Inquire into degradation process of Ni-Co coating in 3.5% NaCl solution by EIS北大核心CSCD

The degradation process of Ni-Co coating on plate of Kovar alloy 4J42 in 3.5%NaCl solution was studied by means of electrochemical impedance spectroscope (EIS). Four distinguished electrical equivalent circuits (EEC) were proposed to simulate the degradation process. At the very beginning of immersion, the coating exhibited excellent corrosion resistance, which could be treated as a barrier layer with a high resistance in parallel with a low capacitance. After a short time of immersion, a double-layer capacitance Cdl and a charge-transfer resistance Rct were introduced, indicating that the electrochemical reactions at the metal/coating interface may take place. In the late stage of immersion, Warburg impedance was adopted to characterize the corrosion products. With the accumulation of the corrosion products, the diffusion process of corrosive medium was affected, and the EEC comprising a diffusion capacitance (Cdiff) and a diffusion resistance (Rdiff) was then introduced to fit the impedance spectra. The evolution of coating resistance and coating capacitance were investigated to illuminate the Ni-Co coating degradation process. The results showed that the degradation process of Ni-Co coating could be described by three stages: the permeation of corrosive medium, the corrosion of metal at the interface of coating/substrate and finally the failure of coating. © 2016, Corrosion Science and Protection Technology. All rights reserved.     

AZ31B镁合金表面微弧电泳复合膜层微观结构及耐蚀性表征

采用微弧氧化技术在AZ31B镁合金表面制备陶瓷层,利用其表面多孔结构借助电泳技术沉积有机膜层,对比研究陶瓷层和复合膜层表面粗糙度、表面及截面形貌、电化学性能及划伤腐蚀特性。结果表明:陶瓷层表面放电微孔被电泳层完全填充并形成均匀膜层,复合膜层表面粗糙度明显降低;微弧电泳复合膜层腐蚀电流密度与陶瓷层和基体相比分别降低2个和4个数量级,极化电阻分别增大2个和4个数量级,腐蚀倾向降低;微弧电泳复合膜层电化学阻值与陶瓷层相比增加4个数量级,同时电容值降低4个数量级,耐蚀性显著提高;由于陶瓷层与电泳层的机械嵌合作用,复合膜层划伤腐蚀过程表现为基体腐蚀及陶瓷层与基体界面的破坏,复合膜层界面处结合完好。     

Corrosion electrochemical characteristics of red iron oxide pigmented epoxy coatings on aluminum alloys

Red iron oxide pigmented epoxy coatings were prepared on aluminum alloys and were characterized by electrochemical impedance spectroscopy (EIS) immersed in NaCl solution. The evolutions of impedance models of coated metals were obtained by the fitting analysis of experimental data using suitable equivalent electrical circuits (EEC). The results indicated that the composite electrode system could be fitted by three impedance models. At the initial immersion stage, coatings acted as a barrier layer and only performed a simple circuit consisting of a coating resistance (R_c) parallel to a coating capacitance (C_c). After a certain time of exposure, water and (or) oxygen arrived at the metal surface through the coating, leading to the formation of electrochemical corrosion sites at metal interface and thereby the appearance of double-layer capacitance (C_dl) and charge transfer resistance (R_ct). After intensive attacking of metal substrates, the mass transfer of corrosion products was in difficulty. In this case, the diffusion elements were added to the EEC. It was found that due to the presence of inert pigment particles, the mass transfer behaviors were interestingly different from those of the varnish polymer coatings. Electrical parameters were also obtained from the EIS data. lnC_c-time curve showed a Case II water sorption kinetics, typical non-Fickian diffusion for water uptake.     

3.5%NaCl溶液中AISI304不锈钢的电化学行为及有机硅涂层的防护

应用电化学交流阻抗技术(EIS)研究了AISI304不锈钢 在35%NaCl溶液中的电化学行为及表面涂敷有机硅涂料后的电化学行为.结果表明，AISI304不锈钢在在开路电位下的交流阻抗表现为单容抗弧，在浸泡初期，随着时间的延长，耐蚀性提高，当浸泡120?d后，耐蚀性明显下降.不锈钢表面涂敷一层有机硅涂料后，EIS发生了较大变化，浸泡初期为单容抗弧，阻抗值明显增大，浸泡1天后表现为双容抗弧，而不锈钢裸样的始终表现为单容抗弧.     

Determination of the protective properties of electrodeposited organic epoxy coatings on aluminium and modified aluminium surfaces

The electrochemical and transport properties and thermal stability of epoxy coatings electrodeposited on aluminium and modified aluminium surfaces (anodized, phosphatized and chromatized-phosphatized aluminium) have been investigated during exposure to 3% NaCl solution. From the results obtained from electrochemical impedance spectroscopy (EIS), gravimetric liquid sorption experiment and thermogravimetric analysis (TGA) it can be concluded that electrochemical and transport properties of epoxy coatings on anodized and chromatized-phosphatized aluminium are significantly improved with respect to the same epoxy coatings on aluminium and phosphatized aluminium: higher values of pore resistance and charge-transfer resistance and lower values of coating capacitance and double-layer capacitance, from EIS; smaller values of diffusion coefficient of water through epoxy coating, from sorption measurements and smaller amount of absorbed water inside the coating, from TGA. On the other hand, the somewhat lower thermal stability of these coatings was obtained.     

The evaluation of coating performance by the variations of phase angles in middle and high frequency domains of EIS

Electrochemical impedance spectra (EIS) of six coating systems in 3.5% NaCl solution were measured and the relations between coating resistances and phase angles at different frequencies were analyzed. The results indicated that in middle frequency range, the phase angle and the coating resistance show similar decreasing tendencies. For the coating systems studied, the variation of phase angles at 10 Hz with immersion time was very close to the variation of coating resistance, hence may qualitatively reflect the coating performance. For the studied coating systems, the phase angle at 10 Hz decreased continuously from the beginning, indicating the permeation of the coating system by the electrolytes. When the phase angle reached a relatively stable stage, for different coating systems which was below 40°–20°, meaning the coating has been permeated through and electrochemical reactions under the coatings occurred. In addition, the phase angle at 15 kHz may reflect the state of coating in later stage. These phase angle parameters may be used as quick measurements to evaluate coating performance.     

The corrosion protection of mild steel by polypyrrole/polyphenol multilayer coating

Electrochemical synthesis of very thin polyphenol (PPhe) film was achieved on polypyrrole coated mild steel electrode (MS/PPy) and a multilayer coating was obtained, cyclic voltammetry technique was used for the synthesis. The corrosion performance of this multilayer coating and single PPy coating were investigated in 0.05 M H₂SO₄ solution by using electrochemical impedance spectroscopy (EIS), anodic polarization curves and open circuit potential (E_ocp)-time curves were used. It was found that the multilayer coating could provide much better protection than the single PPy coating for corrosion of MS for much longer periods and an efficiency of 98.3% was determined for this coating after 340 h exposure time in corrosive medium. It is proposed that the very thin PPhe film coated on top of PPy coating lowered the porosity and improved the barrier effect of the coating significantly.     

Electrochemical impedance spectroscopy study on multi-layered coated steel sheets

Electroplating technique is used to coat nickel over the coated substrates like galvannealed and galvanized, and uncoated substrate of cold rolled closed annealed steel sheets as well. These coated substrates are exposed to 3.5% aqueous NaCl solution in a flat cell to carry out the corrosion tests. The effect of nickel coating on galvannealed, galvanized and cold rolled closed annealing steel sheets is studied for their anti-corrosive performance by electrochemical impedance spectroscopy. Electrochemical impedance data were analysed by using Bode and Nyquist plot by considering the metal-coating-electrolyte interface as an electrical equivalent circuit model. The circuit elements i.e. polarisation resistance and coating capacitance are determined to evaluate the corrosion behaviour of these multilayered coatings. The changes in the impedance characteristics of the systems are found to occur as a function of exposure time in all the three cases. These results have showed differences in the protective characteristics of the three systems, where the nickel coated galvannealed exhibited superior corrosion resistance compared to nickel coated cold rolled closed annealed and galvanised.     

锌粉颜料尺寸对有机富锌涂层电化学行为的影响

利用电化学阻抗谱(EIS)技术，研究了锌粉颜料平均粒度分别为7μm、3．5μm和500nm的有机富锌涂层的电化学行为．研究表明，在阴极保护阶段，含有纳米尺度锌粉颜料的富锌涂层可对基底钢材提供更有效的电流保护，但锌粉颜料尺寸对富锌涂层阴极保护作用时间的长短没有显著影响；在阻挡保护阶段，含有纳米尺度锌粉颜料的富锌涂层中，锌粉的腐蚀速率较低。涂层具有较大的涂层电阻和较小的涂层电容，发展为具有较强阻挡保护作用的涂层．     

Mechanistic changes in cut-edge corrosion induced by variation of organic coating porosity

The scanning vibrating electrode technique (SVET) has been used to investigate the mechanism of corrosion occurring at exposed metallic cut edges of galvanised steel materials coated with identical thickness organic polymeric layers. Organically coated galvanised steel samples have been prepared by application of a 30 μm polyester coating to both sides of a pre-treated hot dip zinc (99.85%) aluminium (0.15%) galvanised steel substrate. In separate samples the coatings were applied to both sides simultaneously and then cured or applied sequentially to each side curing after each application. Electrical impedance spectroscopy (EIS) was used to probe the porosity of the resulting organic coatings. This revealed that simultaneous coating application and curing resulted in both polymer layers showing EIS pore resistance of 0.6 MΩ whereas sequential coating resulted in one side showing a pore resistance of 0.6 MΩ and the other showing a capacitive EIS response with no measurable porosity. When the metallic cut edges of organically coated steel materials, coated with symmetric thicknesses of organic layers of identical pore resistance, are exposed to 5% NaCl the SVET iso-current contour maps show that both zinc layers behaving as local anodes. In addition, there is significant sample passivation in the 24 h exposure period. In the samples coated with materials of identical thicknesses but different porosity, the SVET iso-current contour maps show anodic activity focussed beneath the organic coating with the capacitive EIS signature. The greater porosity of the coating on the opposite side of the exposed cut edge enables oxygen transport to the delaminating surface and this forces anodic activity onto the other zinc layer.     

析氢对钢表面涂层缺陷破坏过程的交流阻抗谱特征

研究了在过保护电位作用下钢表面析氢作用对改性沥青涂层缺陷的破坏;并根据析氢电流变化,将破坏过程分为三阶段,研究了每阶段表面阻抗谱特征.结果表明,当析氢电流明显增大,相应阻抗图出现双容抗弧时,缺陷周围开始形成微观剥离;在-1.20 V、-1.37 V 和-3.07 V(均为CSE)电位作用下,双容抗弧出现时间分别为：55天未发现、8天和0.5天;对-3.07 V下、30天的涂层缺陷观察证实了宏观剥离行为的存在.     

The role of zinc aluminum phosphate anticorrosive pigment in Protective Performance and cathodic disbondment of epoxy coating

Protective performance and cathodic disbondment of epoxy coating pigmented with zinc aluminum phosphate (ZPA) were studied in this work. In solution, superior corrosion inhibition of ZPA extracted from EIS and electrochemical noise data was connected to deposition of a protective layer. EIS evaluation of the pigmented coatings indicated significant effect of modification of zinc phosphate on the protective performance as well as resistance to cathodic disbonding. Compared to ZPA, introduction of zinc phosphate resulted in inferior performance in cathodic disbonding test. In presence of ZPA, precipitation at disbonding front inferred from EIS data was confirmed by SEM.     

循环压力对环氧涂层在模拟深海环境中失效行为的影响

在模拟深海环境下,利用电化学阻抗技术并结合重量法,研究了循环压力对纯环氧涂层在3.5mass%NaCl溶液中失效行为的影响。结果表明,循环压力条件下,涂层的阻抗行为呈周期性变化规律:在高压条件下浸泡时,有机涂层电容较高、涂层电阻较低;而常压条件下两者都较高。循环压力增大,腐蚀介质更容易扩散到涂层内部,使得涂层吸水量增加,涂层电阻降低,涂层防护性能恶化。     

Ni-Fe-P 化学镀层抗 CO2 腐蚀性机理研究

目的研究Ni-Fe-P化学镀层抗CO2腐蚀性机理。方法通过SEM,EDS,XRD以及EIS等技术对经化学镀Ni-Fe-P处理后的35Cr Mo钢表面进行表征,分析其抗CO2的腐蚀性能。结果处理后的35Cr Mo钢表面为非晶态组织,硬度高达570.12HV。Ni-Fe-P镀层钢腐蚀倾向减小,极化电阻增大,镀层对基体形成了较好保护。镀层的腐蚀过程受溶液双电层和钝化膜的影响。结论 Ni-Fe-P镀层在CO2水溶液中具有极强的钝化倾向,可显著提高材料的抗CO2腐蚀性能。     

Statistical evaluation of EIS and ENM data collected for monitoring corrosion barrier properties of organic coatings on Al-2024-T3

This paper describes the statistical treatment of electrochemical noise (electrochemical noise methods, ENM) and impedance (electrochemical impedance spectroscopy, EIS) data collected for corrosion monitoring of epoxy coated aluminum 2024-T3. The epoxy was applied using electrodeposition to Al-2024-T3 panels treated with one of three surface pretreatments. Six coating systems were prepared by varying the electrodeposition parameters and the pretreatment. Linear regression analysis of the data was used to detect the individual contributions relating to the analysis technique, topcoat application and pretreatment type. As a result of the statistical treatment it was found that EIS data has significantly less variance compared to ENM data, that EIS data can be used to differentiate the effects generated from the coating and pretreatment, and that ENM data cannot be used to differentiate the effects generated from the coating and pretreatment due to the high variance in data values associated with ENM. None of this information could be quantified without the statistical treatment.     

A study on corrosion resistance characteristics of PVD Cr-N coated steels by electrochemical method

The corrosion behavior of Cr-N coated steels with different phases (-Cr, CrN and Cr₂N) deposited by cathodic arc deposition on AISI H13 steel was investigated in a 3.5% NaCl solution at ambient temperature. Potentiodynamic polarization tests, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) were the techniques applied to characterize the corrosion behavior. It was found that the CrN coating had a lower current density from potentiodynamic polarization tests than others. The porosity, corresponding to the ratio of the polarization resistance of the uncoated and the coated substrate, was higher in the Cr₂N coating than in the other Cr-N coated steels. EIS measurements showed, for most of the Cr-N coated steels, that the Bode plot presented two time constants. Also, the Cr₂N coating represented the characteristic of Warburg behavior after 72 h of immersion. The coating morphologies were examined in planar view and cross-section by SEM analysis and the results were compared with those of the electrochemical measurement. The CrN coating had a dense, columnar grain-sized microstructure with minor intergranular porosity. From the above results, it is concluded that the CrN coating provided a better corrosion protection than the other Cr-N coated steels.     

Corrosion mechanisms of steel concrete moulds in contact with a demoulding agent studied by EIS and XPS

The behaviour of E24 mild steel was studied by XPS analysis and electrochemical impedance spectroscopy (EIS) in a filtered solution of cement (pH 13), and an alkyl N-aminodiphosphonate aqueous solution called Aquadem^® (7?pH?13). XPS results showed that the corrosion products developed in both media consisted of Fe₂O₃, covered by a very thin layer of goethite. The thickness of this oxide layer was estimated to be 3 nm. XPS analysis also demonstrated the adsorption of Aquadem^® on the outer layer of FeOOH for pH lower than the zero charge pH of goethite (7.55). From XPS and EIS results, physical models of the E24 steel/electrolyte interface are proposed as a function of pH. For 11?pH?13, the steel is covered by a passive film, while for pH?10, pitting corrosion takes place. At pH 7, an additional mass transport phenomenon must be taken into account. The fitting procedure provided values for several physical parameters (electrolyte resistance, passive film resistance), from which the film capacitance and the dielectric constant of the oxide layer were calculated.     

Effect of Si nanoparticles on the corrosion protection performance of organic coating on carbon steel in chloride environment

This work examines the effect of silicon (Si) nanoparticles on the corrosion protection performance of epoxy coating over carbon steel by Electrochemical Impedance Spectroscopy (EIS) and Transmission Electron Microscopy. The EIS was performed in a 0.1 M NaCl solution after a wet/dry cyclic corrosion and continuous immersion test. The addition of Si nanoparticles increased the film resistance (R_f) and the charge transfer resistance (R_ct) of the coated steel. The surface analysis showed that uniform and fine Si-Fe complex oxides layers were formed acting as barrier layers that enhanced the corrosion protection of the coated steel in the wet/dry cyclic corrosion test. The results of the EIS of the coated steel with Si nanoparticles suggested that Si nanoparticles play a beneficial role in enhancing the corrosion resistance of organic coated steel.     

C/SiC/MoSi2–Si multilayer coatings for carbon/carbon composites for protection against oxidation

To improve the oxidation resistance of carbon/carbon (C/C) composites, a C/SiC/MoSi₂–Si multilayer oxidation protective coating was prepared by slurry and pack cementation. The microstructure of the as-prepared coating was characterized by scanning electron microscopy, X-ray diffraction and energy dispersive spectroscopy. The isothermal oxidation and erosion resistance of the coating was investigated in electrical furnace and high temperature wind tunnel. The results showed that the multilayer coating could effectively protect C/C composites from oxidation in air for 300 h at 1773 K and 103 h at 1873 K, and the coated samples was fractured after erosion for 27 h at 1873 K h in wind tunnel. The weight loss of the coated specimens was considered to be caused by the formation of penetration cracks in the coating. The fracture of the coated C/C composites might result from the excessive local stress in the coating.     

铝合金防护涂层老化动力学研究

在紫外/盐雾加速综合环境条件下,研究了铝合金试样上聚酰胺清漆老化过程。采用环境扫描电子显微镜观察了防护涂层表面形貌的变化,采用电化学阻抗(EIS)分析了涂层的老化过程,同时还测量了光泽度、颜色、表面电阻和体积电阻在涂层老化过程中的变化。结果表明：在涂层老化过程中,涂层孔隙率增加,而体积电阻、表面电阻则降低, EIS给出了在涂层老化的不同阶段的特征。采用光泽度、颜色、表面电阻和体积电阻以及电化学阻抗数据作为性能参数,建立了涂层老化动力学方程,并给出了涂层失效判据,并对涂层老化动力学的参数进行了讨论,认为采用体积电阻或低频阻抗模值作为性能参数描述涂层老化动力学过程更为合理。