EIS characterization of thick flawed organic coatings aged under cathodic protection in seawater

Electrochemical impedance spectroscopy (EIS) was used to monitor, up to 20 months, the degradation kinetics of four thick organic coatings under cathodic protection in seawater. EIS experiments were realized onto a flawless zone, which surrounds an artificial hole of the coating using the Luo's cell or a removable cell. EIS spectra were analyzed first with classic equivalent circuits and then with an approach involving the dipolar relaxation of polymer layer. These two models were unable to explain the experimental data, especially for a long immersion experiments. Taking into account the presence of vacuoles, namely pre-existing air pockets that will be then filled by electrolyte, modified equivalent circuits were used and a good representation of experimental data was obtained. The parameters extracted allowed the coating degradation to be followed. It was found that a solvent-free coating exhibited the best compatibility with cathodic protection.     

Degradation Mechanisms of ZrO2–8 wt% Y2O3/Ni-22Cr-10Al-1Y Thermal Barrier Coatings

Duplex ZrO₂–8 wt% Y₂O₃/Ni-22Cr-10Al-1Y thermal barrier coatings (TBCs) on Mar-M247 superalloy were tested under different operating conditions within the temperature range 1000° to 1150°C. Results of experiments in this study show that oxidation of bond coatings is the dominant TBC degradation mechanism whereas the operationally induced stresses exert a conjugate effect. The mechanisms of sintering and phase transformation of top coatings do not contribute to failure of TBCs within the temperature range studied. NiO and Ni(Cr,Al)₂O₄ grown on the surfaces of the bond coatings seem to accelerate spalling of the top coatings along a top coating/bond coating out-grown oxide interface. However, it is also concluded that the lifetime of TBCs is not directly related to a critical specific weight gain under thermal cycling conditions.     

Electrochemical measurements to evaluate the damage due to abrasion on organic protective system

Organic coatings are the most commonly used system for protection of metals from corrosion. In several applications organic coatings have to show, in addition to the protection properties and a good aesthetic appearance, good resistance to impact and abrasion. In fact, the mechanical damage can remarkably decrease the protection properties, even in the case of a very protective organic coating.

To evaluate the abrasion resistance of organic coatings the Taber Abraser test is frequently used. The mechanical damage is determined by measuring the mass loss without considering the form of damage (morphology and influence on corrosion protection performances).

The aim of this work is to evaluate the degradation of protection properties, caused by abrasion in Taber tests, using electrochemical methods.

Polyester powder coated steels were studied. Several parameters were considered such as the number of cycles, hardness of abrasive grinders and imposed weight.

By considering the resistance and capacitance of the organic coatings, obtained by fitting the electrochemical impedance data, it is possible to evaluate the trend of damage evolution as a function of the number of cycles and of the test parameters.

These EIS technique can distinguish the slight difference in aggressiveness of the two types of grinders used. The CS10 grinders produce debris which show the tendency to stick to the grinder itself and to the paint, reducing the abrasive action. Nevertheless, in this case the abrasion of the coating appears more uniform. In contrast, CS17 grinders increase the tendency to produce localised defects, which reduces the performance of the paint.

A different degradation rate and morphology were observed: an initially high damage value, followed by a decrease was observed due to both the presence of debris and the progressive efficiency loss of the abrasive wheels. For this reason, polishing of the grinder after every 1000 cycles is necessary to maintain a constant abrasion efficiency.     

New Thermal Barrier Coatings Based on Pyrochlore/YSZ Double-Layer Systems

Pyrochlore materials La₂Zr₂O₇ and Gd₂Zr₂O₇ have been used to produce thermal barrier coating systems by atmospheric plasma spraying. The materials have been applied as single-layer coatings with only a topcoat made of pyrochlore material. In addition, double-layer systems with a first layer of yttria-stabilized zirconia (YSZ) and a top layer made of pyrochlore material were produced. These systems have been tested in thermal cycling test rigs at surface temperatures between 1200-1450°C and the results were compared to the behavior of YSZ coatings. Single-layer coatings had a rather poor thermal cycling performance. On the other hand, double-layer systems showed similar results to YSZ coatings at temperatures below about 1300°C. At higher temperatures the double-layer coatings produced from our own powders revealed excellent thermal cycling behavior. At the highest test conditions, lifetime was thereby orders of magnitude better than that of YSZ coatings. Results indicate that an increase of the maximum surface temperature in gas turbines by at least 100 K becomes possible with the new coatings. Coatings produced from commercial powders showed a somewhat reduced performance.     

Investigation of Processes Occurring at the Metal/Polymer Coating/Electrolyte Interface

The methodical approach and the cell to study electrochemical processes occurring during cathodic disbondment of a polymer coating are worked out. They permit one to investigate the role of each process separately when supervising the metal substrate potential, electrolyte and polymer coating composition at a metal/polymer/electrolyte interface. The cathodic disbondment of ethylene-vinyl acetate copolymer, polyisoprene and poly(vinyl chloride) coatings are studied. It is found that the cathodic disbondment rate for ethylene-vinyl acetate copolymer coatings depends on double layer parameters at the interface. These parameters are determined by specific volume charge of hydrated cations of the electrolyte, potential of the substrate, the presence of oxygen, surface active substances, etc. Based on the data of IR spectroscopy in internal reflection applied to disbonded films, it is established that during the cathodic disbondment an electron transfer to polymer functional groups, as well as an attacking of the adhesion bonds by active intermediates of oxygen reduction, occurs resulting in an electrochemical degradation of the polymer and an adhesion loss. It is shown that the electrochemical transformations at the steel/poly(vinyl chloride) interface can lead to the appearance of new adhesion bonds, increasing adhesion strength and decelerating the cathodic disbondment.     

Cathodic disbondment resistance with reactive ethylene terpolymer blends

Adhesion to metallic substrates can be improved through the addition of polar functional groups, which bond with surface groups on the metal substrate. Additionally, polar interactions have been shown to increase adhesive strength even in wet environments (such as in the case for cathodic protection). A polymer blend is proposed as a coating material to provide adequate protection against the diffusion of moisture and air to the metallic surface along with superior adhesion even in the presence of wet and corrosive environments to resist cathodic disbondment. A reactive ethylene terpolymer (RET) of ethylene/n-butyl acrylate/glycidyl methacrylate (E/nBA/GMA) was compounded with HDPE to develop a potential coating material. The HDPE component offers high chemical and moisture resistance to permeation, while the RET component provides the material with high polarity and reactivity, which enhances adhesion to the substrates to be coated. The introduction of the reactive ethylene terpolymer decreases the magnitude of cathodic disbondment area of polyethylene coatings. After applying a cathodic potential to the coating substrate, the adhesive strength was observed to remain the same for silane-pretreated steel dollies. Without silane pretreatment, post-CD adhesive loss resembles that of the open circuit “wet” condition. EDAX data in conjunction with oxygen and water vapor transmission rates suggest an initial stage of disbondment where interfacial oxide is dissolved resulting in the delamination of coating around the initial defect. This initial disbondment zone acts like a moving crack tip creating larger areas of disbondment where interfacial bonds are degraded by the ingress of moisture and ions along the interface.     

Acceleration and quantitative evaluation of degradation for corrosion protective coatings on buried pipeline: Part I. Development of electrochemical test methods

The electrochemical degradation of polyethylene coated onto SS400 was examined in synthetic groundwater. Electrochemical techniques (electrochemical impedance spectroscopy, potentiodynamic and potentiostatic polarization tests) and surface analysis (scanning electron microscopy) were used to accelerate and evaluate the coating degradation. The pulsed potentiostatic polarization test accelerating both the cathodic reduction and anodic oxidation reactions was applied to reproduce the coating degradation mechanisms of cathodic disbondment and oxide lifting. The applied potentials were determined to be ±300 mV_SCE versus open-circuit potential from the analysis of the anodic and cathodic polarization data. Results from the EIS confirmed that coating degradation is accelerated effectively by the pulsed potentiostatic polarization testing.     

Assessment of protective properties of organic coatings by thermal cycling

Researchers’ efforts are focused on understanding how coatings can be tested in order to determine their real capabilities and selected for different purposes. Outdoor exposures are certainly reliable and offer a good representation of the actual service life. However, such tests cannot be considered quick.

On the other hand, a quick test, even if reliable, very often disagrees with the actual degradation mechanisms occurring under natural conditions. In fact, in order to determine an acceleration of the natural weathering, it is necessary to increase the effect of natural parameters affecting the protection properties of a coating.

The usual modern way to operate is to take advantage of ageing tests where temperature plays a big role in the ageing of the material, permitting to gather faster information for coating corrosion resistance evaluation.

Following the recent new experience realised by the Bierwagen group, we carried out different thermal cycling tests consisting in daily series of electrochemical measurements on coated samples, carried out using electrochemical impedance spectroscopy (EIS).

The cumulative effects of such a thermal cycling on the film, based on a large variety of theoretical explanations, should permit the ranking of a variety of materials, by constituents, characteristics and application purposes, in a short time while remaining objective and reliable.

The used ageing procedure and data evaluation allowed to quickly and precisely obtain information concerning both barrier properties and adhesion properties of the studied materials.     

Thermal Conductivity of Plasma-Sprayed Monolithic and Multilayer Coatings of Alumina and Yttria-Stabilized Zirconia

The temperature dependence of the thermal conductivity of plasma-spray-deposited monolithic coatings, as well as multilayer coatings that consisted of Al₂O₃ and ZrO₂ that was stabilized by 8% Y₂O₃ (YSZ), was investigated. The coatings exhibited a large reduction in thermal conductivity at all temperatures, when compared to the bulk monolithic Al₂O₃ and YSZ. This reduction was due to porosity as well as thermal resistance that was caused by interfaces in the coatings. The largest decrease in the thermal conductivity of the coatings, relative to monolithic fully dense materials, was due to splat interfaces within each layer, as well as the coating/substrate interface. On the other hand, the multilayer coatings showed little variation in the thermal conductivity, relative to the number of layers, which suggests that the influence of interlayer interfaces on heat transfer is relatively small. A one-dimensional analysis of steady-state heat transfer has been presented to illustrate the significance of porosity, splat interfaces, and interlayer interfaces, with respect to the overall thermal conductivity of multilayer coatings.     

Self-healing coatings: An alternative route for anticorrosion protection

Polymer coating systems are classically applied on a metal surface to provide a dense barrier against the corrosive species. Cathodic protection is used for many applications in addition to coatings to protect the metal structures from corrosive attack when the coating is damaged. However, the current demand will increase with the disbonded areas. Moreover, the reactions that take place at the cathode can cause a progressive enlargement of the unbonded area. Self-healing coatings are considered as an alternative route for efficient anticorrosion protection while maintaining a low demand in cathodic protection. Such coatings typically incorporate micro- or nanocapsules that contain film-formers and repair the coating damage when the coating is scratched. Self-healing systems have been developed for metal structures under cathodic protection using specific-film-formers sensitive to the electrical field and pH encountered in the vicinity of a default on a coated structure under cathodic protection. The present paper describes the principle of this novel self-healing concept and discusses the healing efficiency on the basis of laboratory results. Electrochemical impedance spectroscopy was used to evaluate the performance of the barrier efficiency and continuous current demand monitoring assessed the ability of specific-film-formers to provide self-healing and repair defects generated in the coating to the metal.     

Cathodic disbondment resistance with reactive ethylene terpolymer blends

Adhesion to metallic substrates can be improved through the addition of polar functional groups, which bond with surface groups on the metal substrate. Additionally, polar interactions have been shown to increase adhesive strength even in wet environments (such as in the case for cathodic protection). A polymer blend is proposed as a coating material to provide adequate protection against the diffusion of moisture and air to the metallic surface along with superior adhesion even in the presence of wet and corrosive environments to resist cathodic disbondment. A reactive ethylene terpolymer (RET) of ethylene/n-butyl acrylate/glycidyl methacrylate (E/nBA/GMA) was compounded with HDPE to develop a potential coating material. The HDPE component offers high chemical and moisture resistance to permeation, while the RET component provides the material with high polarity and reactivity, which enhances adhesion to the substrates to be coated. The introduction of the reactive ethylene terpolymer decreases the magnitude of cathodic disbondment area of polyethylene coatings. After applying a cathodic potential to the coating substrate, the adhesive strength was observed to remain the same for silane-pretreated steel dollies. Without silane pretreatment, post-CD adhesive loss resembles that of the open circuit “wet” condition. EDAX data in conjunction with oxygen and water vapor transmission rates suggest an initial stage of disbondment where interfacial oxide is dissolved resulting in the delamination of coating around the initial defect. This initial disbondment zone acts like a moving crack tip creating larger areas of disbondment where interfacial bonds are degraded by the ingress of moisture and ions along the interface.     

Thermal shock resistance of thermal barrier coating with different bondcoat types and diffusion pre-coating

This paper investigates the resistance of two types of thermal barrier coatings and compares their behavior with common coatings. Coatings’ layers in the first and second target sample were fabricated as HVOF/APS/APS (two bondcoats and one topcoat) and APS/APS (one bondcoat and topcoat) with diffusion pre-coating, respectively. Also, to accurately compare the behavior of these two types of coatings with conventional coatings used in gas turbines, this paper explored the resistance of three types of coatings applied as APS/APS, HVOF/APS, and HVOF coatings against thermal shock. In order to create shock loading, five types of laboratory samples were heated under regular cycles and cooled down with water. During the experiment, the sample changes caused by thermal shock loading were investigated through visual inspections. Then, after the experiment, the SEM images were leveraged to inspect the changes. In addition, changes in the structure of coating layers and their degradation process were studied. The results show that using two bond layers increases the resistance and life of the coating against heat shock by up to 1.40 times. Among the samples with one band coat, the sample with a diffusion coating applied under the BC showed the best performance. The sample life increased by 1.25 times compared to the common APS/PAS coating.     

Reduction of cathodic delamination rates of anticorrosive coatings using free radical scavengers

Cathodic delamination is one of the major modes of failure for anticorrosive coatings subjected to a physical damage and immersed in seawater. The cause of cathodic delamination has been reported to be the result of a chemical attack at the coating–steel interface by free radicals and peroxides formed as intermediates in the cathodic reaction during the corrosion process. In this study, antioxidants (i.e., free radical scavengers and peroxide decomposers) have been incorporated into various generic types of coatings to investigate the effect of antioxidants on the rate of cathodic delamination of epoxy coatings on cold rolled steel. The addition of <5 wt% free radical scavengers to epoxy coatings improved the resistance toward cathodic delamination by up to 50% during seawater immersion, while peroxide decomposers had a limited effect. Testing using substrates prepared from stainless steel, copper, aluminum, galvanized steel, and brass also showed a reduction in the rate of cathodic delamination when the coating was modified with a free radical scavenger. The protective mechanism of free radical scavengers investigated for the primers are similar to that of antioxidants used for protection against photochemical degradation by UV-radiation of top coatings. Both substrate corrosion and degradation of a coating exposed to UV-radiation lead to the formation of free radicals as reactive intermediates.     

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.     

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.     

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.     

Response surface analysis to evaluate the influence of deposition parameters on the electrodeposition of Cu–Co alloys in citrate medium

Copper–cobalt alloy coatings were deposited on mild steel substrates using sodium citrate electrolytes at room temperature and under direct current. A set of cathodic polarization curves was plotted by varying the mechanical stirring speed of the solution (0–400 rpm), using a range of current densities during the electrodeposition experiments. Factorial design was used to verify the influence of these deposition parameters on the cathodic efficiency, the copper and cobalt content in the coating, the corrosion current density of the coating/substrate system, and the efficiency of the coating in protecting the substrate. The electroplating experiments showed that, with the studied bath composition, high stirring speed and low current density lead to greater cathodic current efficiency and copper-rich coatings. On the other hand, high current density and low stirring speed yields coatings with high cobalt content and a lower cathodic efficiency. Our results show that the studied parameters affect the corrosion current density and the coating efficiency of the coating/substrate system in opposite ways. The best results were obtained increasing the current density and decreasing the mechanical stirring speed. Additionally, three samples were produced in selected deposition conditions. The coatings morphologies were compact, and their grain sizes seemed to enlarge with increasing stirring speed and decreasing current density.     

Phase Transformations of Plasma-Sprayed Zirconia–Ceria Thermal Barrier Coatings

Phase constituents and transformations of plasma-sprayed thermal barrier coatings (TBCs) with CeO₂-stabilized ZrO₂ (CSZ; 16–26 wt% CeO₂) have been investigated using X-ray diffractometry (XRD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). The as-coated CSZ coatings with 16 and 18 wt% CeO₂ consisted only of the nonequilibrium tetragonal ( t ') phase. A mixture of the t ' and the nonequilibrium cubic ( c ') phases was observed for the as-coated CSZ coatings containing 20–26 wt% CeO₂. During 65 min cyclic oxidation at 1135°C (45 min hold time) in air, the t ' or the mixture of the t ' and the c ' phases decomposed to the equilibrium tetragonal ( t ) and the equilibrium cubic ( c ) phases. Some of the t phase transformed to the monoclinic ( m ) phase on cooling. More m phase was observed to develop in the CSZ coating containing 16 wt% CeO₂ than in the other coatings. More m phase was observed on the top surface than on the bottom surface of the CSZ coating. Spalling of the plasma-sprayed CSZ coating during thermal cycling occurred after 230 cycles for the CSZ coating containing 16 wt% CeO₂, whereas the lifetime of the CSZ coatings with 18–26 wt% CeO₂ ranged between 320 and 340 cycles.     

Precipitation Coating of Rare-Earth Orthophosphates on Woven Ceramic Fibers—Effect of Rare-Earth Cation on Coating Morphology and Coated Fiber Strength

Monazite (La, Ce, Nd, and GdPO₄) and xenotime (Tb, Dy, and YPO₄) coatings were deposited on woven Nextel^™ 610 and 720 fibers by heterogeneous precipitation from a rare-earth citrate/phosphoric acid precursor. Coating phases and microstructure were characterized by SEM and TEM, and coated fiber strength was measured after heat treatment at 1200°C for 2 h. Coated fiber strength increased with decreasing ionic radius of the rare-earth cation in the monazite and xenotime coatings, and correlates with the high-temperature weight loss and the densification rate of the coatings. Dense coatings with trapped porosity and high weight loss at a high temperature degrade fiber strength the most. The degradation is consistent with stress corrosion driven by thermal residual stress from coating precursor decomposition products trapped in the coating at a high temperature.     

Superior Performance of Ablative Glass Coatings Containing Graphene Nanosheets

Glass compositions in the Y₂O₃–Al₂O₃–SiO₂ (YAS) system are envisaged as promising coatings for high‐temperature protection, in particular for the thermal protection systems (TPS) looked for aerospace applications. Recently, thermally sprayed YAS hybrid coatings containing a small amount of graphene nanoplateletes (GNPs) showed enhanced performance as compared to the blank YAS coating, demonstrated by the occurrence of unusual electrical conductivity for these glasses and the development of better mechanical compliance, both phenomena associated with the presence of GNPs. Nevertheless, a crucial issue is to demonstrate if these kinds of coatings would also have superior behavior under ablation conditions, particularly regarding the mentioned TPS applications. This work goes far beyond, exploring the ablative behavior of new YAS/GNPs coatings flame sprayed over SiC substrates. These essential tests were carried out under laboratory conditions, reaching limit temperatures of 1350°C while blowing gas. Results evidence that hybrid coatings having just 1.05 vol% GNPs show enhanced ablation resistance, actually withstanding up to 30 thermal cycles (between 200°C and 1350°C) without apparent damage. This satisfactory performance is linked to the benefits of the GNP additions, and fundamentally to the higher emissivity and the directional thermal conduction characteristics of the hybrid coatings—produced by the formation of a GNP network with a preferential surface parallel arrangement—that preclude the creation of hot spots and also hinder heat propagation toward the substrate; accordingly, coating degradation is constrained to the uppermost layer of these coatings.