Corrosion of steel under the defected coating studied by localized electrochemical impedance spectroscopy

Corrosion of steel under the defected coating in near-neutral pH solution was investigated by localized electrochemical impedance spectroscopy (LEIS) measurements. The LEIS response is dependent on the size of the defect. For small defects, e.g., less than 200 μm in diameter, localized corrosion process and mechanism of steel, as indicated by the measured LEIS plots, change with time. The diffusion process dominates the interfacial corrosion reaction, which is due to the block effect of the deposited corrosion product combined with the geometrical factor of a large coating thickness/defect width ratio. In the presence of a big defect, e.g., up to 1000 μm, the LEIS responses measured at the defect are always featured by a coating impedance in the high-frequency range and an interfacial corrosion reaction in the low-frequency range. The block effect of corrosion product does not apply due to the relatively open geometry. Conventional EIS measurements on a macroscopic-coated electrode reflect the “averaged” impedance results from both coating and defect. The information of the localized electrochemical corrosion processes and mechanisms at the small defect is lost, and the coating impedance information is “averaged” out when a big defect is contained. LEIS measurement provides an essential technique to characterize microscopically the local electrochemical corrosion reaction of steel under the defected coating.     

锌镀层的铬磷化处理与浸有机膜工艺

提出将磷化与纯化处理工序合二为一的铬磷化处理工艺，论述了该工艺与浸有机膜工艺结合起来处理锌层的优点。     

镁-锂合金的锌系及锰系磷化膜的比较

观察了镁-锂合金锌系磷化膜和锰系磷化膜的宏观形貌及微观形貌,分析了2种膜层的化学组成,通过极化曲线、交流阻抗对比了基体、锌系磷化膜、锰系磷化膜的电化学性能,并比较了2种膜层的综合性能.结果表明:锌系磷化膜与锰系磷化膜对镁-锂合金基体具有较大的防护作用,尤其是锌系磷化膜膜厚,膜电阻大,自腐蚀电流密度小,耐蚀性更优.     

Defect dimension evaluation in organic coated galvanized steel by electrochemical impedance spectroscopy

The protective effectiveness of organic coatings, in controlling corrosion processes by the barrier effect, is dominated by the absence of defects passing through the coating and reaching the substrate. It is, however, difficult in general to identify and quantify the presence of defects. This work is an effort to reach a more precise quantification of the size of defect in organic coatings by means of electrochemical impedance spectroscopy (EIS) measurements. Artificial defects with controlled dimensions between 60 and 200 m were produced on organic coated galvanized steel (coil coating). After optimization of the experimental procedure for EIS data acquisition, the parameters obtained, according to a classical electrical model, were correlated with the defect dimensions. The results show that the double layer capacitance (C _dl) values depend in linearly on the defects area, while this is not true for the pore resistance (R _p) values, as the electrolyte resistivity inside the defects is a function of the defect size. Further work is necessary to extend the results to smaller defects and different systems, that is, different organic coatings and substrates.     

电解磷化工艺对锌系磷化膜耐蚀性影响的研究

为提高碳钢的耐蚀性与冷加工性能,采用电解磷化法制备了锌系电解磷化膜,通过盐雾试验、Tafel曲线及交流阻抗等方法研究了电解磷化工艺对锌系电解磷化膜耐蚀性的影响,并通过X-射线衍射仪分析了电解磷化膜的成分。结果表明,磷化膜成分为Zn_3(PO_4)_2、Fe_3(PO_4)_2,在Jκ为45 A/dm~2,磷化t为10 s,θ为60℃的条件下,电解磷化膜盐雾试验35 h不锈蚀。     

Comparative EIS and XPS studies of the protective character of thin lacquer films containing CR or P salts formed on galvanised steel, galvanneal and galfan substrates

X-ray photoelectron spectroscopy (XPS) is used to analyse variations during exposure to humidity and UV radiation (UVCON test) in the chemical composition of the outer surface of organic coatings (lacquers) containing phosphating or chromating reagents applied on galvanised steel, galvanneal and galfan substrates. By means of electrochemical impedance spectroscopy (EIS) measurements the protective character of the coatings analysed by XPS is studied and an attempt is made to establish possible relationships between the chemical composition of the surface of the lacquered substrates after exposure to the UVCON test and their electrochemical characterisation in immersion in a 3% NaCl solution. In general, the formation of defects or the loss of adhesion of the lacquer film leads to a significant reduction in charge transfer resistance values and, at the same time, an increase in interfacial capacitance values. The special behaviour of the galfan/lacquer “with chromating reagents” system is associated with the presence of a thin insulating film of chromium and aluminium oxides at the base of the pores in the lacquer. Interfacial capacitance values tend to evolve in close correspondence with the content of some elements on the surface of the materials.     

镁合金磷化处理与磷化膜的耐蚀性

通过正交试验得到了镁合金无铬最优锌系磷化配方,所得到的磷化膜在扫描电镜下观察呈针尖状结构,能谱仪分析表明磷化膜的主要成分为锌的磷酸盐,腐蚀试验和电化学测量结果表明最优磷化配方处理可以显著提高镁合金的耐腐蚀性能.     

A novel approach to heal the sol-gel coating system on magnesium alloy for corrosion protection

Sol-gel-based coatings exhibit high potentiality to be as an alternative to toxic chromate coatings for surface pre-treatment of metals and alloys. However, as soon as even small defects appear in the coating, the coating cannot stop the development of corrosion process. Present work demonstrates the possibility to use zinc nitrate as healing agent to repair the organic silane coatings in NaCl solution. The zinc nitrate was added to the 0.005 M NaCl solution where AZ91D magnesium alloy coated with organic silane coating was immersed. The healing process and the healing mechanism were investigated by electrochemical measurements and scanning electron microcopy coupled with energy dispersive spectroscopy. The results demonstrated the introduction of zinc nitrate to the electrolyte could stop the development of corrosion process of the coating system and a remarkable recovery on corrosion resistance could be obtained. This effect may be attributed to the formation of zinc oxide/hydroxide on the defective areas, hindering the corrosion activities.     

不锈钢表面电化学磷化及膜层性能

采用由4.0 g/L ZnO、4 g/L CaCl2、5%(体积分数)H3PO3、4 g/L酒石酸和3 g/L氯酸钠组成的锌钙系磷化液,在温度为70°C和电流密度为4 mA/cm2的条件下对1Cr18Ni9Ti不锈钢表面进行电化学磷化20 min。对比了所得磷化膜与采用相同磷化液化学磷化2 h所得膜层的表面形貌、相结构和耐蚀性。结果表明,与化学磷化相比,电化学磷化所需时间较短,所得膜层的结晶大小和分布均匀,耐腐蚀性更好。     

In situ electrochemical Scanning Kelvin Probe Blister-Test studies of the de-adhesion kinetics at polymer/zinc oxide/zinc interfaces

Fundamental investigations of the polymer/zinc oxide/zinc interface corrosion stability were performed in situ by means of the electrochemical Height Regulated Scanning Kelvin Probe Blister-Test (HR-SKP-BT) under controlled atmospheric conditions. A hole under an adhesive layer film served as electrolyte reservoir to initiate cathodic de-adhesion processes. Then a combinatorial approach was undertaken to simultaneously study the influence of electrolyte pressure at constant defect polarisation and of relative atmospheric humidity on the de-adhesion rate. The time resolved blister growth and the propagation of the three phase boundary polymer/oxide covered zinc/interfacial electrolyte layer could be detected. It could be proven that the oxygen reduction induced electrochemical damage of the interface precedes the subsequent mechanical de-adhesion process. By variation of the relative atmospheric humidity the water concentration within the bulk adhesive and its interphase adjacent to the metal substrate could be adjusted. These processes were further analysed by peel-tests and in situ Attenuated-Total-Reflection Infrared Spectroscopy (ATR-IR) studies of water diffusion. A decrease of the interphasial water concentration led to a deceleration of the de-adhesion kinetics for constant defect conditions and to smaller interfacial ion transport rates. This could be assigned to an inhibition of the electron transfer reactions at the front of de-adhesion and an increased adhesion force between polymer film and oxide covered metal preventing the formation of an extended interfacial electrolyte layer.     

铝合金磷化膜性能的研究

采用中温锌系磷化工艺对LY12硬铝合金进行磷化处理获得磷化膜.通过硫酸铜点滴试验,电化学测试等考查了磷化膜的耐蚀性;利用扫描电子显微镜、能谱仪等对磷化膜的表面形貌、化学成分进行分析.结果表明,该磷化膜外观颜色呈浅灰色,均匀光亮,耐蚀性好,硫酸铜试验耐蚀t为63 s,线性极化电阻为4.174 kΩ;表面形貌为片状晶体层层...     

In situ X-ray analysis under controlled potential conditions: An innovative setup and its application to the investigation of ultrathin films electrodeposited on Ag(1 1 1)

An innovative setup to combine electrochemical and in situ surface X-ray diffraction (SXRD) measurements is described. This electrochemical cell has a different design from the other ones commonly used for X-ray diffraction studies. It allows the sample surface to stay always completely immersed into the solution under controlled potential conditions even during the SXRD measurements. The X-ray beam crosses the liquid (about 1 cm) and the cell walls. Because of the high X-ray energy, the beam attenuation is negligible and by an appropriate positioning of the detector arm slits it is possible to minimize the diffuse scattering induced by the liquid and cell walls in order to still detect the minima of the crystal truncation rods (CTRs). The liquid solution in the cell is managed by a special device, which allows the controlled exchange of the electrolyte solutions necessary in the electrochemical atomic layer epitaxy (ECALE) growth. The whole setup can be remotely controlled from outside the experimental hutch by a dedicated computer. As an example we report measurements on S layers deposited at underpotential on the Ag(1 1 1) surface, and on CdS films of increasing thickness.     

Amphiphilic amido-amine as an effective corrosion inhibitor for mild steel exposed to CO2 saturated solution: Polarization, EIS and PM-IRRAS studies

The corrosion behavior of mild steel in CO₂-saturated 5% NaCl solution with N-[2-[(2-aminoethyl) amino] ethyl]-9-octadecenamide corrosion inhibitor at 25 °C has been studied by using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) measurements. Both potentiodynamic polarization and EIS measurements reveal that this amido-amine precursor inhibits the carbon steel corrosion and the inhibition efficiency increases with increasing the inhibitor concentration. The corrosion inhibitor exhibits high corrosion efficiencies as a mixed-type inhibitor, with a predominant influence on the anode process. The organic inhibitor acts blocking surface sites at low concentrations and by modifying the adsorption mechanism forming a protective barrier against corrosive ions at high concentrations. EIS results show that the mechanism of its corrosion inhibition at concentrations higher than 0.82 × 10⁻⁵ M is by forming a protective bilayer with small pore sizes that hinders the passage of the reactive species. PM-IRRAS measurements demonstrate that the inhibitor is chemisorbed to surface steel. Therefore, its spectrum reveals that the inhibitor monolayer has an amorphous structure.     

低温高效钢铁磷化及其成膜机理的研究

由于常温磷化存在沉渣多 ,耐磨、耐蚀性差等缺点 ,低温磷化的研究正日益受到人们的重视。本文研制了一种低温、高效锌系钢铁磷化液。探讨了磷化膜的成膜机理 ,沉渣的形成条件及抑制沉渣生成的方法。该磷化液具有处理温度低、成膜快、沉渣少、耐磨、耐蚀性好等特点。     

锌钙系磷化的最新应用研究

研究了3种新的锌钙系磷化工艺和配方，中温高耐蚀黑色磷化，磷化膜细致，耐蚀性优异，可用于钢铁的防锈磷化；钙改良的低温低锌磷化，钙的加入有利于镀锌板，铝板，钢板的复合件的磷化，可用于电泳涂装，中温耐热锌钙系磷化可用于需高温烘烤涂料涂装前的磷化处理，锌钙系磷化是磷化技术发展的一个方向。     

Monitoring of a military vehicle coating under Prohesion exposure by embedded sensors

Two-layered organic coatings protect metallic structures against corrosion by reducing the transport of water, ions, and oxygen from the environment to the substrate and storing species that provide corrosion inhibition. The topcoat and the primer provide the former and latter, respectively, with the primer also providing adhesion between the topcoat and the substrate. A standard testing method for coatings is the ASTM G85 Prohesion^® test. This test involves alternating between a wet exposure of 1-h salt spray at 25 °C and a dry exposure of 1-h air at 35 °C. Apart from visual inspection, conventional monitoring of coating properties is achieved by ex situ electrochemical tests under immersion in a suitable electrolyte. In situ monitoring during a Prohesion^® test was performed for a military vehicle coating system using embedded sensors located between the topcoat and primer. In situ results associated with the dry and wet exposures are presented from electrochemical impedance spectroscopy and electrochemical noise measurements. In situ single-frequency impedance measurements were used to monitor the water uptake/loss associated with the exposures of the test conditions. Ex situ monitoring was also performed for comparison with the in situ embedded sensor monitoring.     

稀土元素对机械镀锌层性能的影响

采用机械镀锌工艺,在镀层形成过程中添加某种稀土盐获得机械镀锌层。测定了镀层的电化学腐蚀参数、镀层孔隙率、元素谱线及镀层断面形貌。讨论了稀土含量对镀锌层电化学腐蚀性能、孔隙率的影响。研究结果表明:稀土能显著改善机械镀锌镀层的耐蚀性能和提高镀层的致密性;镀层耐蚀性随稀土添加量增加呈先提高后降低趋势;当稀土加入量为2%时,锌镀层耐蚀性最好,致密性最高。     

铅-3%锑合金电化学磷化工艺及影响因素研究

提出了一种以锌钙系磷化液为主体的铅-3%锑合金电化学磷化新工艺。电化学测试结果表明:合金经过磷化后,表面形成的磷化膜能有效阻止其在3%NaCl溶液中的腐蚀,使合金的稳定性得到提高。该工艺所用试剂不含有害促进剂,磷化过程无污染,技术环保,具有工业推广价值。     

Electrochemical studies of the inhibition of the cathodic delamination of organically coated galvanised steel by thin conversion films

Scanning Kelvin Probe (SKP) measurements of thin amorphous conversion film coated galvanised steel in combination with current density-potential curves and electrochemical impedance spectroscopy (EIS) were performed with the aim to improve the understanding of electrode potentials at the coating/metal interface and their influence on corrosive de-adhesion. The thin hybrid conversion films contained Zn-phosphates, titanates and also complexing organic compounds and led to an inhibition of the cathodic oxygen reduction and anodic zinc dissolution. In the polymer coated area the conversion film leads to a cathodic shift of the potential as measured by means of the SKP. This cathodic potential shift is explained by the substitution of the n-semiconducting Zn-oxide with an insulating inorganic layer. When the SKP detects the potential of freely corroding iron at a defect, where no protective coating layer is, the interfacial potential for the conversion film coated zinc layer is more negative than the defect potential. This leads to a diminished driving force for an oxygen reduction induced delamination process which is of relevance for the understanding of cut-edge corrosion.     

快速电化学磷化实验研究

在常温工况下,将电化学方法与磷化处理相结合,加速磷化液中各离子的扩散,使磷化时间保持在10 min以内。对电化学磷化方法中的各影响因素进行对比实验后发现,在常温工况下的最优磷化处理条件为马日夫盐浓度30~50 g/L,硝酸锌浓度50~70 g/L,电流密度1.00~1.50 A/dm2,电化学磷化时间5~7 min。在此条件下所制得的结晶型磷化膜综合性能最佳。分析测试表明:磷化膜主要包括O、Zn、P、Mn、Fe元素,且磷化膜耐腐蚀性强,晶体均匀致密,富有层次感,易于涂层材料附着。