缓蚀剂在阳极电泳涂装中的应用

在电泳涂装工艺中使用缓蚀剂，可提高阳极电泳涂层的防腐蚀性，实验表明，沥青电泳漆与缓蚀剂的电泳共沉积涂层对基底金属具有较高的防护性能，探讨了共沉积涂层中缓蚀剂的缓蚀机理。     

金属缓蚀剂Gemini型咪唑啉双季铵盐的合成及其性能的研究

合成了系列新型咪唑啉双季铵盐阳离子缓蚀剂（S-HSJ）,研究并讨论了其在5%盐酸介质中对铜、铝等金属的缓蚀性能及缓蚀剂结构中亲油基部分碳链长度、缓蚀时间、缓蚀剂浓度等对缓蚀效果的影响。研究表明：S-HSJ系列咪唑啉双季铵盐对红铜、黄铜、铝及马口铁四种金属均表现出较传统单季铵盐与苯并三氮唑缓蚀剂好的缓蚀性能,S-HSJ-16双季铵盐添加量0.1%时缓蚀效率可达94~99%,S-HSJ与阴离子表面活性剂复配对铜腐蚀表现出明显协同效应。     

盐酸介质中水杨醛缩氨基硫脲对碳钢的缓蚀作用

合成了新型席夫碱缓蚀剂:水杨醛缩氨基硫脲(ST),并考察了其在1 mol/L盐酸溶液中对碳钢的缓蚀性能。通过静态失重、动电位极化曲线、交流阻抗等技术手段研究缓蚀剂浓度对腐蚀速率及缓蚀效率的影响,阐明缓蚀作用机理。结果表明,ST在盐酸介质中对碳钢具有良好的缓蚀性能。随着缓蚀剂浓度的增加,缓蚀效率逐渐增大。ST的加入显著降低了自腐蚀电流密度,为抑制阴极反应为主的缓蚀剂。ST在碳钢表面的吸附符合Langmuir吸附模型,为物理吸附与化学吸附共同作用。     

Gemini型咪唑啉双季铵盐金属缓蚀剂的合成及其性能

合成了系列新型咪唑啉双季铵盐阳离子缓蚀剂(S-HSJ),研究并讨论了其在5%HCl介质中对铜、铁、铝等金属的缓蚀性能及缓蚀剂结构中亲油基部分碳链长度、缓蚀时间、缓蚀剂浓度等对缓蚀效果的影响. 研究表明,S-HSJ系列咪唑啉双季铵盐对红铜、黄铜、铝及马口铁四种金属均表现出较传统单季铵盐与苯并三氮唑缓蚀剂好的缓蚀性能,S-HSJ-16双季铵盐添加量0.1%时缓蚀效率可达94%~99%,S-HSJ与阴离子表面活性剂复配对铜腐蚀表现出明显协同效应.     

金属缓蚀剂的研究进展

金属以及合金具有良好的延展性、导热性、导电性等优点,是人类生产和生活中不可或缺的材料之一,广泛应用于化工、制造、建筑以及航空航天等众多领域.除了少数重金属(如金、铂和银等)以外,绝大多数的金属以及合金都存在一个致命的缺点,就是它们的不稳定性,会与环境中的物质发生化学或者电化学反应从而产生腐蚀现象.而且,这个反应过程是自发进行的、不可逆的.腐蚀问题不仅会造成直接或者间接的经济损失,而且还会导致重大的安全隐患和事故.因此,延缓金属的腐蚀历来是工业界和学术界广泛关注的课题.目前,延缓金属腐蚀的手段和方法很多,主要有以下几种,改变金属的组成,加入耐腐蚀的金属形成相应的合金;使用抗腐蚀能力较强的金属;在金属表面形成耐腐蚀的涂层;加入缓蚀剂等.其中,添加缓蚀剂是一种操作简单、成本低廉、适用范围广的金属缓蚀方法.经过多年的研发,目前已知的缓蚀剂种类很多并且还在不断增加.有机小分子缓蚀剂是其中最重要的一类缓蚀剂.它的缓蚀原理是缓蚀剂吸附在金属表面形成保护膜,隔离了金属和环境价质,阻止金属和环境中的物质发生反应,从而达到缓蚀的目的.这类缓蚀剂的种类繁多、适用范围广、缓蚀效率高,而且有机小分子易于合成、原料丰富易得、价格低廉.但是,无论是合成还是应用有机小分子缓蚀剂,都会造成严重的环境污染问题,不符合可持续发展的观念.而且,绝大多数的有机小分子缓蚀剂具有毒性,无法应用于医疗或者食品领域.因此,科学家们开始致力于寻找绿色、环保和天然的缓蚀剂.离子液体、氨基酸以及天然植物提取物是其中三类重要的缓蚀剂.本文详细介绍了近20年来上述三种缓蚀剂的发展历程,总结了它们的分子结构、缓蚀效果和相应的缓蚀机制.最后,总结了目前缓蚀剂发展中存在的问题,希望在了解缓蚀剂发展思路和缓蚀机制的前提下,设计和合成缓蚀效率更高和更为环保的缓蚀剂.     

胡麻籽油咪唑啉类缓蚀剂的制备及其缓蚀性能

以胡麻籽油、羟乙基乙二胺为原料合成咪唑啉中间体,用苄基氯进行改性,得到阳离子咪唑啉衍生物。利用FT IR对合成产物进行了表征,用静态失重法、电化学极化曲线和FESEM对其缓蚀性能进行了评价,并考察了不同缓蚀剂浓度、腐蚀浸泡时间对缓蚀效果的影响,探讨了其在A30钢表面的吸附行为。结果表明,合成的缓蚀剂在盐酸体系中对A30钢有较好的缓蚀性能,在浓度为100mg/L时对低碳钢的缓蚀效率可达87%,并且其产物为阳离子型缓蚀剂,吸附满足Langmuir等温吸附方程。最后采用量子化学方法对其缓蚀剂的缓蚀机理进行了分析。     

胡麻籽油咪唑啉缓蚀剂的制备及其对A30钢的缓蚀效果

以胡麻籽油、羟乙基乙二胺为原料合成咪唑啉中间体,用苄基氯进行改性,得到阳离子咪唑啉衍生物。利用FT IR对合成产物进行了表征,用静态失重法、电化学极化曲线和FESEM对其缓蚀性能进行了评价,并考察了不同缓蚀剂浓度、腐蚀浸泡时间对缓蚀效果的影响,探讨了其在A30钢表面的吸附行为。结果表明,合成的缓蚀剂在盐酸体系中对A30钢有较好的缓蚀性能,在浓度为100mg/L时对低碳钢的缓蚀效率可达87%,并且其产物为阳离子型缓蚀剂,吸附满足Langmuir等温吸附方程。最后采用量子化学方法对其缓蚀剂的缓蚀机理进行了分析。     

多点位吸附型咪唑啉季铵盐缓蚀剂的合成及其缓蚀性能

以对二甲氨基苯甲酸、二乙烯三胺和氯化苄为原料,两步法合成了一种新型具有多个潜在吸附中心的季铵盐型咪唑啉缓蚀剂（MIQ）,利用傅里叶变换红外光谱对合成的产物进行了表征。 通过失重法研究了该缓蚀剂在6%盐酸溶液中对碳钢的缓蚀性能。 讨论了缓蚀剂用量、温度、时间对缓蚀性能的影响,并研究了其与某些物质复配后的协同作用。 结果表明,合成的季铵盐型咪唑啉缓蚀剂在6%的盐酸腐蚀环境中,用量为0.5%时对碳钢的缓蚀率可达97%以上,缓蚀率随温度的升高和时间的延长而降低。 MIQ与乌洛托品、KSCN以及KI等复配后可以显著改善缓蚀剂的缓蚀率。 从吸附等温线推测,该缓蚀剂抑制腐蚀的机理是缓蚀剂在碳钢表面吸附成膜,进而有效阻挡了碳钢表面与酸性清洗试剂的接触。     

氨基酸缓蚀剂在盐酸溶液中对钢的缓蚀作用

应用极化曲线、电化学阻抗谱等测试技术,研究了以谷氨酸作缓蚀剂在10%盐酸介质中对X65钢的缓蚀作用,测试腐蚀参数包括腐蚀电位(Ecorr)、极化电阻(Rp)、缓蚀效率(η)等.研究表明:该缓蚀剂是一种抑制阴极为主的混合型缓蚀剂,在较低的浓度具有良好缓蚀效果;缓蚀效率随着浓度的增加而提高,并在0.3g.L-1时达到最大值(90%以上).     

具有表面活性的杂环缓蚀剂的合成及性能评价

以2-氨基苯并咪唑、氰尿酰氯、正己胺以及N,N-二甲基-1,3-丙二胺为原料,合成一种具有表面活性的杂环类缓蚀剂。通过测定含不同浓度缓蚀剂的盐酸溶液的表面张力来研究其表面性能。采用失重法和动电位极化及电化学阻抗谱方法考察了其与2-氨基苯并咪唑在盐酸介质中对碳钢的缓蚀行为,并通过扫描电镜观察了腐蚀碳钢试片的外貌形态。结果表明,表面活性以及多活性吸附中心的引入提高了缓蚀剂在碳钢表面的吸附能力,合成的缓蚀剂的缓蚀性能比2-氨基苯并咪唑有显著提高。在实验范围内,缓蚀剂的缓蚀效率随浓度增大而提高,电化学测试表明其为一种混合型缓蚀剂。     

Influence of inhibitor structure and metal/solution interface on the corrosion resistance of the protected metal

Seven systems of more than 60 compounds with possible inhibiting properties are investigated. Several methods are used: electrochemical, gravimetric, XPS, and SEM analyses. The inhibition efficiency Z is related to the chemical structure of inhibitors (sequences of compounds with regard to Z are found), their electronic structure, the surface area of the inhibiting molecule, and the structure and composition of the metal/solution interface (impedance, adsorption equilibrium parameters, etc.). The most efficient of the investigated inhibitors have Z = 94–99%. Conclusions are drawn which allow identification of compounds with prognosticated inhibiting action. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 11, pp. 1352–1364. Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22, 2005, Moscow. The text was submitted by the authors in English.     

Sources of electrochemical noise in corroding systems

The electrochemical noise method is reasonably well established as a technique that can estimate corrosion rate through the electrochemical noise resistance or impedance. A more interesting potential application is the identification of the nature of the corrosion process. In this paper, a number of corrosion types are examined, and it is concluded that the majority constitute a form of shot noise, possibly with a superimposed baseline current. Methods by which parameters describing the shot noise process can be estimated from the measured data are presented. It appears to be feasible to extract the charge in the shot noise events, and their frequency, providing all of the anodic or cathodic current, is associated with these events. However, the analysis requires a number of assumptions that are not always valid, and these are discussed. Finally, some alternative methods that have been used to identify the type of corrosion are briefly discussed. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 5, pp. 557–566. The text was submitted by the author in English.     

Analysis of pitting corrosion rate

A method for estimating pitting corrosion rate is proposed. The method is based on the analysis of anodic and cathodic voltammograms that were measured on the specimens of two types: on the test specimen coated with an oxide film, which formed under the open-circuit conditions, and on the specimen, whose surface was totally activated with aggressive ions. The use of Tafel portions of these voltammograms in various combinations enables us to estimate the corrosion potential and corrosion current for general corrosion proceeding in the induction period, for pitting corrosion at the initial stage of its development, for a highly developed pitting corrosion, when the major area of specimen surface is occupied with pits, and also in the intermediate case.     

金属腐蚀与防护简谈

本文简要阐明了为什么金属的腐蚀主要以电化学腐蚀的形式出现,剖析了腐蚀过程电化学动力学参数的物理意义,以及金属腐蚀的防护原理、常用的腐蚀防护方法乃至腐蚀过程的一些特殊应用。     

Adsorptive passivation of iron by organic acid anions

Studies on the iron passivation by organic acid anions in aqueous solutions are briefly reviewed. It is shown that the passivation can be caused only by their adsorption, retarding both the iron dissolution and the formation of oxide films. Earlier, it had been believed that oxide films play a dominant role in the iron passivation in neutral solutions. The recent viewpoint is that such nonoxide iron passivation can occur in solutions of salts of not only aromatic amino acids (sodium phenylantranilate and its substitutes), but other carboxylic acids as well. An important role of chemisorption and hydrophobic properties of anions for the formation of adsorption passive films is emphasized. New possibilities for inhibitor protection of iron against corrosion, which is based on adsorptive passivation, are pointed out.Translated from Elektrokhimiya, Vol. 40, No. 12, 2004, pp. 1503–1507.Original Russian Text Copyright © 2004 by Kuznetsov.     

Corrosion fatigue on 2024T3 and 6056T4 aluminum alloys

Fatigue corrosion phenomenon is a form of degradation that is because of the combined occurrence of a mechanical cyclical stress and a corrosive environment. Fatigue corrosion can be an issue in commercial and military aircraft, and has the potential to affect the structural integrity and the useful life of an aerostructure. Although the distinct consequences of both fatigue and corrosion have been extensively documented for aluminum alloys, their synergistic action is not completely understood and continues to be an area of considerable scientific and industrial interest. In this paper, a novel approach is proposed and applied for monitoring the electrochemical behavior of different types of aluminum alloy samples while they are subjected to fatigue loading. Cyclic load experiments were conducted on bare 2024T3 and 6056T4 aluminum alloy samples in the presence of an aggressive aerated solution of 3.5% NaCl over a range of frequencies. The R‐ratio was 0. Two different aluminum alloys have been tested in both high‐ and low‐cycle fatigue. In the former case, the maximum stress experienced by the specimen is lower than the material yield strength, which means that the average expected number of cycles to failure is high; in the latter case, the maximum stress experienced by the specimen during the test is higher than the material yield strength, which means that the average expected number of cycles to failure is low. The open circuit potential(OCP) was monitored versus time during the tests described above. The observed OCP variations are interpreted as the occurrence of corrosion during crack initiation and propagation at the air formed oxide/solution interface film. As expected, there is a more pronounced influence of corrosion at lower fatigue frequencies. Crack propagation allows bulk material to be progressively more exposed to the aggressive environment, which stimulates accelerated crack propagation, resulting in a lower fatigue resistance. Copyright © 2010 John Wiley & Sons, Ltd.     

化学/电化学腐蚀法快速制备超疏水金属铝

提出一种金属铝超疏水表面的快速制作方法. 先以化学腐蚀在铝表面形成微米级粗糙结构, 再通过电化学腐蚀构筑纳米结构, 在20 min内完成了超疏水表面所需粗糙结构的制备. 这种化学腐蚀/电化学腐蚀两步法比单独化学或电化学腐蚀方法在时间上缩短了1~2个数量级, 且不受铝材晶形限制, 同时电化学腐蚀所用电流密度也降低了1个数量级, 降低了对电源设备的要求, 可望大规模应用于工业生产和其它金属的超疏水表面制备.     

RESEARCH ON POWDERY CORROSION OF THE SERIALS BELLS FROM CAI HOU TOMB

"Powdery corrosion" is called "cancer" of cultural relics of bronze. For many years theexperts concerned at home and abroad cannot make distinct progress in the control or cure ofpowdery corrosion. This paper introduces in detail analyses of XRD, SEM. TEM and XRFA on afragment of serials bells with serious powdery corrosion from the Cai Hou Tomb, pointingout that the components of powdery corrosion are mainly atacamite (Cu_2(OH)_3Cl), cuprite(Cu_2O) and cassiterite (SnO_2) in the worse crystalline state. In the bell's matrix, there arecorrosion gullies which has the same phase components as the powdery corrosion. Obviously,this discovery has very important significance for studying the formation mechanism ofpowdery corrosion.     

Characteristics of CO2 corrosion scale formed on P110 steel in simulant solution with saturated CO2

The SEM, X‐ray diffraction (XRD), and XPS were employed to systematically characterize the component and microstructure of the corrosion scale formed on P110 steel exposed to carbon dioxide (CO₂) environment. A loose and porous microstructure in corrosion scale was observed under turbulent flow condition for 120 h at 100 °C with a carbon dioxide partial pressure of 4 MPa in which the principal component was iron carbonate (FeCO₃), whereas at 160 °C the corrosion scale was composed mainly of FeCO₃ and a little amount of FeO(OH). In addition, complex carbonate (Mg,Fe)CO₃ was produced because some Fe positions in FeCO₃ lattice were substituted by Mg. It showed that a double‐layer structure of corrosion scale was observed at 160 °C compared with the result at 100 °C. Copyright © 2008 John Wiley & Sons, Ltd.     

季铵化聚乙烯亚胺对低碳钢缓蚀性能与机理

采用叔胺化反应与季铵化反应2步高分子反应过程,制备季铵化的聚乙烯亚胺(QPEI),采用静态挂片失重法与电化学极化曲线测定法,研究了在H2S04溶液中QPEI对低碳钢的缓蚀性能与缓蚀机理,并使用扫描电子显微镜对缓蚀样片表面膜层进行了分析. 实验结果表明,QPEI对低碳钢具有优良的缓蚀作用,在0.5 mol/L的H2S04介质中,QPEI的质量浓度仅为5 mg/L,A3钢片的腐蚀时间为72 h时,缓蚀率高达91%;QPEI可同时抑制阴极过程与阳极过程,其缓蚀作用属混合型;在物理吸附与化学吸附的协同下,QPEI在碳钢表面会形成致密的吸附膜,它在钢板表面的吸附行为符合Langmuir单分子层吸附等温式.