes (especially nu(1), nu(6a)) are blue-shifted substantially (by up to 50 cm(-1)). These shifts were identified by DFT as arising from mode coupling to the nitrile substituent, especially involving the C-CN bond that is compressed upon nitrile coordination, associated with metal-adsorbate back-donation. The small (<5 cm(-1)) red-shifts seen for ring vibrations not involving coupled substituent motion apparently arise from increased antibonding aromatic electron density. The metal-dependent frequency shifts seen for these coupled aromatic vibrations as well as for the more localized C-N nitrile stretching mode are consistent with increased back-donation anticipated in the sequence d(10) < d(9) < d(8) within a given Periodic row. Overall, the findings provide a benchmark illustration of the virtues of DFT in interpreting complex vibrational spectra for larger polyatomic adsorbates.
Surface-enhanced Raman scattering (SERS) spectroscopy of corrosion inhibitors: high-resolution detection, adsorption property, and inhibition mechanism
[J].
Review on the Raman spectroscopy of different types of layered materials
[J].Two-dimensional layered materials, such as graphene and transition metal dichalcogenides (TMDs), have been under intensive investigation. The rapid progress of research on graphene and TMDs is now stimulating the exploration of different types of layered materials (LMs). Raman spectroscopy has shown its great potential in the characterization of layer numbers, interlayer coupling and layer-stacking configurations and will benefit the future explorations of other LMs. Lattice vibrations or Raman spectra of many LMs in bulk have been discussed since the 1960s. However, different results were obtained because of differences or limitations in the Raman instruments at early stages. The developments of modern Raman spectroscopy now allow us to revisit the Raman spectra of these LMs under the same experimental conditions. Moreover, to the best of our knowledge, there were limitations in detailed reviews on the Raman spectra of these different LMs. Here, we provide a review on Raman spectra of various LMs, including semiconductors, topological insulators, insulators, semi-metals and superconductors. We firstly introduce a unified method based on symmetry analysis and polarization measurements to assign the observed Raman modes and characterize the crystal structure of different types of LMs. Then, we revisit and update the positions and assignments of vibration modes by re-measuring the Raman spectra of different types of LMs and by comparing our results to those reported in previous papers. We apply the recent advances on the interlayer vibrations of graphene and TMDs to these various LMs and obtain their shear modulus. The observation of the shear modes of LMs in bulk facilitates an accurate and fast characterization of layer numbers during preparation processes in the future by a robust layer-number dependency on the frequencies of the shear modes. We also summarize the recent advances on the layer-stacking dependence on the intensities of interlayer shear vibrations. Finally, we review the recent advances on Raman spectroscopy in the characterization of anisotropic LMs, such as black phosphorus and rhenium diselenide. We believe that this review will benefit the future research studies on the fundamental physics and potential applications of these various LMs, particularly when they are reduced down to monolayers or multilayers.
Surface-enhanced Raman spectroscopic studies on the inhibition mechanisms for imidazole on zinc surfaces
[J].
咪唑对锌缓蚀机理的表面增强拉曼光谱研究
[J].
Monitoring the adsorption of volatile corrosion inhibitors in real time with surface-enhanced Raman spectroscopy
[J].
Study on the preparation and corrosion inhibition of Schiff-base self-assembled membranes
[J].This paper aims to evaluate the inhibitive effect and adsorption behavior of the 2-amino-5-thiol-1,3,4-thiadiazole vanillin (A) on copper in 3 per cent NaCl solution.
adsorption and corrosion inhibition studies of some selected dyes as corrosion inhibitors for mild steel in acidic medium: gravimetric, electrochemical, quantum chemical studies and synergistic effect with iodide ions
[J].The corrosion inhibition properties of some organic dyes, namely Sunset Yellow (SS), Amaranth (AM), Allura Red (AR), Tartrazine (TZ) and Fast Green (FG), for mild steel corrosion in 0.5 M HCl solution, were investigated using gravimetric, potentiodynamic polarization techniques and quantum chemical calculations. The results showed that the studied dyes are good corrosion inhibitors with enhanced inhibition efficiencies. The inhibition efficiency of all the studied dyes increases with increase in concentration, and decreases with increase in temperature. The results showed that the inhibition efficiency of the dyes increases in the presence of KI due to synergistic interactions of the dye molecules with iodide (I(-)) ions. Potentiodynamic polarization results revealed that the studied dyes are mixed-type inhibitors both in the absence and presence of KI. The adsorption of the studied dyes on mild steel surface, with and without KI, obeys the Langmuir adsorption isotherm and involves physical adsorption mechanism. Quantum chemical calculations revealed that the most likely sites in the dye molecules for interactions with mild steel are the S, O, and N heteroatoms.
Inhibition behavior of chitooligosaccharide derivatives for carbon steel in 3.5% NaCl solution
[J].
Caprylate salts based on amines as volatile corrosion inhibitors for metallic zinc: Theoretical and experimental studies
[J].The interaction of volatile corrosion inhibitors (VCI), caprylate salt derivatives from amines, with zinc metallic surfaces is assessed by density functional theory (DFT) computer simulations, electrochemical impedance (EIS) measurements and humid chamber tests. The results obtained by the different methods were compared, and linear correlations were obtained between theoretical and experimental data. The correlations between experimental and theoretical results showed that the molecular size is the determining factor in the inhibition efficiency. The models used and experimental results indicated that dicyclohexylamine caprylate is the most efficient inhibitor.
Theoretical evaluation of 2-aminofluorenic double schiff base corrosion inhibitor based on quantum chemistry
[J].
基于量子化学的2-氨基芴双希夫碱缓蚀剂的理论评价
[J].
Cabbage extract as an eco-friendly corrosion inhibitor for X70 steel in hydrochloric acid medium
[J].
Mechanism of temperature influence on adsorption of schiff base
[J].
温度影响席夫碱缓蚀剂吸附的机理研究
[J].研究了所合成的两种含有苯基基团的席夫碱缓蚀剂 (BB-S缓蚀剂和B-S缓蚀剂) 在不同温度下对N80钢在0.5%盐酸溶液中的缓蚀作用，探讨了温度影响席夫碱缓蚀剂的吸附机理。结果表明，BB-S缓蚀剂和B-S缓蚀剂的缓蚀效率随着温度的升高而降低，且B-S缓蚀剂的缓蚀效率在不同温度下始终大于BB-S缓蚀剂的缓蚀效率。分子动力学和量子化学计算方法表明，两种席夫碱缓蚀剂的缓蚀效率随温度的升高而降低，该现象与席夫碱缓蚀剂中苯环较大的空间位阻、分子热运动、分子吸附构型以及前线轨道能级密切相关。
