环氧富锌/氯化橡胶涂层体系腐蚀过程的电化学阻抗谱

采用环氧富锌作为底漆、氯化橡胶作为面漆,研究了涂层体系腐蚀过程中电化学阻抗谱(EIS)的变化。结果表明,腐蚀初期环氧富锌/氯化橡胶涂层体系中底漆的厚度比例与涂层的防护性能无关,而在腐蚀中后期,随底漆厚度比例适当增大,涂层自修复能力增强,离子等腐蚀介质在涂层中的传输速度得到显著延缓,涂层吸水率和孔隙率明显降低,涂层防护性能出现短时间升高。当环氧富锌底漆为涂层总厚度的2/3左右时,涂层体系的防护性能最好,而仅有底漆或面漆的体系则不具备良好的防护性能。     

EIS方法对有机涂层在海水介质中的耐腐蚀性研究

运用电化学阻抗图谱(EIS)实验方法,对不同种类的有机涂层在海水介质中的耐腐蚀性能进行研究。     

环氧/聚氨酯涂层在4种环境中失效行为的EIS

用电化学交流阻抗法(EIS)研究了环氧富锌底漆/环氧云铁中间漆/丙烯酸聚氨酯面漆这一涂层体系在3.5%NaCl溶液、3.5%NaCl溶液+紫外辐射、湿热和盐雾这4种环境中的失效行为,探讨了特征频率下的相位角和涂层电阻值之间对应的关系。结果表明:中频区10Hz处涂层相位角随时间的变化曲线和涂层电阻值随时间的变化曲线有良好的相似性,据此可以对所研究的涂层体系失效程度进行快速评价;所试验的4种腐蚀环境对所研究的涂层体系的破坏作用由小到大依次为:3.5%NaCl溶液盐雾湿热3.5%NaCl溶液+紫外辐射。     

利用EIS高频区参数评价两种环氧涂层的性能

利用10 kHz下的相位角、10 kHz下的相对介电常数和对应于45°相位角的特征频率这3种EIS高频区的参数对两种环氧涂层体系在盐水浸泡+紫外照射的腐蚀条件下的失效过程进行了表征,并与涂层阻抗值进行了对比。测量结果表明,上述3种高频区参数的结果一致,都能够反映涂层性能的变化及相对优劣。当频率10 kHz处的相位角下降到40°,相对介电常数增大到40,或特征频率接近10 kHz时,所研究的两种环氧涂层体系的阻抗值都对应降低到10⁶ Ω•cm²左右,涂层保护性能接近失效。由于这几种EIS高频区参数能够很快测得,因此可以利用这些参数快速评价该涂层的保护性能与失效程度。     

聚天门冬氨酸酯聚脲涂层湿热失效行为的电化学

采用电化学阻抗谱研究了聚天门冬氨酸酯聚脲涂层在湿热环境作用下的失效行为,采用SEM研究了聚天门冬氨酸酯聚脲涂层失效前后表面形貌的变化。电化学研究结果表明:涂层湿热失效过程分为3个主要阶段:前期电解质在涂层中的渗透、中期基体金属腐蚀发生起始的过渡、后期基体金属的腐蚀扩展并导致涂层的失效。湿热试验中,涂层孔隙率和涂层吸水率均呈3个阶段变化,即快速增长阶段、缓慢增长阶段和稳定阶段,很好地验证了PAEP涂层湿热失效的3个过程。表面形貌研究发现,湿热试验4572 h后,涂层表面粗糙度增加,出现了裂缝等缺陷,表明涂层已经失去防护作用。     

海洋微生物介质中碳钢腐蚀电化学行为研究

采用电化学阻抗谱、极化曲线等测试技术,研究了碳钢在不同培养周期下的海水微生物介质中的腐蚀行为.结果表明,海水中未经纯化的微生物使碳钢电极的腐蚀电位负移;电极表面完整均匀微生物膜的存在不改变阴极的极化类型和控制步浇骤,只对阳极腐蚀过程起加速作用;电化学阻抗谱证实,在有菌存在的条件下,电极的阻抗值下降,微生物的存在会加速碳钢电极的腐蚀作用.     

不同表面处理条件下复合涂层体系失效过程的EIS特征

研究了不同表面处理条件下环氧富锌/环氧云母氧化铁/氯化橡胶涂层体系的电化学阻抗谱特征。利用Bode图、涂层吸水率、涂层电阻及特征频率的变化评价了表面处理对涂层防护性能的影响。结果表明,基材表面状态不同的复合涂层体系吸水率相对稳定阶段所持续的时间长短顺序为：手工打磨>表面锈蚀>表面未处理,与涂层的防护寿命长短、涂层/基材间的黏附力大小顺序一致。此外,不论基材表面处理程度如何,当涂层体系的特征频率增加到1400 Hz左右时,涂层电阻均发生较快降低,吸水率发生较大增长,涂层失去防护作用。     

氧化铝增强无机硅酸锌涂层的电化学阻抗谱研究

无机硅酸锌涂层是一种广泛使用的钢铁重防腐涂层。采用在涂料填料中加入氧化铝的方法可以得到具有更好耐磨性能的富锌涂层。本实验研究利用电化学阻抗谱法(EIS)研究了氧化铝的加入对涂层腐蚀防护性能的影响,结果表明氧化铝颗粒的加入使涂层的腐蚀防护性能略有提高。     

基于SOM技术的有机涂层电化学阻抗谱的自动识别分析

本实验建立了用于识别分析有机涂层电化学阻抗谱的SOM人工神经网络。应用该网络对几种常见的有机涂层电化学阻抗谱进行了识别分析,实验表明3种数据组合θ和|Z|、θ和d|Z|/dlogf、dθ/dlogf和|Z|既包含了阻抗谱形状的变化,又可以反映研究对象阻抗大小的变化,可以获得较好的识别效果,其中θ和d|Z|/dlogf的数据组合效果最好。该网络技术可以为涂料研究机构提供比较便捷的阻抗谱分析手段,用于考察涂层状态的变化。     

聚酯粉末涂层在工业污染环境中的腐蚀行为研究

采用金相显微镜和交流阻抗谱研究了涂层缺陷以及不同前处理工艺对建筑铝合金6063在0.04 mol/LNa2SO4溶液(pH=3.0)中的腐蚀行为。研究结果表明:未经铬酸钝化处理的铝合金缺陷粉末涂层在0.04 mol/L Na2SO4(pH=3.0)溶液中浸泡50 d后,其划痕处堆积满腐蚀产物,划痕两侧局部出现明显翘起和气泡;浸泡相同时间的经铬酸钝化处理的铝合金粉末涂层其腐蚀速率低约1个数量级,铝合金钝化膜能延缓腐蚀,提高缺陷涂层和完整涂层的阻抗。     

Study on corrosion electrochemical behavior of several different coating systems by EIS

Corrosion electrochemical behavior of chlorinated rubber top coating (single-layer), inorganic zinc-rich primer/chlorinated rubber top coating (double-layers) and inorganic zinc-rich primer/epoxy middle paste/chlorinated rubber top coating (tri-layers) in 3.5 wt% NaCl solution was studied by electrochemical impedance spectroscopy (EIS). A series of impedance spectra of the three coating systems during immersion were measured; and their protective properties were compared according to the spectra. The experimental results showed that, the protective properties of the double-layers coating system were even worse than that of the single-layer coating system; and the tri-layers coating system had the best protective properties in the three coating systems; epoxy middle paste had played a very important role for protective properties of the composite coating system.     

In-situ AFM and EIS study of a solventborne alkyd coating with nanoclay for corrosion protection of carbon steel

A solventborne alkyd composite coating containing modified montmorillonite (MMT) nanoclay was made on carbon steel, and its corrosion protection was investigated by in-situ atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS) measurements in 3 wt.% NaCl solution. X-ray diffraction (XRD) analysis indicated intercalation of the MMT sheets in the composite coating. Thermo-gravimetric analysis (TGA) demonstrated improved thermal stability of the composite coating due to the modified nanoclay. Scanning electron microscopy (SEM) and AFM examination revealed dispersion and also some aggregation of the nanoclay particles in the coating. In-situ AFM images show a stable coating surface at nano-scale during relative long time exposure in the NaCl solution, indicating an enhanced stability of the composite coating. The EIS results confirmed that the composite coating provides an enhanced barrier type corrosion protection for carbon steel in the corrosive solution, which could be attributed to the intercalated lamellar MMT sheets in the coating that block the defects and decrease the transport of water and corrosive species.     

The failure behavior of a polyurethane composite coating in 3.5% NaCl solution under ultraviolet irradiation

The failure process of inorganic zinc‐rich/micaceous iron oxide epoxy/aliphatic polyurethane composite coating in 3.5% NaCl solution under ultraviolet irradiation (UV) was studied with electrochemical impedance spectroscopy (EIS) and Fourier transform infrared (FTIR) spectroscopy. UV irradiation significantly accelerated failure process of the composite coating in NaCl solution. The effect of UV on failure process of the coating system in 3.5% NaCl solution may be divided into two stages: in the early stage, the thermal effect generated by the ultraviolet irradiation is the main reason leading to the increase in coating porosity, but this effect is not serious and the coating remains high impedance and good protection ability. In the latter stage, the fracture of polymer chains in the top coating by UV irradiation is the main factor resulting in quick decrease of coating performance. C N and C O bonds in polyurethane coating are broken by UV irradiation, leading to quick increase of the coating porosity and decrease of the coating resistance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Monitoring the degradation of a high solids epoxy coating by means of EIS and EN

This paper reports a study of the degradation processes suffered by steel samples painted with a high solid content epoxy coating. Because this coating shows a high resistance when exposed to NaCl solutions, HCl solutions were employed to accelerate the corrosion processes. Macroscopic images were used to observe the coating degradation. Then electrochemical techniques, electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) were employed to monitor the corrosion behaviour of the system studied. A close correlation was found between EIS and EN data. Several parameters were estimated using these techniques: R_po, R_ct, C_c, C_dl and Z_0.1 Hz using EIS, and R_n using EN. In addition, a new parameter estimated by means of EN was employed, Z_0.1 Hz(EN). The evolution of all these parameters with time enabled the effective monitoring of the degradation stage of the coating.     

Electrochemical deposition and characterization of ZnCo alloys and corrosion protection by electrodeposited epoxy coating on ZnCo alloy

ZnCo alloys electrochemically deposited on steel under various deposition conditions were investigated. The influence of deposition current density, temperature and composition of deposition solution on the phase structure and corrosion properties of ZnCo alloys were studied. It was found that ZnCo alloy obtained from chloride solution at 5 A dm⁻² showed the best corrosion properties, so this alloy was chosen for further examination. Epoxy coating was electrodeposited on steel and steel modified by ZnCo alloy using constant voltage method. The effect of ZnCo alloy on the corrosion behavior of the protective system based on epoxy coating is interpreted in terms of electrochemical and transport properties, as well as of thermal stability.     

Evaluation of a high resistance paint coating with EIS measurements: Effect of high AC perturbations

Electrochemical impedance spectroscopy (EIS) was used to evaluate a high resistance paint coating immersed in 10% sodium chloride solution. Although this method was valuable in evaluating this type of coating there were many fluctuations in measured data at low AC perturbations. In this work the role of high AC perturbation to fit EIS data of high resistance coating with equivalent electrical circuit (EEC) was studied. EIS measurements showed that these fluctuations could be reduced by high AC perturbation. The impedance plots showed best fitting at 400 mV AC perturbation at the initial time of immersion and at 100 mV AC perturbation after 90 days of immersion. The coating resistance and coating capacitance were extracted from the Bode and Nyquist plots during the period of 90 days of immersion.     

Some comments on the use of the EIS phase angle to evaluate organic coating degradation

The impedance of a disc electrode protected by an organic coating, with a thickness profile along its radius, was considered by EIS. The local and global impedances, the ohmic resistance corrected phase angle, and raw phase angle were calculated. The thickness profile leads to a well-defined minimum in the calculated phase angle curves, which can be observed in the high frequency domain. This effect is enhanced with higher permittivity, thinner coatings and low conductivity immersion baths. From these results, it appears that the graphical treatment of experimental phase angle curves to evaluate the coating degradation may lead to erroneous conclusions.     

The uneven corrosion of deep drawn coil-coatings investigated by EIS

The corrosion distribution along a coil-coating sample formed by deep-drawing is reported. The formed rectangular cup was divided in five different regions and their impedance response investigated independently. The response of each region was compared with the overall sample response and the morphology of degradation was studied by scanning electron microscopy. Severe attack was observed in the most strained regions (corners and edges). Micro-defects in the shape of pinholes and cracks developed as a consequence of the forming process, apparently nucleating in the vicinity of the inorganic particles present in the paint. Immersion increased the size and number of defects. The overall impedance was reconstructed from the impedance measured in the local regions by two methods: (a) calculation using the local experimental data and (b) simulation using an equivalent electrical circuit with the values taken from the fitting of the local experimental data.