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.     

Electrochemical approach to evaluate the interlayer adhesion of organic coatings

In this work we used the electrochemical impedance spectroscopy (EIS) to quantify the interlayer adhesion of coatings. Different automotive basecoat/clearcoat systems were tested on their interlayer adhesion with EIS. For EIS measurements, two thin electrode stripes of an electroconductive ink were applied between two coating layers. The impedance measurements were conducted to find out the effect of moisture on the interlayer adhesion. The data obtained show a strong sensitivity of the interlayer impedance on the outer air humidity and point out at the possibility of following the water accumulation in the interlayer and the formation of the conductive paths. Such phenomena lead to the adhesion loss and delamination between the coating layers. We found that the interlayer adhesion loss follows the same trend as the changes of the activation energy of the ion mobility, which can be derived from the interlayer resistance, measured with EIS.

For the verification of EIS measurements blister test measurements were carried out. With this method, it is possible to evaluate directly the interlayer adhesion of coatings. A good correlation was found between EIS and blister test data.     

Comparative EIS study of pretreatment performance in coated metals

Various coated metal samples with different pretreatments were investigated by electrochemical impedance spectroscopy (EIS). Variables were the substrate (cold-rolled steel and hot-dipped galvanized steel), phosphate system (iron and zinc phosphate), post rinse (chromate and silane/zirconium rinse) and paint systems. The corrosion performance was determined on the basis of coating degradation, water uptake and interface delamination of the tested samples. The zinc phosphate performed better than iron phosphate on CRS. The silane/Zr rinse did not perform well in the CRS/iron-phosphate system. However, it showed a better performance than the chromate when used as a post rinse of zinc phosphate. Salt spray test (SST) and adhesion test results of the same samples are also reported in this paper and compared to the EIS data. The correlation among three test methods was poor.     

Correlation of morphology and barrier properties of thin microwave plasma polymer films on metal substrate

The barrier properties of thin model organosilicon plasma polymers layers on iron are characterised by means of electrochemical impedance spectroscopy (EIS). Tailored thin plasma polymers of controlled morphology and chemical composition were deposited from a microwave discharge. By the analysis of the obtained impedance diagrams, the evolution of the water uptake ?, coating resistance and polymer capacitance with immersion time were monitored and the diffusion coefficients of the water through the films were calculated. The impedance data correlated well with the chemical structure and morphology of the plasma polymer films with a thickness of less than 100 nm. The composition of the films were determined by means of infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The morphology of the plasma polymer surface and the interface between the plasma polymer and the metal were characterised using atomic force microscopy (AFM). It could be shown that, at higher pressure, the film roughness increases which is probably due to the adsorption of plasma polymer nanoparticles formed in the plasma bulk and the faster film growth. This leads to voids with a size of a few tens of nanometers at the polymer/metal interface. The film roughness increases from the interface to the outer surface of the film. By lowering the pressure and thereby slowing the deposition rate, the plasma polymers perfectly imitate the substrate topography and lead to an excellent blocking of the metal surface. Moreover, the ratio of siloxane bonds to methyl-silyl groups increases which implies that the crosslink density is higher at lower deposition rate. The EIS data consistently showed higher coating resistance as well as lower interfacial capacitance values and a better stability over time for the film deposited at slower pressure. The diffusion coefficient of water in thin and ultra-thin plasma polymer films could be quantified for the smooth films. The measurements show that the quantitative evaluation of the electrochemical impedance data requires a detailed understanding of the film morphology and chemical composition. In addition, the measured diffusion coefficient of about 1.5×10⁻¹⁴ cm² s⁻¹ shows that plasma polymers can act as corrosion resistant barrier layers at polymer/metal interfaces.     

Fundamental investigation on the stability of the steel/coating interfaces contaminated by submicroscopic salt particles

It is known that the presence of hydrosoluble species, mainly chlorides and sulphates, at the metal/paint interface, promotes osmotic blistering of the coating and underfilm metallic corrosion when the concentration exceeds a critical level. However, since the interface is not easily accessible by experiment, not much is known about interfacial structure, reactions and the processes causing degradation. Scanning Kelvin Probe (SKP) is an ideal tool for the in situ monitoring of the degradation processes at the buried interface. In the present paper, a study of the fundamental aspects of the stability of the contaminated buried steel/coating interfaces, specially focused on the initial stages of blistering and underfilm corrosion, has been carried out. Results of the characterization study performed with a height-regulated SKP (HR-SKP) on coated steel contaminated at the interface by different salt concentrations with well-defined crystal size and distribution are shown. An effect of crystal size and distribution has been observed. While, small crystals or low density of salt spots do not show macroscopic blistering, bigger crystals or a local accumulation of them can cause significant de-adhesion and macroscopic blistering.     

Studies of the impedance models and water transport behaviors of cathodically polarized coating

Cathodic protection (CP) is usually combined with organic coatings to protect metallic structures exposed to seawater. However, the application of CP would enhance coating failure, such as cathodic delamination. To date, there has been few works characterizing the impedance models and water transport behaviors of cathodically polarized coating. In the present article, the analyses of impedance models and water uptake processes of chlorinated rubber coating subjected to various levels of cathodic protection were studied during coatings aging process by electrochemical impedance spectroscopy (EIS).Four distinguished electrical equivalent circuits (EEC) were used to fit the EIS plots of coatings without CP, while only two were employed for samples with CP. Since no corrosion was expected to take place at the metal/coating interface for sample which was polarized cathodically. Coating capacitance was used to investigate the sorption characteristic of water in coating since the increase of C_c was associated with water penetration into the coating. Compared with the sample without CP, those coating systems under CP have a smaller water diffusion coefficient and a further water uptake process after the saturation period.     

Determination of the adhesion properties of an alkyd pigmented coating by electrochemical impedance spectroscopy

One of the most modern methods of characterizing the electrical properties of coatings is by electrochemical impedance spectroscopy (EIS). EIS can provide useful information about the transport of water and corrosive species through a coating. In this study, impedance measurements were performed in different frequency ranges at open circuit potential for an alkyd coating with TiO₂ as a mineral pigment in 3% NaCl. The most probable impedance equivalent circuit method (MPI) was considered for data analysis. The interpretation of the impedance spectra permitted the determination of water permeation, the formation of blisters, swelling of the coating, and the loss of adhesion.     

Determination of water uptake and diffusion of Cl ion in epoxy primer on aluminum alloys in NaCl solution by electrochemical impedance spectroscopy

The electrochemical impedance spectroscopy (EIS) of epoxy-coated aluminum alloy LY12 has been investigated during exposure to 3.5% NaCl solution. Using the continuous simulation of EIS by expanded general electrical model, the time-dependent impedance model of the alloy/coating/solution system was deduced. The results shown that the composite electrode displayed a barrier behavior before water and oxygen penetrated to alloy base. After water and oxygen reached the base, the impedance associated with corrosion of alloy base changed with the immersion time as following: (i) active corrosion period at the beginning (double-layer capacitance, C_dl, in parallel to the charge transfer resistance of electrochemical corrosion R_ct), (ii) impeding of the diffusion of corrosion production at the intermediate period as a result of the presence of coated film (a constant phase element Z_diff was additionally in series with R_ct), and (iii) appearance of the characteristic impedance related to Cl⁻ ion-participating reaction with alloy base at the later stage. From the linear part of ln C_c–t^0.5 curve in the early immersion stage, the apparent diffusion coefficient of water was obtained. The diffusion coefficient of water and Cl⁻ ion through the coating was also calculated by the required time for diffusion of permeation species through the coating to the metal interface obtained from the simulation of EIS data by which the occurrence of characteristic impedance element(s) corresponding to special species arrival can be determined.     

Corrosion protective performances of commercial low-VOC epoxy/urethane coatings on hot-rolled 1010 mild steel

The protective properties of low-VOC epoxy/urethane paint systems of commercial grade have been investigated using a variety of techniques such as electrochemical impedance spectroscopy (EIS). One epoxy-polyamide mastic/urethane, three high-solid epoxy-amine/urethane coatings, one solvent-free epoxy-amine/urethane, one water-based epoxy-amine and one high-VOC alkyd paint system (used as paint reference system) were applied on hot-rolled 1010 mild steel panels and exposed for up to 2000 h in the salt spray cabinet (SSC) or for 1 year at an outdoor marine test site. These paints were tested for their barrier properties, corrosion-induced adhesion loss and visual defects, as well as for their flexibility and resistance to direct impact. The barrier properties increased in the following order: alkyd相似文献   

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。     

Investigation on zinc phosphate effectiveness at different pigment volume concentrations via electrochemical impedance spectroscopy

This research is based on studying corrosion inhibitive effect of zinc phosphate at different pigment volume concentration (PVCs) in epoxy-polyamide system. EIS has been examined at open circuit potential (OCP) after 7 days of immersion in 3.5% NaCl solution to indicate electrochemical properties of epoxy coated mild steel at different levels of pigmentation. Coating capacitance, coating resistance, double layer capacitance and charge transfer resistance have been extracted from fitting of EIS results with an electrical circuit, while impedance magnitude at 100 mHz and phase angle (θ) at 10 kHz have been extracted directly from bode plots. Also OCP behavior was examined. Results showed best performance at PVC = 36.5%.     

Electrochemical Sensors for Nondestructive Evaluation of Adhesive Bonds

An in-situ corrosion sensor based on electrochemical impedance spectroscopy (EIS) has been used to detect moisture ingress into aluminum-aluminum and aluminum-composite adhesive bonds. Both wedge tests and tensile button tests (aluminum-aluminum bonds only) were performed. Upon moisture absorption, the impedance spectra change shape with the low-frequency region becoming resistive. The low-frequency impedance decreases by several orders of magnitude, depending on the adhesive and the experimental conditions. For bonds with stable interfaces, such as phosphoric acid anodized (PAA) aluminum, the absorbed moisture causes an initial weakening of the adhesive resulting in reduced strength or small crack propagation. A substantial incubation time prior to substrate hydration and bond degradation allows warning of potential joint deterioration and enables condition-based maintenance. For bonds with smooth interfaces with little or no physical bonding (mechanical interlocking), crack propagation can proceed interfacially with minimal moisture absorption. A comparison of the incubation times for Forest Products Laboratory (FPL, or sulfuric acid-sodium dichromate) etched surfaces, both bonded to epoxy adhesives and freely exposed to water or humidity at different temperatures, shows that hydration occurs with the same activation energy and, hence, the same mechanism, independent of whether or not the surface is covered with adhesive. However, the pre-exponential factor in the rate constant is dependent on the concentration of free moisture at the interface so that the hydration rate varies by several orders of magnitude.     

In situ capacitance measurements for in-plane water vapor transport in paint films

A capacitance technique has been adapted to study in-plane water vapor transport in paint films. The technique requires an application of electrical contact materials on the paint film surface for capacitance measurements by electrochemical impedance spectroscopy (EIS). The capacitance obtained by EIS using Cu tape and Ag paste as the contact materials are presented. A direct comparison of capacitance and gravimetric measurements demonstrates that the change in the coating capacitance is quantitatively correlated with the total amount of in-plane water vapor transported in paint films. The water vapor diffusion coefficient derived from the capacitance technique agrees with one from the gravimetric method.     

A Comparative Study of Anticorrosion Paints Based on Silicone-Urethane Binders: a Multilayer Primer

Using zinc phosphate, micaceous iron oxide and their combination in the composition of the undercoat, a series of novel multilayer paint systems based on different silicone-urethane binders with the same R/Si and Ph/R ratio have been formulated. The developed paint systems showed excellent mechanical, adhesion and chemical properties. Scanning Electron Microscopy (SEM) analysis of the surface of the paint systems shows no fractures or holes. The electrochemical impedance spectroscopy (EIS) evaluation of the developed paint systems confirms their excellent protective and anticorrosion properties, especially for Silicone-Urethane-Urea (SPUU) based paint systems with a combination of pigments in the composition of the undercoat. SPUU-based paint systems show low water uptake. The new multilayer silicone-urethane-based paint systems can be used as a anticorrosion primer.     

Studies of double layer capacitance and electron transfer at a gold electrode exposed to protein solutions

Electrochemical impedance spectroscopy (EIS) was used to investigate the electrochemical behaviour of a gold electrode exposed to proteins prepared in phosphate buffer. Exposure to solutions of human serum albumin (HSA) and immunoglobulin G (Ig.G) resulted in a decrease of the double layer capacitance (C_dl) and an increase in the charge transfer resistance (R_ct) at the gold electrode solution interface. The greatest capacitance decrease for both proteins was observed when exposure occurred at or more positive to the electrode open circuit potential (OCP). Exposure to Ig.G resulted in a greater decrease in capacitance as compared to HSA under identical conditions. These capacitance and charge transfer resistance variations were attributed to the formation of a proteinaceous layer on the electrode surface during exposure.     

The role of stress and topcoat properties in blistering of coil-coated materials

The effect of topcoat properties on the tendency of painted materials to blistering was studied. Six topcoats were applied on identical panels of hot-dip galvanized steel painted with a polyester primer. The tendency to blistering was assessed under the conditions of permanent condensation in a Q-panel condensation test at 60 °C. Internal tensile stress and stress development in organic coatings during temperature and relative humidity cycling were investigated by the cantilever curvature method. Although blisters originated from the metal/polymer interface, the extent of blistering was strongly influenced by the topcoat. Available data suggest that it may increase with the coating thickness, glass transition temperature (T_g) and thermal expansion properties. Connection was found between the internal tensile stress formed in topcoats during the paint film preparation and the extent of blistering. A hypothesis that stress-assisted interfacial bond hydrolysis was responsible for blister initiation is proposed. Other experiments suggested that local paint buckling over non-adherent sites can be caused by plastic deformation of the paint due to relief of compressive stress generated at elevated temperature or by ingress of water.     

In situ measurement of water at the organic coating/substrate interface

In situ and quantitative information on the water layer at the organic coating/substrate interface is crucial for understanding and preventing the failure of organic coating systems. A technique, based on a two-layer model derived rigorously from internal reflection theory, has been developed for measuring in situ the thickness and amount of the water layer at the organic coating/substrate interface. The technique gives new insight into the processes by which water degrades the coating/substrate bonds. In this technique, a transparent or an opaque organic coating of sufficient thickness is applied to an internal reflection element (IRE) with or without a thin metallic film, which is used as the substrate. A water chamber is attached to the organic-coated specimen. After adding water to the chamber, Fourier transform infrared-multiple internal reflection (FTIR-MIR) spectra are taken automatically at specified time intervals without disturbing the specimens or the instrument. Water uptake in the coating and FTIR-MIR spectra of water on the coating-free substrate are also used for the analysis. Examples of clear and pigmented coatings on untreated and treated substrate surfaces are given to demonstrate the technique. Results of water accumulation at the coating/iron interface with and without applied electrical potentials are given. In addition to measuring water at the coating/substrate interface, the technique provides a means for studying the transport of water through a coating adhered to a substrate. Information on water at the interface and its transport properties through coatings applied to a substrate is valuable for interpreting corrosion, blistering and delamination of organic coating systems, and for developing models for use in predicting the serivce lives of protective coatings.     

管道用酚醛环氧树脂内涂层失效分析

使用电化学工作站中的交流阻抗实验、结合高温高压釜实验以及端口扫描电镜(SEM)分析技术,研究了酚醛环氧树脂管道内涂层在含饱和H2S/CO2的3.5%NaCl(质量分数)水溶液中不同温度下的失效规律。结果表明,在电化学交流阻抗测试中,随着温度(50℃、70℃、90℃)的升高,涂层失效减缓;在高温高压釜16 h实验后,涂层表观正常(未出现起泡、开裂、表面颜色无明显变化)、附着力良好;结合端口扫描电镜(SEM)技术,进一步证明温度升高会导致涂层在含H2S/CO2的3.5%NaCl溶液中失效减缓。     

Capacitive properties of promising energy storage material based on thiophene containing perylenediimide polymer

In this study, electropolymerization of pre-synthesized N,N′-di-[3-[2-(3-thienyl)ethyl] phenyl] perylene-3,4,9,10-bis(dicarboximide) (ThPDITh) was performed on Au button electrode and the properties of the resultant polymer P(ThPDITh) were investigated by electrochemical techniques. Effect of the polymerization charge on the redox behaviors of the polymer film was investigated by cyclic voltammetry (CV) and the polymer film was further characterized by electrochemical impedance spectroscopy (EIS) measurements. Corresponding electrical equivalent circuit was applied to the experimental data to explain the electrochemical phenomenon on the interface of the Au/P(ThPDITh). In order to obtain information on the energy storage properties of P(ThPDITh) as a pseudo-capacitive electrode material, important cell characteristics, such as redox process in anodic and cathodic potential ranges, stability of galvanostatic charge–discharge (GCD) curves, coulombic efficiency, capacitance, energy and power density values were determined. Capacitance values, obtained through different measurements (CV, EIS and GCD) are all in good agreement with each other. All the results suggested that P(ThPDITh) is capable of undergoing multiple reversible redox processes, and a good candidate for improving the capacitance and energy density of electrode material while still offering high power capability.     

Influence of ultrasound irradiation on the adsorption of bovine serum albumin on copper

The effect of irradiation by power ultrasound on the adsorption of proteins on copper has been investigated, using bovine serum albumin (BSA) as a model protein in pH 7 phosphate buffer solution. Open circuit potential measurements, cyclic voltammetry and electrochemical impedance spectroscopy were used to characterise the copper/solution interface. Electrochemical impedance measurements at potentials close to the open circuit potential showed that pulsed ultrasound irradiation removes the naturally formed copper oxide films in phosphate buffer solution, and that their re-formation can lead to an oxide film with different electrical characteristics. Adsorption of BSA blocks the surface, decreasing or increasing the interfacial resistance, depending on the applied potential and the oxide characteristics, as well as changing the interfacial capacitance. This study augurs well for application of the combination of electrochemical impedance plus ultrasound to other systems. Special issue dedicated to Prof. Tony Wragg.