A fracture analysis of cathodic delamination at polyurea/steel interfaces

A fracture mechanics approach to accelerated life testing of cathodic delamination between steel and polyurea is presented. This required the hyperelastic behavior of the polyurea to be described by the Marlow model based on uniaxial tension and plane strain compression tests. Time-dependence was also considered but could be neglected if proper test protocols were followed in cathodic delamination tests using a strip blister specimen. The variation of J-integral with specimen geometry and loading parameter was obtained, which allowed the resistance to cathodic delamination to be expressed in terms the J-integral and the crack speeds obtained from the tests at several temperatures. The approach established that both temperature and stress can be used to accelerate the cathodic delamination, thereby providing a quantitative and rational basis for conducting accelerated testing. In addition, the discriminating nature of the approach for design purposes was exemplified by quantitatively establishing differences in the delamination resistance of three surface treatments.     

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.     

Degradation of rubber to metals bonds during its cathodic delamination, validation of an artificial ageing test

Rubber-metal assemblies used for submarine applications are often associated to cathodic protection which can lead to cathodic disbonding of the polymer/metal interface.The degradation mechanisms of polychloroprene/epoxy adhesive/copper-aluminium substrate systems associated to an accelerated ageing test are compared to the degradations resulting from natural ageing conditions in the Mediterranean sea. From destructives tests, a kinetic in four steps is identified for both ageing conditions. This kinetic is confirmed by Electrochemical Impedance Spectroscopy data during ageing. In order to further identify the failure mode, the disbonded surfaces on polymer and steel sides are analyzed using SEM and FTIR. Both ageing conditions present the same type of degradation which validates the fact that the accelerated ageing protocol reproduces the natural conditions. The chemical transformations in delaminated epoxy are very similar to the chemical transformation in epoxy coatings under high energy electron-beam irradiation. However, bidendate metal carboxylates rather than carboxylic acid chain ends are the main oxidation products due to the alkaline environment at the coating-metal interface. It was shown that the metal/polymer interface is not destroyed by an alkaline attack but by a strongly oxidative attack caused by the intermediates of the oxygen reduction.     

Effectiveness of a conductive cementitious mortar anode for cathodic protection of steel in concrete

The paper reports a study on the behaviour of a cementitious conductive overlay anode used for cathodic protection (CP) of steel in concrete. The anode is made of nickel-coated carbon fibres in a cementitious mortar. Tests were carried out on concrete specimens with two layers of rebars that simulated reinforced concrete slabs. Anodic current densities in the range 10-100 mA/m² with respect to the anode surface were imposed. Steel and anode potentials, as well as feeding voltage, were monitored. Four-hour decay and the distribution of current and potential were regularly measured. Galvanostatic polarisation tests were also carried out on the anode material immersed in saturated calcium hydroxide solutions. The maximum anode current output was evaluated. The effectiveness of patch repair of the anode, on areas damaged by excessive current output, is also discussed.     

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.     

Microscopic aspects of electrochemical delamination: an SKPFM study

While the basic mechanisms of anodic and cathodic delamination, i.e. the de-adhesion of polymer coatings from the metal substrate, are already well understood [Industrial Adhesion Problems, Orbital Press, Oxford (1985); Polymeric Materials for Corrosion Control, American Chemical Society, Washington (1986); Corrosion Control by Organic Coatings, NACE, Houston, TX; MRS Bull. 24 (1999) 43; Corros. Sci. 43 (2001) 207; Corros. Sci. 43 (2001) 229; Corros. Sci. 43 (2001) 243; Corros. Sci. 41 (1999) 547; Corros. Sci. 41 (1999) 579; Corros. Sci. 41 (1999) 599], only little is known about the microscopic and submicroscopic aspects of delamination. The main difficulty for a detailed investigation of delamination with a suitably high resolution is that the de-adhesion is a process occurring at a buried interface. On the macroscopic scale Scanning Kelvin Probe Microscopy (resolution of about a few 10 μm) has been the most important method to elucidate the fundamental processes of cathodic and anodic delamination, which in combination with other methods such as photoelectron spectroscopy (XPS) and measurement of the adhesion strength in dependence on distance from the defect helped to develop detailed models [MRS Bull. 24 (1999) 43; Corros. Sci. 43 (2001) 207; Corros. Sci. 43 (2001) 229; Corros. Sci. 43 (2001) 243; Corros. Sci. 41 (1999) 547; Corros. Sci. 41 (1999) 579; Corros. Sci. 41 (1999) 599]. The development of the scanning Kelvin probe force microscopy (SKPFM) opened application of the Kelvin probe technique to the submicroscopic scale. In this paper, first results of these submicroscopic investigations are presented and discussed in view of the earlier results.     

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.     

Argon plasma treatment techniques on steel and effects on diamond-like carbon structure and delamination

We demonstrate alteration in diamond-like carbon (DLC) film structure, chemistry and adhesion on steel, related to variation in the argon plasma pretreatment stage of plasma enhanced chemical vapour deposition. We relate these changes to the alteration in substrate structure, crystallinity and chemistry due to application of an argon plasma process with negative self bias up to 600 V.Adhesion of the DLC film to the substrate was assessed by examination of the spallated fraction of the film following controlled deformation. Films with no pretreatment step immediately delaminated. At 300 V pretreatment, the spallated fraction is 8.2%, reducing to 1.2% at 450 V and 0.02% at 600 V. For bias voltages below 450 V the adhesion enhancement is explained by a reduction in carbon contamination on the substrate surface, from 59 at.% with no treatment to 26 at.% at 450 V, concurrently with a decrease in the surface roughness, R_q, from 31.5 nm to 18.9 nm. With a pretreatment bias voltage of 600 V a nanocrystalline, nanostructured surface is formed, related to removal of chromium and relaxation of stress; X-ray diffraction indicates this phase is incipient at 450 V. In addition to improving film adhesion, the nanotexturing of the substrate prior to film deposition results in a DLC film that shows an increase in sp³/sp² ratio from 1.2 to 1.5, a reduction in surface roughness from 31 nm to 21 nm, and DLC nodular asperities with reduced diameter and increased uniformity of size and arrangement. These findings are consistent with the substrate alterations due to the plasma pretreatment resulting in limitation of surface diffusion in the growth process. This suggests that in addition to deposition phase processes, the parameters of the pretreatment process need to be considered when designing diamond-like carbon coatings.     

Protective properties of intact unpigmented epoxy coated mild steel under cathodic protection

Electrochemical Impedance Spectroscopy (EIS) has been used to characterise intact unpigmented epoxy coated mild steel with and without the application of cathodic protection (CP). Coated specimens were exposed to 0.6 M NaCL solution. Cathodic protection was applied at −0.78 V and −1.1 V (SCE). Coated specimens were also tested at Open Circuit Potential (OCP). The application of cathodic protection at −1.1 V was shown to affect the protective properties of the coating, causing the coating resistance to fall below the border line between fair and poor coating. The coating maintained a resistance in the order of 1 × 10⁶ Ω cm² when CP was applied at −0.78 V but a resistance of 1 × 10⁵ Ω cm² when CP was applied at −1.1 V. It was shown that water uptake by the coated specimens was considerably affected by the application of CP. The water uptake by the coated specimens was increased as a result of increasing the level of CP. The application of CP at −0.78 V, and −1.1 V was found to reduce the extent of corrosion on the coated specimens.     

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.     

Electrochemical studies on the alternating current corrosion of mild steel under cathodic protection condition in marine environments

Alternating current (AC) corrosion of mild steel in marine environments under cathodic protection (CP) condition was studied. Electrochemical studies at the two protection potentials namely −780 and −1100 mV versus SCE were examined by different techniques. DC polarization study was carried out for mild steel in natural seawater and 18.5 g/L NaCl solution to evolve corrosion current density. The corrosion rate determination, pH of the end experimental solution and surface morphology of the mild steel specimens under the influence of different AC current densities were studied. The amount of leaching of iron into the solution was estimated using inductively coupled plasma spectrometry. All these techniques revealed that AC influences the corrosion of mild steel in the presence of marine environments even though CP was given. Surface micrographs revealed that spreading of red rust products noticed on the mild steel surface. At −780 mV CP, red rusts are visually seen when the AC source was above 10 A/m² in both the media but red rusts are appeared after 20 A/m² in the case of −1100 mV CP. Weight loss measurements coupled with surface examination and solution analysis is a effective tool to characterize and quantify the AC corrosion of mild steel in marine environments.     

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.     

A study of the bond degradation of rebar due to cathodic protection current

Bond degradation of rebar embedded in concrete due to impressed cathodic protection current was studied and is reported in this paper. Different mix designs of concrete are found to have influence on the degradation percentage of bond strength. More specifically, bond strength degradation percentage with higher water-to-cement (w/c) ratio is found to be larger than that with lower w/c ratio. The microstructure scanning electron microscope (SEM) photos of the concrete near the rebar-concrete interface showed that a loose structure with larger microvoids existed in the interface zone. Further, microhardness tests on the concrete near the interface and chemical titration to determine contents of potassium and sodium ions were performed to ensure that the main cause of bond degradation is the softening effect of concrete. A unified parameter, which combined the effects of cathodic current density and polarization time, is used to build up the relationship between experimental data. This concept allows engineers to quickly obtain design information from the experimental data of accelerated tests.     

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.     

Role of sulphate ions on the formation of calcareous deposits on steel in artificial seawater; the formation of Green Rust compounds during cathodic protection

Cathodic protection of steel in seawater could be optimized by taking into account the calcareous deposits forming on the steel surface. The aim of this work was to study the influence of sulphate ions on the kinetics and mechanisms of formation of these deposits. The experiments were performed at 20 °C, with an applied potential of −1.0 V/saturated calomel electrode (SCE), in artificial seawater-like solutions with various SO₄²⁻ concentrations. The deposition was monitored by chronoamperometry and electrochemical impedance spectroscopy (EIS). Micro-Raman analyses were performed in situ in a specific electrochemical cell to identify the solids forming on the steel surface. It could be demonstrated that sulphate ions had an important effect on the formation of both Ca(II)- and Mg(II)-containing phases. In the solution enriched with sulphate ions, the deposition of CaCO₃ was almost totally inhibited. Experiments performed in Ca²⁺-free solutions demonstrated that the Mg-based deposit was, in contrast, favoured by the increase of the sulphate concentration. In situ Raman spectra of the solid forming at the early stages of the cathodic protection proved to be characteristic of Green Rusts (GRs). This compound was favoured by the presence of Ca²⁺ and/or Mg²⁺ cations, and is more likely a GR-like M(II)-Fe(III) hydroxysulphate, with M = Fe, Mg and Ca.     

Cathodic protection of carbon steel in natural seawater: Effect of sunlight radiation

Cathodic protection of metals in seawater is known to be influenced by chemical–physical parameters affecting cathodic processes (oxygen discharge, hydrogen evolution and calcareous deposit precipitation). In shallow seawater, these parameters are influenced by sunlight photoperiod and photosynthetic activity. The results presented here represent the first step in studies dedicated to cathodic protection in shallow photic seawater. This paper reports on carbon steel protected at −850 mV vs. Ag/AgCl (oxygen limiting current regime) in the presence of sunlight radiation but in the absence of biological and photosynthetic activity, the role of which deserves future research. Comparison of results obtained by exposing electrochemical cells to daylight cycles in both biologically inactivated natural seawater and in NaCl 3.5 wt.% solutions showed that sunlight affects current densities and that calcareous deposit interfere with light-currents effects. Sunlight radiation and induced heating of the solution have been separated, highlighting results not otherwise obvious: (1) observed current waves concomitant with sunlight radiation depend fundamentally on solar radiation, (2) solar radiation can determine current enhancements from early to late phases of aragonite crystal growth, (3) a three-day-old CaCO₃ layer reduces but does not eliminate the amplitude of the current waves. Theoretical calculations for oxygen limiting currents and additional field tests showed that sunlight, rather than bulk solution heating, is the main cause of daily current enhancements. This was confirmed by polarizations performed at −850 and −1000 mV vs. Ag/AgCl (constant bulk temperature), during which the electrode was irradiated with artificial lighting. This test also confirmed O₂ discharge to be the cathodic process involved. A mechanism of radiation conversion to heat in the oxygen diffusion layer region is proposed.     

Influence of surface pretreatment and electrocoating parameters on the adhesion of cathodic electrocoat to the Al alloy surfaces

Adhesion of cathodic electrocoat films to the aluminum alloys 2024-T3 bare and Alclad 2024-T3 with different pretreatments and with different cathodic electrocoat process parameters was investigated. The pretreatments studied were acetone wipe and alkaline cleaning. The cathodic electrocoat process parameters studied include variation of cathodic electrocoating voltage and time. Adhesion performance was evaluated by measuring the delamination time and percent delamination of the electrocoat from the alloy surface by placing the small specimen of the sample in the N-methyl pyrrolidinone (NMP) solution at 60°C until the film lifts off or for 2 h whichever comes first. NMP times for electrodeposited film delamination from alkaline cleaned surfaces were found to be higher than the acetone wiped and or those of as-supplied metal surfaces. There was not much effect of acetone cleaning of these alloy surfaces on the adhesion performance of the cathodic electrocoat. The voltage–current (of cathodic electrocoating process) relationships for alkaline cleaned surfaces were also found to be significantly different from the other two types of surfaces. The NMP times of cathodic electrocoat delamination at lower cathodic electrocoating voltage and lower electrocoating times were higher than those at higher cathodic electrocoating voltage and electrocoating times for alkaline cleaned 2024 bare surfaces. Electrocoat thickness developed on the surfaces during the electrodeposition process increased with increasing electrodeposition voltage and time as anticipated.     

Effects of cathodic prevention on the chloride threshold for steel corrosion in concrete

This paper presents the results of long-term experimental tests aimed at studying the effects of cathodic prevention on the critical chloride threshold for the onset of pitting corrosion on steel bars in concrete. Cathodic prevention is applied when the structure is new and rebars are still passive being in contact with alkaline and chloride-free concrete. The results obtained showed that even very low values of current densities can increase the critical chloride threshold and, therefore, contribute to increase the service life of reinforced concrete structures in chloride-bearing environments.     

Surface treatment of pigments. Treatment with inorganic materials

The surface treatment of pigment particles plays an ever more important role in the pigment industry — especially in paint and ink applications. The use of pigment derivatives shows some strong limitations with respect to bleeding and coloristics. Novel treatments of pigments with inorganic materials are presented. This type of colorless and insoluble treatment has a marked positive effect on the rheological behavior of paints without changing the other pigment properties. These treatments allow a broad modification of the surface characteristics of the pigment particles which leads to novel improved products.     

Surface properties of oxyfluorinated PAN-based carbon fibers

In this study, the oxyfluorination of PAN-based carbon fibers was undertaken at room temperature using fluorine-oxygen mixtures, and the influence of oxyfluorination on properties such as wettability, surface polarity, surface free energy, conductivity and tensile strength was investigated. As the oxyfluorination time increased at a total pressure of 5 kPa, both the fluorine/carbon and oxygen/carbon ratios increased. The contribution of semicovalent C-F bond to F1s spectra is considerably decreased with increasing total pressure from 5 to 80 kPa, and at the same time, the contribution of covalent C-F bond is increased. As the total pressure of fluorine-oxygen mixtures increased, the contact angle of water significantly decreased and again increased to a similar value to that of as-received carbon fiber. A short oxyfluorination of carbon fibers considerably increased the wettability, that is, hydrophilicity.The electrical conductivity of oxyfluorinated carbon fiber is larger than that of the as-received fiber. This is because the surface region of carbon fiber is fluorinated. An increase in the tensile strength of about 18% after oxyfluorination is observed. The increase in tensile strength of oxyfluorinated carbon fibers can be understood as being due to a decrease in the diameter of the fiber.