Cathodic disbondment of epoxy coating with zinc aluminum polyphosphate as a modified zinc phosphate anticorrosion pigment

As an approach to improve the resistance of protective coatings to the disbondment, modification of the formulation through incorporation of zinc aluminum polyphosphate anticorrosion pigment representing third generation phosphates was examined in this paper. The data obtained from cathodic disbonding test, electrochemical impedance spectroscopy and pull-off indicated that introduction of zinc aluminum polyphosphate within epoxy coating could provide improved resistance to cathodic disbonding as well as superior adhesion strength. The superiority in the presence of the modified pigment was connected to deposition of a layer at the disbonding front and locally controlled pH as well. The precipitation restricting active zone available for electrochemical reaction was confirmed by SEM.     

Localized EIS characterization of corrosion of steel at coating defect under cathodic protection

Localized electrochemical impedance spectroscopy (LEIS) technique was used to investigate localized corrosion of steel at defect of coating and, furthermore, to determine the effects of cathodic protection (CP) on local electrochemical environment and the resultant corrosion reaction at the base of coating defect. The results demonstrated that corrosion of steel is dependent on CP potential and the defect geometry. For coated steel containing defect under appropriate CP potentials, cathodic reaction is dominated by reduction of oxygen. Mass-transfer of oxygen through solution layer and the defect with a narrow, deep geometry (the depth/width ratio is about 5.5) is the rate-limiting step for the corrosion process of steel. Even at a very negative potential, e.g., −1200 mV (SCE), the measured impedance spectroscopy is still associated with the diffusion-controlled charge-transfer reaction of steel at the base of defect. It is attributed to the fact that the applied CP is partially shielded by the defect with a narrow, deep geometry. With the negative increase of cathodic potential, charge-transfer resistance and the local impedance of electrode increase. It is attributed to the elevation of local alkalinity at the base of defect when the coated steel is under CP. This conclusion is subject to the condition that a significant cathodic disbonding of coating has not occurred. Furthermore, with the increase of test time, the charge-transfer resistance increases, which is attributed to the enhancement of the alkaline environment at the base of defect under CP with time.     

Evaluation of thick organic coatings degradation in seawater using cathodic protection and thermally accelerated tests

Organic coatings are often associated with cathodic protection to fight against the corrosion of metallic structures when immersed in seawater. However, cathodic protection leads to the generation of a strong alkalinity at the metal/coating interface, which causes the degradation of the coating. It is then necessary to develop a reliable method to evaluate the compatibility between organic coatings and the application of cathodic protection.

On one hand, cathodic disbonding tests (ASTM G-8 and G-80) can be driven with an artificial defect but this defect is mainly responsible for the electrochemical response. In addition, calcareous deposit rapidly forms onto the defect zone when cathodic protection is applied which can make difficult the evaluation of coating delamination. On the other hand, immersion of defect-free specimens requires very long testing periods (several months or even years) in order to detect the coating degradation.

In this work, an attempt to accelerate the coatings degradation by imposing a high temperature and thermal cycles were made in order to decrease the test-time duration. The influence of the applied cathodic potential was also investigated. The coating degradation was evaluated by EIS, considering the defect-free zone of coatings. It was shown that the coating degradation is faster in the presence of a defect and for high temperature (45 °C). Moreover, thermal cycles allow to greatly accelerate the degradation of defect-free coatings and then to compare the compatibility of both coatings with cathodic protection.     

The impact of pigment volume concentration on the protective performance of polyurethane coating with second generation of phosphate based anticorrosion pigment

In this study the effect of conventional zinc phosphate and zinc aluminum phosphate, which represents second generation of phosphate based anticorrosion pigments, on the performance of a polyurethane coating was studied. While zinc phosphate modification was proved to be effective on the corrosion resistance, EIS data facilitated the determination of the optimum pigment volume concentration in which the coating offered the most efficient protection. The superiority of zinc aluminum polyphosphate was attributed to the release of more inhibiting species, leading to the formation of a protective layer at the coating/substrate interface. In addition to the assessment of the impact of pigment content on the resistance of polyurethane primer to cathodic disbonding, the dependency of adhesion strength on the pigment type was also studied using pull-off test.     

海洋环境下抗阴极剥离重防腐涂层的研究

海洋环境中浸泡在海水中的涂层由于阴极保护而产生的剥离是涂层失效的主要原因之一。针对这种失效现象,讨论了影响涂层抗阴极剥离的主要因素并研制了适应于阴极保护的海洋浸泡涂层。涂料包含不同环氧值的环氧树脂基料、烷基酚醛胺固化剂以及相适应的颜填料。通过调整涂料的颜基比,得到抗阴极剥离性能优异的涂层,涂层能够满足海洋环境中涂层与阴极保护相结合使用的需要。     

Electrochemical impedance spectroscopy as a tool to measure cathodic disbondment on coated steel surfaces: Capabilities and limitations

The disbondment of protective organic coatings under excessive cathodic protection potentials is a widely reported coating failure mechanism. Traditional methods of evaluating cathodic disbondment are based on ex situ visual inspection of coated metal surfaces after being exposed to standard cathodic disbondment testing conditions for a long period of time. Although electrochemical impedance spectroscopy (EIS) has been employed as an effective means of evaluating various anti-corrosion properties of organic coatings; its application for assessing the cathodic disbondment resistance of coatings has not been sufficiently exploited. This paper reports an experimental study aimed at developing EIS into a tool for in situ measurement and monitoring of cathodic disbondment of coatings. A clear correlation between EIS parameters and the disbonded coating areas has been confirmed upon short term exposure of epoxy-coated steel electrodes to cathodic disbondment conditions; however the degree of this correlation was found to decrease with the extension of exposure duration. This observation suggests that EIS loses its sensitivity with the propagation of coating disbondment, and that in order to achieve quantitative determination of the coating cathodic disbondment localized EIS measurements are required to measure the parameters related to local disbonded areas.     

Disbondment Mechanisms for a Heat Shrink Polyethylene Coating on a Cathodically Protected Hot Pipeline

Interfacial adhesive failure of a pipeline coating was found to be related to the operating temperature of the pipeline, the presence of moisture at the coating/steel interface and cathodic polarisation of the steel. The application of cathodic protection was found to be more detrimental to a pipeline coating than was the immersion of the coating specimens in alkaline environments without polarisation. It is suggested that in the system examined cathodic disbondment is initiated at a coating holiday by the electrochemical reduction of Fe₃O₄ in the interfacial oxide film and that propagation of the disbondment is associated with electrocapillary action which reduces the surface tension between the steel and the crevice solution. This process increases the thermodynamic disbonding force between the adhesive and the steel in the aqueous environment.     

The effect of interfacial chemistry on coating adhesion and performance: A mechanistic study using aminobutylphosphonic acid

Failure of adhesion of organic coating (paints) to steel and other metallic substrates is one of the key mechanisms for local coating failure and for consequent restriction of coating lifetime. This study thus focuses on modification to the chemistry of the metal interface in order to promote enhanced (dry and wet) coating adhesion. The work uses an appropriate bi-functional amino alkyl phosphonate to provide the desired interfacial properties. The study uses X-ray photoelectron spectroscopy and water contact angle measurement to examine changes in the interfacial surface chemistry and electrochemical impedance spectroscopy and cathodic disbonding to determine improvements to the anti-corrosion performance. Choosing 4-amino-butyl-phosphonic acid as the surface modifier a significant influence on its efficiency as an adhesion promoter was observed as a function of pH. Thus, when the amino group was protonated at a pH of 5.3, the molecule demonstrated attachment to carbon steel at both ends with no significant improvement in performance. However at pH 8 the molecule demonstrated greatly improved surface packing density with the amino group outwards from the surface in the preferred orientation. In this condition, an epoxy coating demonstrated substantial resistance to interfacial hydrolysis with overall improved adhesion and reduced cathodic disbondment rate.     

Disbondment Mechanisms for a Heat Shrink Polyethylene Coating on a Cathodically Protected Hot Pipeline

Interfacial adhesive failure of a pipeline coating was found to be related to the operating temperature of the pipeline, the presence of moisture at the coating/steel interface and cathodic polarisation of the steel. The application of cathodic protection was found to be more detrimental to a pipeline coating than was the immersion of the coating specimens in alkaline environments without polarisation. It is suggested that in the system examined cathodic disbondment is initiated at a coating holiday by the electrochemical reduction of Fe₃O₄ in the interfacial oxide film and that propagation of the disbondment is associated with electrocapillary action which reduces the surface tension between the steel and the crevice solution. This process increases the thermodynamic disbonding force between the adhesive and the steel in the aqueous environment.     

The effect of benzimidazole and zinc acetylacetonate mixture on cathodic disbonding of epoxy coated mild steel

Electrochemical behavior of mild steel in the presence of zinc acetylacetonate (Zn(acac)₂) and benzimidazole (BIMIDA) was evaluated by electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution and compared to zinc phosphate (ZP) pigment and zinc potassium chromate (ZPC) pigment extracts. Results showed superior performance of Zn(acac)₂ and BIMIDA mixture (ZBM) compared to ZP pigment, while it introduced inferior inhibitive action compared to ZPC pigment. The epoxy coatings were formulated with ZBM as anticorrosive additive, ZP and ZPC pigments. The disbonding rate of coated steel follows the order: Blank > ZP > ZBM > ZPC. EIS results showed a complex film could be formed at the hole area for the coatings formulated with ZP, ZBM and ZPC. It is concluded that the stronger the complex film on the surface, the lesser the cathodic disbonding rate would be.     

Cathodic Delamination of an Epoxy/Polyamide Coating from Steel

X-ray photoelectron spectroscopy (XPS) has been used to determine the mechanism responsible for debonding of an epoxy/polyamide coating from steel during cathodic delamination in 3.5% aqueous NaCl solutions. Coating failure always occurred near the interface between the coating and the oxide. The nitrogen content of the free surface of the prepared coatings was about 10%. However, the nitrogen content of the free surface dropped to only 5% after exposure to 1 N NaOH for four weeks and that of the coating failure surface after cathodic delamination was only about 2%, implying that the failure involved degradation of the polyamide curing agent by hydroxide ions formed at the steel surface by reduction of oxygen. That conclusion was supported by results obtained from curve fitting of C(1s) and O(1s) spectra. The intensity of components in the C(1s) spectra due to C—N and C≡O bonds in amide functional groups decreased significantly after coatings were exposed to NaOH or subjected to cathodic delamination. Small amounts of organic materials characteristic of the coating were observed on the substrate failure surface, perhaps indicating that the failure was cohesive within the coating but very close to the interface or that some products from degradation of the curing agent precipitated on the substrate. Use of silane coupling agents to retard cathodic delamination was also investigated. Coupling agents were added directly to the coating or applied to the substrate as a primer before application of the coating. Significant reduction in the rate of cathodic delamination was seen only when the silane coupling agent was applied to the substrate and cured at elevated temperatures before the epoxy/polyamide coating was applied.     

Characterization of high performance composite coating for the northern pipeline application

High performance composite coating (HPCC) provides a potential, excellent coating alternative for integrity maintenance of pipelines in the northern area. In this work, the physical, chemical and mechanical properties of HPCC were investigated to determine the microstructure, water permeability, cathodic disbondment resistance, electrochemical impedance, adhesion and impact resistance of the coating. It is shown that the addition of polyethylene layer significantly improves the compactness of the coating and enhances its resistance to water and chemical penetration, resulting in a small water vapor transmission rate and permeance. There is a quite small cathodic disbondment of HPCC under the standard test. The impedance characteristic measured on HPCC-coated steel shows a capillary behavior, indicating an effective protection over the underlying steel from corrosion. The adhesion of HPCC to the substrate ranks top one according to both ASTM and CSA standards. The impact energy of HPCC is 9.7 J at 22 °C, and about 10.2 J around 0 °C.     

Cathodic Delamination of an Epoxy/Polyamide Coating from Steel

X-ray photoelectron spectroscopy (XPS) has been used to determine the mechanism responsible for debonding of an epoxy/polyamide coating from steel during cathodic delamination in 3.5% aqueous NaCl solutions. Coating failure always occurred near the interface between the coating and the oxide. The nitrogen content of the free surface of the prepared coatings was about 10%. However, the nitrogen content of the free surface dropped to only 5% after exposure to 1 N NaOH for four weeks and that of the coating failure surface after cathodic delamination was only about 2%, implying that the failure involved degradation of the polyamide curing agent by hydroxide ions formed at the steel surface by reduction of oxygen. That conclusion was supported by results obtained from curve fitting of C(1s) and O(1s) spectra. The intensity of components in the C(1s) spectra due to C—N and C≡O bonds in amide functional groups decreased significantly after coatings were exposed to NaOH or subjected to cathodic delamination. Small amounts of organic materials characteristic of the coating were observed on the substrate failure surface, perhaps indicating that the failure was cohesive within the coating but very close to the interface or that some products from degradation of the curing agent precipitated on the substrate. Use of silane coupling agents to retard cathodic delamination was also investigated. Coupling agents were added directly to the coating or applied to the substrate as a primer before application of the coating. Significant reduction in the rate of cathodic delamination was seen only when the silane coupling agent was applied to the substrate and cured at elevated temperatures before the epoxy/polyamide coating was applied.     

Performance of zinc phosphate coatings obtained by cathodic electrochemical treatment in accelerated corrosion tests

The formation of zinc phosphate coating by cathodic electrochemical treatment and evaluation of its corrosion resistance is addressed. The corrosion behaviour of cathodically phosphated mild steel substrate in 3.5% sodium chloride solution exhibits the stability of these coatings, which lasts for a week's time with no red rust formation. Salt spray test convincingly proves the white rust formation in the scribed region on the painted substrates and in most part of the surface on unpainted surface. The protective ability of the zinc corrosion product formed on the surface of the coated steel is evidenced by the decrease in the loss in weight due to corrosion of the uncoated mild steel, when it is galvanically coupled with cathodically phosphated mild steel. Potentiodynamic polarization curves reveal that E_corr shifts towards higher cathodic values (in the range of −1000 to −1100 mV versus SCE) compared to that of uncoated mild steel and conventionally phosphated mild steel substrates. The i_corr value is also very high for these coatings. EIS studies reveal that zinc dissolution is the predominant reaction during the initial stages of immersion. Subsequently, the non-metallic nature of the coating is progressively increased due to the formation of zinc corrosion products, which in turn enables an increase in corrosion resistance with increase in immersion time. The zinc corrosion products formed may consist of zinc oxide and zinc hydroxychloride.     

Determination of the oxygen reduction products on ASTM A516 steel during cathodic protection

The electrochemistry of steel in aerobic and anaerobic aqueous alkaline solutions was studied with or without forced convection to investigate the cathodic processes occurring on steel exposed by defects in polymer coated steel pipe. The results are relevant to the mechanistic understanding of the effect of cathodic protection on the disbonding of fusion bonded epoxy (FBE) coatings on steel. Moderate (pH9.8) and strongly (pH14) alkaline aqueous solutions were used to simulate the water layers at the cathodically polarized steel surface on the soil-side of buried pipe. A rotating gold ring and steel disc electrode (RRDE) in alkaline aqueous electrolyte equilibrated with 1atm oxygen over solution was used to measure the rotation rate dependent current for the electroreduction of oxygen, O2, on an ASTM A516 steel disc and the resulting peroxide generation, which was determined by monitoring the oxidation current on the gold ring. An appreciable fraction of the oxygen reduction current on the steel disk gave rise to peroxide generation over a wide range of potentials, from –0.2 to –0.9V vs SCE in 1M KOH. The observation of peroxide generation is noteworthy, because oxidizing agents, such as peroxide and its decomposition products, superoxide and hydroxy radical, can degrade the polymers used for coating pipelines. As result, oxidative degradation of polymer or interfacial compounds may be a cause of the accelerated disbonding observed for protective coatings on steel pipelines under cathodic protection.     

The effect of surface modification on the cathodic disbondment rate of epoxy and alkyd coatings

Surface modification of carbon steel substrates using appropriate functionalised silanes was carried out to investigate their effect on the dry and wet adhesion strength, and the cathodic disbondment rate, of coating binders based on epoxy and alkyd chemistries. Results show that pre-treatment of the steel substrate with 3-glycidoxypropyltrimethoxy silane (3-GPS) enhanced the dry and wet adhesion of an epoxy-based coating. Similarly, pre-treatment with 3-aminopropyltriethoxy silane (3-APS) enhanced the dry and wet adhesion of alkyd-based systems. However, although pre-treatment with 3-GPS reduced the cathodic disbondment rate for epoxy by a factor of 3, no effect on the disbondment rate for alkyd-based binders on substrates pre-treated with 3-APS was found. This strongly suggests that cathodic disbondment of epoxy proceeds by disruption of interfacial bonds (i.e. at the binder/substrate interface) but that disbondment of alkyds proceeds by direct degradation of the binder and that the interface plays little part in the process.     

Effect of zinc-free phosphate-based anticorrosion pigment on the cathodic disbondment of epoxy-polyamide coating

In the field of protective coatings, zinc-free pigments are proposed as promising anticorrosion compounds due to their excellent environmentally-friendly profile. In this paper, cathodic disbonding performance of a solvent-borne epoxy primer incorporating strontium aluminum polyphosphate (SAPP) as a zinc-free phosphate-based anticorrosion pigment was investigated. Regardless of the applied potential, the presence of SAPP in the coating formulation caused slower growth of the delamination area in comparison to ZP. According to the data obtained from EIS and SEM/EDX, this behavior was attributed to locally controlled pH and the precipitated film restricting active zones available for electrochemical reactions.     

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.     

An investigation of cathodic oxygen reduction beneath an intact organic coating on mild steel and its relevance to cathodic disbonding

An epoxy-coated mild steel panel was coupled with bare mild steel to characterise the cathodic reaction underneath the paint and study the short term change in properties of the coating under cathodic polarisation. It showed that the cathodic reaction obeys the Tafel law and is not controlled by either the high coating resistance or oxygen transport through the coating.     

Evaluation of red mud as surface treatment for carbon steel prior painting

Red mud (RM) is the waste product of the Bayer process for obtaining alumina from bauxite. The alkaline nature of RM suspensions together with the presence of Fe³⁺ species point towards the possibility of using RM as a good corrosion inhibitor for carbon steel. Based on this idea, the possible use of RM suspensions as pre-treatment for carbon steel was studied by recording the electrode potential and the electrochemical impedance spectroscopy (EIS) evolution with immersion time. Different parameters regarding the steel surface finishing (grinding, pickling or degreasing) and RM suspension condition (stirred or steady, decanted or filtered) have been considered in the study; the passivation was obtained when ground samples were immersed in decanted RM suspensions and subjected to continuous stirring. The influence of chlorides and pH were analysed by potentiometric titration. The obtained results indicate that treated samples depassivate at lower Cl⁻/OH⁻ ratio than untreated ones. Regarding the pH parameter, treated samples remain passive at lower pH values than the untreated ones. Finally, some treated and untreated samples were painted and subjected to cathodic polarisation experiments, including an artificial defect in the coating. The comparative study was done using EIS technique; the impedance diagrams would indicate an effective passivation of the steel surface for treated samples.