Corrosion protection assessment of sacrificial coating systems as a function of exposure time in a marine environment

The present investigation assessed the corrosion protection performance of 17 different Zn and Al sacrificial coating system configurations during marine atmospheric exposure at Kure Beach, NC. The coating systems incorporated several conversion coating layers, primers and organic topcoats. Visual observations and electrochemical measurements (including electrochemical impedance spectroscopy, EIS) were made on six different occasions throughout the 20-month exposure time. Milled scribes on each of the coating specimens allowed for defect protection as well as barrier protection to be investigated. A novel corrosion analysis technique utilizing a specialized conducting agar (SCAR) cell enabled impedance measurements to be made on both intact and defect areas. Visual observations, E_oc's, and EIS as a function of atmospheric exposure time provided complementary results. Impedance results were found to be useful in determining a coating's barrier protection and scribe damage analysis accurately represented defect protection.     

Comparative electrochemical studies of zinc chromate and zinc phosphate as corrosion inhibitors for zinc

The anticorrosive performance of two inhibitive pigments, zinc chromate and zinc phosphate, was compared using electrochemical impedance spectroscopy (EIS) and the scanning vibrating electrode technique (SVET) in pigment extracts in 0.1 M NaCl. It was observed that zinc was protected from corrosion in both extracts. In tests using hot dip galvanised steel painted with an epoxy primer incorporating the pigments, the SVET detected the anodic and cathodic distribution along the scribes, although no significant differences were observed among the various primers. On the contrary, EIS was able to distinguish processes occurring on the metal surface exposed by the scribe in different samples. For primers with anticorrosive pigment, a time constant at high frequencies was attributed to a layer of protective nature, probably formed by metal ions from the substrate and inhibitive ions leached from the anticorrosive pigments.     

Corrosion protection assessment of sacrificial coating systems as a function of exposure time in a marine environment

The present investigation assessed the corrosion protection performance of 17 different Zn and Al sacrificial coating system configurations during marine atmospheric exposure at Kure Beach, NC. The coating systems incorporated several conversion coating layers, primers and organic topcoats. Visual observations and electrochemical measurements (including electrochemical impedance spectroscopy, EIS) were made on six different occasions throughout the 20-month exposure time. Milled scribes on each of the coating specimens allowed for defect protection as well as barrier protection to be investigated. A novel corrosion analysis technique utilizing a specialized conducting agar (SCAR) cell enabled impedance measurements to be made on both intact and defect areas. Visual observations, E_oc's, and EIS as a function of atmospheric exposure time provided complementary results. Impedance results were found to be useful in determining a coating's barrier protection and scribe damage analysis accurately represented defect protection.     

Laboratory evaluation of corrosion resistance at metallic substrates by an organic coating: delamination effects

The corrosion behaviour of an epoxy-polyamide primer applied on galvanized steel specimens during immersion in 3% NaCl aqueous solution was examined by electrochemical impedance spectroscopy (EIS). The investigation of both intact and defective coatings allowed for the comparison of their electrochemical behaviours in order to assess the anticorrosive characteristics of the system. The impedance response of the intact coating was found to correspond to a porous film presenting localised electrochemically active areas, in which the precipitation of zinc-containing corrosion products contributes to the sealing of the coating. Conversely, scribed defects cannot be spontaneously sealed and no effective protection of the metal can be achieved.     

颜填料体积浓度对水性环氧导静电防腐蚀涂层性能的影响

考察了颜填料体积浓度（PVC）对水性环氧导静电防腐蚀涂料涂层导静电性能和防腐蚀性能的影响,运用X射线能谱（EDX）分析了导电填料的元素组成,采用电化学阻抗谱（EIS）、扫描电镜（SEM）等手段对不同颜填料体积浓度的涂层进行了性能测试及表征,根据不同颜填料体积浓度涂层的物理机械性能、盐水浸泡实验结果和电化学阻抗谱分析,确定该水性环氧导静电防腐蚀涂料的最佳颜填料体积浓度为35%。     

Real time mapping of corrosion activity under coatings

Current accelerated testing of aircraft coating systems for corrosion protection relies heavily on salt spray methods. Electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and electrochemical noise methods (ENM) provide insight into the global properties of a coating system, and both techniques are being used on a limited basis. However, there is a need to investigate corrosion events with greater spatial resolution under coatings at the metal/coating interface. Such corrosion activity may be related to coating defects and variations in the surface chemistry of the underlying metal.

The scanning vibrating electrode technique (SVET) has been developed to allow high spatial resolution investigation of localized corrosion activity that may be associated with coating defects or galvanic coupled regions of the metal surface. The SVET offers high resolution in current measurements of the order of 0.5 μA/cm² and is able to detect in-situ initiation and progress of corrosion activity under a protective coating. Using the SVET, minute variations in d.c. current associated with localized corrosion activity are detected and used to map both anodic and cathodic corrosion activities in a localized area. The difference in initial corrosion activity under various coatings can be correlated to the performance life of the coatings. The application of SVET to aircraft coatings and corrosion is reported to demonstrate the utility of this important new electrochemical tool.

In the current study, the SVET was used to discriminate the corrosion protection performance of selected sol–gel based coating systems. Sol–gel based surface treatments are being developed as part of an environmentally compliant coating system alternative to the currently used chromate-based systems. The SVET results are compared with data obtained from chromium inhibition coating systems. The SVET analyses are compared with electrochemical impedance measurements. The comparison of such data will provide the basis to adopt SVET measurements as an early performance discriminator for newly developed coating systems.     

电化学阻抗技术在金属腐蚀及涂层防护中的研究进展

本文论述了交流阻抗谱(EIS)在金属腐蚀与涂层防护中的研究进展,重点探讨了交流阻抗技术在钢铁材料腐蚀、有机涂层和金属涂层以及模拟深海环境中有机涂层的耐蚀性能和腐蚀机理的研究进展。最后指出了交流阻抗数据分析拟合中存在的问题,并对电化学阻抗谱在腐蚀领域及其他方面的应用进行了展望。     

A new class of corrosion inhibitors for waterborne coatings: 4-methyl-γ-oxo-benzene-butanoic acid complexes

Amine and transition metal based complexes with 4-methyl-γ-oxo-benzene-butanoic acid represent a new class of corrosion inhibitors specifically designed for long-term corrosion protection in waterborne coatings. Today, corrosion protection in waterborne technology is typically achieved using traditional anticorrosive pigments initially developed for use in solventborne coatings. Regulations concerning heavy metals and limitations regarding the compatibility and performance of such materials in waterborne coatings have created a need for novel approaches. Mechanistic aspects are discussed for the 4-methyl-γ-oxo-benzene-butanoic complexes based on electrochemical solution experiments (electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV)) and investigations performed on coated substrates. Exposure results underline the high efficiency of such complexes for both long-term corrosion protection and weld seam rust control in waterborne coatings.     

Synergic enhancement of the anticorrosion properties of an epoxy coating by compositing with both graphene and halloysite nanotubes

The aim of this research was to improve the corrosion resistance of metal surfaces with polymer coatings. Both graphene and halloysite nanotubes (HNTs) were introduced together into the epoxy resin coating for the enhanced barrier protection of the metallic surface. The anticorrosion behaviors of different coatings were comparatively evaluated by the potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), and neutral salt spray (NSS) tests. The potentiodynamic polarization curves showed that the coating containing 0.5 wt % HNTs and 0.8 wt % graphene (H05G08EP) together had the most positive corrosion potential and the minimum corrosion current density. The EIS results revealed that graphene endowed the composite coatings with excellent electrochemical performance for anticorrosive purposes. The NSS tests indicated that H05G08EP endured the longest NSS time. These results suggest that H05G08EP had the best corrosion resistance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47562.     

Corrosion study of hybrid sol–gel coatings containing boehmite nanoparticles loaded with cerium nitrate corrosion inhibitor

To improve the corrosion protection of sol–gel derived hybrid silica/epoxy coatings containing boehmite nanoparticles, inorganic corrosion inhibitor was introduced into the coating via encapsulation in the nanoparticles. The morphology and chemical structure of the deposited films were studied by Scanning Electron Microscopy (SEM) and Fourier Transformed Infra-red Spectroscopy (FT-IR). The anticorrosion and self-healing properties of the coatings were evaluated by Electrochemical Impedance Spectroscopy (EIS). The high corrosion resistance performance of such coatings is due to the presence of encapsulated cerium nitrate corrosion inhibitor that can be released at the defects within the coating, hindering the corrosion reactions at defective sites.     

Corrosion study of hybrid sol–gel coatings containing boehmite nanoparticles loaded with cerium nitrate corrosion inhibitor

To improve the corrosion protection of sol–gel derived hybrid silica/epoxy coatings containing boehmite nanoparticles, inorganic corrosion inhibitor was introduced into the coating via encapsulation in the nanoparticles. The morphology and chemical structure of the deposited films were studied by Scanning Electron Microscopy (SEM) and Fourier Transformed Infra-red Spectroscopy (FT-IR). The anticorrosion and self-healing properties of the coatings were evaluated by Electrochemical Impedance Spectroscopy (EIS). The high corrosion resistance performance of such coatings is due to the presence of encapsulated cerium nitrate corrosion inhibitor that can be released at the defects within the coating, hindering the corrosion reactions at defective sites.     

Improved mechanical and anticorrosion properties of metal oxide-loaded hybrid sol–gel coatings for mild steel in a saline medium

Abstract

A hybrid organic–inorganic sol–gel coating was successfully prepared and subsequently functionalized individually with five different metal oxide additives. The effect of the incorporated oxides on the corrosion protection performance and scratch-resistance properties of the hybrid base coating on mild steel substrates was investigated using electrochemical techniques, namely electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP) as well as mechanical testing. The steel-coated specimens were immersed in 3.5?wt.% NaCl corrosive medium for two weeks and the results reveal an excellent corrosion protection performance by all coating formulations with a significant high corrosion-resistance property for the sample loaded with molybdenum oxide. Scanning electron microscopy (SEM) images proved the absence of corrosion signs, defects, micro cracks, or delamination on the surface of the coated samples. Compared with the pure hybrid coating, all the metal oxide-embedded coatings (except for the sample loaded with yttrium(III) oxide) show comparable aqueous contact angle values as well as enhanced hardness and adherence properties. No noticeable dependence was observed for the surface roughness parameters as a function of the type of incorporated metal oxide within the sol–gel matrix. Overall, the results of this study demonstrate that metal oxides can be advantageous to the desired properties of hybrid sol–gel coatings applied to steel surfaces.     

Study on preparation and anticorrosive performance of a new high hydrophobic anticorrosive coating

Water-based anticorrosive coatings have poor water resistance, which easily lead to coating deterioration and metal corrosion. In order to improve the anticorrosion performance of waterborne coating, herein, the polytetrafluoroethylene/dimethyl siloxane/epoxy resin (PTFE/PDMS/EP) hydrophobic anticorrosive coating was prepared by layer-by-layer construction. The spatial structure and microscopic morphology of the hydrophobic coating were analyzed by XRD, FTIR, and SEM. The hydrophobicity and corrosion resistance of the composite coating were analyzed by hydrophobicity test, electrochemical polarization curve, hydrophobicity and corrosion resistance test of the mixed layer, Tafel polarization curves, and AC impedance spectrum. The results showed that the water contact angle of PTFE/PDMS/EP coating reached 141° and the protection efficiency of PTFE/PDMS/EP coating was 98.62%. After soaking for 7 days, the corrosion process still stays at the initial stage, which was mainly due to the good sealing and barrier properties and high anticorrosion efficiency of PTFE/PDMS/EP coating. The coating has high corrosion protection efficiency and long service life, which is of great significance to metal corrosion protection in harsh marine environments.     

Stearic acid grafted chitosan/epoxy blend surface coating for prolonged protection of mild steel in saline environment

Chitosan (CS) is a promising candidate for green anticorrosive coating owing to its film forming nature, complexation with metals, biocompatibility, and varied surface functionalization. This paper illustrates the surface properties of chitosan film which is modified by grafting with stearic acid via a water-soluble coupling agent, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC). The interaction between chitosan and stearic acid were investigated theoretically by Gaussian 09 package. The purified co polymeric films so formed were characterized by FTIR-ATR, NMR, XRD, TGA, CHNSO, SEM, AFM and EDX techniques. Stearic acid grafted CS film was developed on mild steel surface via dip coating technique and investigated for its corrosion resistance in 3.5% NaCl via electrochemical techniques. EIS measurements and potentiodynamic polarization studies have proven that the grafted CS when blended with epoxy resin offers better corrosion protection to mild steel in saline environment. The coating offers prolonged protection for the metal surface with enhanced barrier properties and hydrophobic nature.     

新疆某成品油管道防腐及阴极保护系统的应用

长输管线在运行过程中防腐层产生破损在所难免,导致管材与土壤电位存在差异,产生电化学腐蚀,目前常采用阴极保护法防止电化学腐蚀。本文描述阴极保护法在埋地钢质中的安装方式及应用效果。     

Electrochemical characterisation of protective organic coatings for food packaging

A very common material for food packaging is steel, in the form of metallic containers (cans), in particular for beverage packaging. The corrosion degradation of the packaging must be carefully controlled, not only because the packaging integrity must be preserved, but also in order to avoid any significant contamination of the food or drink, compromising the flavour. In order to increase the coating performance and the food compatibility, new organic coatings are under development with very high protective properties, with the final aim to increase the shelf life of the product. An electrochemical characterisation is often used to study the protective performance of organic coatings on metal substrate for various applications. Some different coatings for food packaging were considered in the present study, including materials with different chemical composition and different pigments content. The protective properties were quantified using electrochemical impedance spectroscopy (EIS) measurements, comparing the electrochemical substrate activity with electrochemical noise (EN) and scanning Kelvin probe (SKP) measurements. The influence of mechanical deformations on the protective properties was also investigated. The results obtained on the studied coatings confirmed the validity of the electrochemical approach and showed that, in general, the coatings containing pigments (TiO₂) have better performance than clearcoats, while comparing the different polymers, epoxy–phenolic coatings have a better corrosion protection than epoxy–melamine coatings.     

Study of degradation of organic coatings in seawater by using EIS and AFM methods

In this article, electrochemical behaviors and their topography observation for four organic coatings used in seawater, by using both electrochemical impedance spectroscopy (EIS) and atomic force microscopy (AFM) methods to study environment behaviors of different coatings as well as the effects of their film formation, pigments, and fillers on anticorrosion behaviors, were measured. The results show that polyurethane, epoxy, and chlorinated rubber coatings all present one capacitive loop in their tested EIS which contains phenomenally only one time constant, whereas alkyd coating presents two capacitive semicircle arcs. With two capacitive loops, the capacitive semicircle in the high frequency range represents barrier layer property, but the semicircle in the low frequency range represents corrosion reaction of metals under the film. Polyurethane coating used in seawater has well anticorrosion property in seawater immersion test. The appearance features of different layers are visible different between different layers of tested coatings at their surface topography. The property of polyurethane paint film coated on metal is better than other layers, and film of alkyd coating has many pits at its surface by observing the layer's images. AFM photos imaged have also been used to further detail surface topography for four organic coatings, and to approve effects of topography of these coatings on its electrochemical behaviors, from two views of both height and phase modes. It is beneficial to explain deeply the environment behaviors and degradation mechanism of organic coatings. To further study failure of these organic coatings and dynamic processes of corrosion of metal under the film, two equivalent circuit models, according to these tested EIS, have been suggested to explain the corrosive kinetics of these four coatings. To polyurethane, epoxy, and chlorinated rubber coatings used in seawater which have good protection effects for substrate metal, the diffusion process for water, from their layer's surface to interface of film/metal, is mainly controlled factor for degradation. However, the electrochemical reaction process has may become a control procedure for corrosion of alkyd coated metal. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

An EIS study of the influence of imperfections on the corrosion behaviour of an organic coated steel system

Three different coating conditions influencing the quality of a silicon polyester galvanized steel system were investigated by means of EIS. The first aim was to investigate the influence of different types of pores or discontinuities on the corrosion resistance of the above-mentioned coating system. A second aim was to study the influence of mechanical deformation and damage of the coating on the corrosion behaviour of the coating system. Finally, degradation due to ultraviolet exposure was investigated. In each of these investigations it was possible to distinguish different time constants for different electrochemical events in the Bode phase diagram. Since the difference in magnitude of the values of the resistances was large, they could not be distinguished in the Nyquist plots. Therefore, this type of plot was not used in this work. From the build-up of the coating system and the number of time constants deduced from the EIS measurements, it was possible to model the system. From the model, the physical and electrochemical phenomena occurring during the service life of an imperfect organic coating system was explained.     

EIS study of environmentally friendly coil coating performances

The corrosion protection of metal structures by the application of organic coatings is obtained using complex paint cycles. The metal pretreatment as well as primer, intermediate and top coat are the usual layers composing the protection system. Although chromate pretreatment processes and chromate containing primers are widely used, they require highly toxic chromic acid solutions, with consequent effluent disposal and ecological problems. This fact pushed many research laboratories to develop new chromium-free pretreatments and primer inhibitors. Electrochemical impedance spectroscopy (EIS) proved to be a very useful technique to study the protection properties of the organic coating because of the possibility of evaluating the corrosion process on the metal substrate and to measure the electric and dielectric characteristics of the coating. In this study, new chromium-free pretreatments and new primers containing ecological inhibitors were applied to steel substrates coated using an Al-Zn alloy. The results were compared with those obtained using traditional protection systems. The characterization of the complete system (pretreatment and primer) in sodium sulfate solution clearly showed the different water uptake behavior of the two primers, which highlights the better barrier properties of the one containing phosphate. However the corrosion protection of the primer containing chromates is also due to the inhibitive action of the chromates. Hence such a type of primer better withstands the presence of defects in the coating. Moreover the presence of environmentally friendly pretreatments do not worsen the corrosion protection which appears comparable to that observed when chromatation is employed.     

Mechanisms of non-toxic anticorrosive pigments in organic waterborne coatings

Investigations have been carried out concerning the mechanism of the behaviour of non-toxic anticorrosive pigments belonging to the group of phosphates, ferrites and ion exchange pigments in waterborne systems. The mechanism controlling the protective effectiveness of organic coatings is complex and results from simultaneous activity of various agents, from among which the kind of the corrosion inhibitor and the structure of the coating are of fundamental importance. The effect of pigments on the protective properties of coatings was tested by means of electrochemical impedance spectroscopy (EIS), scanning vibrating electrode technique (SVET) as well as the salt spray and Prohesion tests. For the investigation of the structure of coatings the porosymetric method and modulated-force thermomechanical analysis (mf TMA) were applied. The results of these investigations have shown that calcium zinc phosphate and zinc ferrite are the most effective. These pigments take part in the passivation of steel, which has been proved by the results of electrochemical investigations and by the presence of the passive layers as has been found out by X-ray diffraction (XRD), energy dispersive X-ray analysis (EDXA) and scanning electron microscopy (SEM). Calcium zinc phosphate and zinc ferrite affect the structure of the coatings, increasing the glass transition temperature (Tg) of the coatings. Zinc phosphate and calcium-exchanged silica do not act in compliance with electrochemical mechanism neither do they improve the barrier properties of the binder.