镁合金丝状腐蚀研究进展

目的镁合金具有许多独特的性能及光明的应用前景,但耐蚀性差制约了其发展。丝状腐蚀作为一种常见的局部腐蚀形态,其破坏性非常大。结合国内外丝状腐蚀的研究成果,从丝状腐蚀产生的原因及发展过程,重点叙述了镁合金丝状腐蚀的特点、腐蚀机理,以及腐蚀环境和微观结构对镁合金丝状腐蚀发展的影响规律。指出了镁合金丝状腐蚀阴极发生的是析氢反应,且腐蚀丝具有折射生长、相随生长等特点;腐蚀介质会优先吸附在自然形成氧化膜的缺陷处,导致腐蚀萌生;第二相、晶粒尺寸和表面处理等微观结构对腐蚀丝的发展有重要影响。同时总结了微区原位技术在镁合金丝状腐蚀研究中的应用,并指出了微区原位技术和传统的腐蚀研究方法相结合是揭示镁合金丝状腐蚀机制的有效途径。最后,对未来镁合金丝状腐蚀机理的研究进行了分析和展望。     

铝合金丝状腐蚀研究综述

在综合国内外相关研究的基础上,对铝合金丝状腐蚀这一现象进行了描述,指出了铝合金发生丝状腐蚀的四个必要条件(高湿度、涂层缺陷、氧气及腐蚀性离子)。分析了腐蚀丝的引发和发展机理,列举了影响丝状腐蚀发展的重要因素(大气环境、基体金属、表面预处理和涂层),总结对比了国内外常用的丝状腐蚀试验标准和研究方法(扫描开尔文探针检测法、电化学阻抗谱法、电化学仿真法以及自然环境试验法)。从环境控制、表面预处理和涂层使用等三个方面讨论了丝状腐蚀的抑制及防护措施。最后提出了尚需解决的四个问题:标准丝状腐蚀试验与实际大气腐蚀的相关性、有机涂层耐丝状腐蚀性能标准的制定、航空铝合金的丝状腐蚀研究、表面预处理方法的改进。     

建筑铝型材聚合物膜下的丝状腐蚀

综述了建筑铝型材聚合物膜下丝状腐蚀的特征和影响丝状腐蚀的环境,基体,预处理和结构等因素,介绍了建筑铝型材聚合物膜的加速腐蚀试验和预测丝状腐蚀试验。     

FCO试验法简介

FCO试验法,是用于钢铁涂漆后丝状腐蚀加速试验法.是五四所401组与协作单位共同研究试验的.用于检验钢制药筒的抗丝状腐蚀性能.由于丝状腐蚀过程比较复杂,影响因素较多,缺乏有效而快速的试验方法.近年来,结合库存试验,对钢铁的丝状腐蚀机理及影响因素进行了探讨研究,在此基础提出了一种用于     

预处理对铝合金喷涂层丝状腐蚀性能的影响

选择铬化和无铬化预处理对6063-T6、6082-T6和6005A-T6三种铝合金进行静电粉末喷涂,通过丝状腐蚀试验研究预处理工艺对不同铝合金喷涂层耐丝状腐蚀性能的影响。结果表明:铬化处理会减少丝状腐蚀的生成,延缓丝状腐蚀的生长;与6082和6005A铝合金喷涂层相比,6063铝合金喷涂层具有更好的耐丝状腐蚀性能。     

挤压时效态MB8镁合金在盐水中的腐蚀行为

采用光学显微镜(OM)、扫描电镜(SEM)和能谱分析(EDS)等手段研究挤压时效态MB8镁合金在盐水浸泡条件下的腐蚀特征,并探讨合金的腐蚀机理。结果表明:合金以丝状腐蚀和点蚀这两种局部腐蚀为主要的腐蚀形式。合金经过一定时间的诱导期后发生丝状腐蚀,腐蚀前端的丝头处发生镁基体的阳极溶解,已发生腐蚀的丝尾处作为活性阴极发生析氢反应;第二相粒子对丝状腐蚀的扩展具有重要影响,横截面上丝状腐蚀随着弥散分布的第二相粒子向四周扩展,而纵截面上腐蚀丝随着第二相粒子的带状分布呈长条带状形貌特征;在丝状腐蚀还未扩展到的区域由于第二相粒子与基体之间的腐蚀微电偶作用导致基体发生阳极溶解,从而产生点蚀。     

基于扫描Kelvin探针和FT-IR的7B04铝合金/涂层体系丝状腐蚀研究

对7B04铝合金进行硫酸或铬酸阳极氧化后再喷涂底漆或底漆+面漆,从而制备四类试样,而后开展标准丝状腐蚀试验,利用扫描 Kelvin 探针（SKP）和傅里叶变换红外光谱（FT-IR）技术对7B04铝合金/涂层体系的腐蚀行为和机理进行研究。光学显微镜观察发现四类试样上腐蚀丝的数量较少,且长度不超过3 mm,表明四类试样均具有较好的耐蚀性。SKP测试结果表明,四类试样跨划痕区域的伏打电位随试验时间的变化规律相似,划痕处与周围的涂层-金属界面之间的电位差引起丝状腐蚀的发生,腐蚀机理为阳极破坏;单个腐蚀丝的伏打电位值朝着头部降低,朝着尾部升高,头部和尾部之间的电位差促进腐蚀丝的传播。FT-IR分析显示丝状腐蚀产物的成分主要为Al(OH)3 、Al2O3和AlCl3及其部分水解产物,发生的电化学反应类似于7B04铝合金在氯离子作用下的点蚀过程。对比分析结果表明两种阳极氧化方式对丝状腐蚀的影响差异性较小。     

含钇AZ91镁合金在连续浸泡与干湿交替环境中的腐蚀行为

研究添加不同含量稀土钇(Y)的AZ91镁合金在连续浸泡及干湿交替腐蚀环境中的腐蚀行为。结果表明:添加稀土Y的AZ91镁合金,腐蚀形貌转变为"丝状"腐蚀;在连续浸泡溶液环境中,腐蚀沿着同一条"丝"发展。而在干湿交替腐蚀环境中,腐蚀主要在湿环境下产生和发展,在干环境下停滞。重新置入湿环境时,旧的腐蚀"丝"不会明显发展,而会形成新的腐蚀"丝",镁合金表面"丝状"腐蚀数量随干湿交替循环腐蚀次数增加而增多。"丝状"腐蚀形貌的形成是由于稀土添加降低了Al元素在晶界上的分布,使得表面析氢腐蚀不易受到阻碍,腐蚀以"腐蚀丝"末端持续析氢向前发展。电化学阻抗测试结果表明:干湿交替腐蚀环境中的电荷转移电阻明显低于连续浸泡环境中对应的电荷转移电阻,这是因为干湿交替过程中,薄液膜的存在延长了镁合金的析氢时间,而干环境的干燥作用破坏了镁合金表面膜的完整性。     

镁合金的腐蚀及其防护措施

介绍了镁合金的腐蚀特性、影响镁合金腐蚀的因素以及镁合金腐蚀的类型。镁合金腐蚀的类型有电偶腐蚀、点蚀、丝状腐蚀和高温氧化。综述了腐蚀防护措施为通过研究开发高纯镁合金,应用快速凝固工艺,实施表面处理技术等。镁合金表面技术中的化学转化膜、阳极氧化、微弧氧化及金属镀层等对镁合金的腐蚀防护有很好的作用。     

基于扫描Kelvin探针和FT-IR的7B04-T74铝合金/涂层体系丝状腐蚀研究

对7B04-T74铝合金进行硫酸或铬酸阳极氧化后再喷涂底漆或底漆+面漆,从而制备4类试样,而后开展标准丝状腐蚀试验,利用扫描Kelvin探针(SKP)和傅里叶变换红外光谱(FT-IR)技术对7B04-T74铝合金/涂层体系的腐蚀行为和机理进行研究。光学显微镜观察发现4类试样上腐蚀丝的数量较少,且长度不超过3 mm,表明4类试样均具有较好的耐蚀性。SKP测试结果表明,4类试样跨划痕区域的伏打电位随试验时间的变化规律相似,划痕处与周围的涂层-金属界面之间的电位差引起丝状腐蚀的发生,腐蚀机理为阳极破坏;单个腐蚀丝的伏打电位值朝着头部降低,朝着尾部升高,头部和尾部之间的电位差促进腐蚀丝的传播。FT-IR分析显示丝状腐蚀产物的成分主要为Al(OH)_3、Al_2O_3和AlCl_3及其部分水解产物,发生的电化学反应类似于7B04-T74铝合金在氯离子作用下的点蚀过程。对比分析结果表明,2种阳极氧化方式对丝状腐蚀的影响差异性较小。     

The influence of surface treatment on filiform corrosion resistance of painted aluminium alloy sheet

Filiform corrosion of AA 5005 H14 aluminium alloy sheet has been investigated. Painted and scribed panels, with different surface treatments, were inoculated in HCl and exposed in a constant humidity cabinet maintained at 40 °C and 75-85% RH for 1000 h. After exposure, the panels were examined by optical and electron microscopy. It is evident that filiform corrosion susceptibility is determined largely by the near-surface microstructure. Heavily deformed layers, comprising oxide-decorated fine grains and dispersoids on as-rolled and mechanically ground alloy surfaces, are readily susceptible to filiform corrosion. Removal of these deformed layers, by caustic etching and acid cleaning, results in a high filiform corrosion resistance. On such surfaces, underfilm corrosion progresses by localized corrosion of the substrate; with comparatively slowly growing filaments propagating by repeated blistering of the overlying lacquer.     

Characterisation of initial atmospheric corrosion carbon steels by field exposure and laboratory simulation

The early stages of the evolution of atmospheric corrosion of carbon steels exposed in both a laboratory simulated and a natural atmosphere environment in Shenyang have been observed by in situ scanning electron microscopy. In the case of laboratory cyclic wet-dry tests, even though the chloride content level is very low, filiform corrosion is initiated in the early stage. The filiform corrosion grows in random directions, forming a network of ridges. White nodules nucleate and grow on the ridges during continued corrosion and eventually connect with each other to form the initial corrosion scale. Pits were also found on the surface beneath corrosion products. In the case of a natural atmospheric environment, both filiform corrosion and other localized corrosion, such as pitting and inter-granular attack take place in the initial stage. It is obvious that there is variety of localized corrosion in the initial stage of atmospheric corrosion.     

An integrated study on the effect of pre- and post-extrusion heat treatments and surface treatment on the filiform corrosion properties of an aluminium extrusion alloy

The effect of pre- and post-extrusion heat treatments on the filiform corrosion behaviour of a well-known aluminium extrusion alloy AA6063 is studied by a combination of accelerated filiform corrosion exposure tests and potentiodynamic polarisation measurements for four different surface treatments. It is shown that the post-extrusion heat treatment of this AlMgSi alloy can influence the filiform corrosion properties significantly, in particular for the milder surface treatments. In contrast, the relative effect of the pre-extrusion treatment on the filiform corrosion properties is minimal for all treatments. The alloys are most susceptible to filiform corrosion in the β′ condition. The susceptibility decreases with coarsening of the Mg₂Si particle distribution. For the post-extrusion heat and surface treated AA6063 material a clear correlation between the polarisation characteristics and the two principal filiform corrosion characteristics, i.e. the propagation rate and total area of attack after accelerated exposure, is observed. The observed correlation is attributed to a pitting corrosion mechanism with a rate depending on the (coupled) Mg₂Si precipitate size and fraction.     

Filiform corrosion attack on pretreated aluminum alloy with tailored surface of epoxy coating

In the study, on the basis of material analysis of 6016 aluminum alloy widely used in Europe automotive industry, the influences of surface pretreatment on filiform corrosion and adhesion of epoxy coating/aluminum alloy interface were investigated, and the effect of rolling direction and coating property on filiform corrosion was also examined. The alloy surfaces were pretreated with etching solution, and then, respectively, with Aminopropyl silane solution, Aminopropyl phosphonate solution, and hexamethyldisiloxane plasma.The results showed that the susceptibility of pretreated surface to filiform corrosion was basically consistent with the distribution of intermetallic particles, and that water permeation and the tensility of coating were necessary for filament to grow. HMDSO plasma pretreatment could not only efficiently cover the matrix of 6016 aluminum alloy and cathodic intermetallic particles containing Al, Si, Mn, and Fe, but also apparently promote the adhesion of epoxy coating/aluminum alloy, as a result, the specimens with plasma pretreatment exhibited the superior performance in the filiform corrosion and peeling tests, so it was suitable to apply for the pretreatment of aluminum alloy in automotive industry.     

Filiform corrosion behaviour on machined AA7150 aluminium alloy

The microstructure and the filiform corrosion behaviour of machined AA7150 aluminium alloy were investigated using scanning and transmission electron microscopies combined with potentiodynamic polarization and filiform corrosion testing, respectively. It is found that the grain refinement, redistribution of alloying elements, and elements segregation at grain boundaries are evident within the near-surface region on the machined AA7150 aluminium alloy. The corrosion susceptibility of machining introduced near-surface deformed layer is significantly improved caused by the modified microstructure associated with severe deformation. Filiform corrosion resistance on the machined surface is obviously decreased, due to the surface roughness associated with machining tracks and the presence of the electrochemically more active near-surface deformed layer introduced by machining.     

A morphological study of filiform corrosive attack on cerated AA2024-T351 aluminium alloy

SEM and EDS studies were carried out to characterise filiform attack on a cerated AA2024-T351 aluminium alloy with a polyurethane topcoat. The filiforms developed on AA2024-T351 were sectioned, stripped of corrosion product and etched to reveal the grain structure. Examination of sections through the filaments and the filaments themselves, revealed severe local attack in the form of pitting resulting in grain etch out, grain boundary attack and subsurface etch out. Chloride ions were detected deep within pits and the subsurface etch out. The observations were similar to those found with filiform corrosion on chromated and coated surfaces. The observations led to development of a filiform corrosion model naming the volume expansion of the corrosion product as the principal cause for delamination.     

Evaluation of the localized corrosion on Mg electrode surface by electrochemical noise technique

The symmetrical and asymmetrical electrodes made of Mg were studied in 0.1-M NaCl electrolyte adjusted at pH 12. The statistical and wavelet methods were employed for analyzing the electrochemical current noise (ECN) signals. The asymmetric configuration was used for electrochemical detection of filiform corrosion on Mg electrode. The real time scale of the dominant transients of the asymmetric electrodes was detected on the basis of the maximum peak in the SDPS plots. The SDPS values of the real time scale crystals of the ECN signals resulting from asymmetrical electrodes increased with the increase in immersion time due to the onset of filiform corrosion.