Modeling pipeline crevice corrosion under a disbonded coating with or without cathodic protection under transient and steady state conditions

Underground steel pipelines are protected by coatings and cathodic protection (CP). The pipeline corrosion occurs when the coating is disbonded away from a defect or holiday to form a crevice and the corrosion rate varies temporally and spatially in the crevice. In the presence of dissolved oxygen (O₂) in soil ground water, a differential O₂ concentration cell may develop in the crevice because O₂ diffuses more readily into the crevice through the holiday than through the disbonded coating. CP can decrease or eliminate the O₂ concentration cell depending on the potential applied at the holiday. Since the coatings are usually non-conductive, CP is unable to protect the steel surface deep inside the crevice. The transport of dissolved O₂, and that of dissolved carbon dioxide (CO₂) if present, into the crevice through holiday can be key to determining the crevice corrosion rate. In this work, the transient and steady state behavior of the corrosion process is investigated. The effect of the cathodic portion of iron vs. ferrous ion redox reaction on the crevice corrosion rate, which is often neglected traditionally, is further studied. At steady state, the effect of dissolved O₂ on the crevice corrosion rate and the added effect of dissolved CO₂ are mathematically modeled.     

Stress corrosion cracking initiation under the disbonded coating of pipeline steel in near-neutral pH environment

A novel test setup has been used in this study to simulate stress corrosion cracking initiation under a disbonded coating on an X-65 pipeline steel. In this setup, the synergistic effects of cyclic loading, cathodic protection and soil solution environment under disbonded coatings have been considered. When the X-65 pipeline steel was exposed to the test environment, there existed a wide range of corrosion products on the steel surface in the gradient of cathodic protection. Increasing the test time and the maximum stress increased the possibility of stress corrosion cracking initiation in regions with a high susceptibility to pitting corrosion.     

Impact of transient chemistry on the corrosion potential of a steam turbine disc steel

The adoption of two-shifting in coal-fired power generation (switching from on-load to off-load conditions on a daily basis and off-load for the weekend) results in regular cycling of the solution chemistry of the condensed steam on the turbine discs. A first stage investigation has been made of the effect of such chemistry cycling on the corrosion potential of the disc steel. The corrosion potential is typically about +0.05 V (SCE) in off-load chemistry (aerated pure water) and below −0.6 V (SCE) in on-load chemistry (deaerated solution containing chloride or chloride and sulphate anions). The critical observation was the sluggish response of the corrosion potential upon restoration of deaerated on-load conditions with the implication of a likely increase in pit and stress corrosion crack development.     

FEP/PPS共混涂层微观结构及其与钢基体的结合强度

以机械共混法在普通碳钢基体上制备了多种FEP/PPS共混改性防腐涂层,利用光学显微镜(OM)、电子探针(EPMA)研究了FEP/PPS共混涂层的微观结构、成分分布,采用拉伸法测定了FEP/PPS共混涂层与钢基体的结合强度,研究了共混组分PPS对复合防腐涂层结合强度的影响.结果表明,随着共混涂层中PPS组分的增加,共混涂层由典型的"海-岛结构"变为两相连续的"海-海结构",使涂层/钢基体结合强度有大幅度提高,拉断形式由涂层与基体界面光滑开裂,转变为涂层内聚开裂.     

Effect of CO2 and R-ratio on near-neutral pH stress corrosion cracking initiation under a disbonded coating of pipeline steel

This study investigates the role of CO₂ and cyclic stress R-ratio (R = minimum stress/maximum stress) on near-neutral pH SCC initiation mechanism(s) under a disbonded coating of pipeline steel protected by cathodic protection (CP). It was found that depending on CO₂ concentration and level of CP, different localized environments with various pH could be formed under the disbonded coating. When cyclic loading was applied, different SCC initiation mechanisms were involved depending on the pH of the localized environments. Reducing the R-ratio had different effects on the initiation mechanisms.     

Effect of a laser pre-quenched steel substrate surface on the crack driving force in a coating–steel substrate system

A mechanical model of a coating/laser pre-quenched steel substrate specimen with a crack oriented perpendicular to the interface between the coating and the hardened layer is developed to quantify the effects of the residual stress and hardness gradient on the crack driving force in terms of the J-integral. It is assumed that the crack tip is in the middle of the hardened layer of the pre-quenched steel substrate. Using a composite double cantilever beam model, analytical solutions can be derived, and these can be used to quantify the effects of the residual stress and the hardness gradient resulting from the pre-quenched steel substrate surface on the crack driving force. A numerical example is presented to investigate how the residual compressive stress, the coefficient linking microhardness and yield strength and the Young’s modulus ratio of the hardened layer to the coating influence the crack driving force for a given crack length.     

Temperature as a pitting and crevice corrosion criterion in the FeCl3 test

The FeCl₃ test is applied to an increasing extent for examining the resistance to pitting and crevice corrosion. Two methods having proved their value are described, the chemical properties of the FeCl₃ solution with regard to hydrolysis, pH and redox potential behaviour at various test temperatures are set forth and finally numerous results of the application of this test to high-alloy stainless steels and nickel alloys are presented. These results have been used to establish, be means of multiple regression, two empirical equations that allow to estimate rather accurately the critical pitting and crevice corrosion temperatures (CPT, CCT) from the contents of the decisive alloying constituents. These temperatures vary by about 2.5°C in the CPT test and by approx. 10°C in the CCT test, which can be reduced, however, by extending the test period beyond 24 hours. This is due to the fact that corrosion potentials in a 10% FeCl₃ · 6H₂O solution take a long time to stabilize. The variation of the critical crevice temperature can be further reduced by pressing the crevice blocks at a higher torque to the specimen. Another section particularly deals with the application of the CPT test for determining the influence of the matrix on the resistance to local corrosion. Consequently, the CPT test lends itself excellently to the examination of welds and as a quality control. Finally, CPT test results are compared with pitting data determined electro-chemically in artificial seawater. This shows that the ranking order with regard to corrosion resistance is identical, although media and processes differ considerably from each other.     

Correlation between corrosion rate and AE signal in an acidic environment for mild steel

The AE method is an effective technique for inspecting corrosion damage of mild steel, such as tank bottom floors. However, the correlation between AE signals and corrosion behaviour for mild steel has not yet been fully clarified. In the present study, the authors considered that the corrosion regions of bottom floors become a strong acid environment by Cl⁻, as reported in a previous study. Thus, the polarization resistance for the test pieces of mild steel was measured with an AC impedance method under a strong acid environment. It was clear that the polarization resistance indicated the corrosion rate for a test piece of mild steel in the experiments. While measuring the AE signals, the corrosion rate was monitored with a test piece. As a result, the AE signal showed good correlation with the corrosion rates of the test pieces. The corrosion behaviour of the test pieces was then discussed with the corrosion potential measured during the experiments. Furthermore, the cathode current was changed to control the generated hydrogen gas volume. The volume of the hydrogen gas generated from the cathode reaction was correlated to the AE signals.     

On the tensile behaviors of a hard chromium coating plated on a steel substrate with periodic subsurface inclusions

The tensile behaviors of a hard chromium coating plated on a steel substrate with periodic laser pre-quenched regions have been investigated by experimental and theoretic analysis. In the experiment, three specimens are adopted to study the differences between homogeneous and periodic inhomogeneous substrates as well as between periodic inhomogeneous substrate of relatively softer and stiffer materials. The unique characteristics have been observed in the specimen of periodic inhomogeneous substrate under quasi-static tension loading. With the periodic laser pre-quenched regions being treated as periodic subsurface inclusions (PSI), the unique stress/strain pattern of the specimen is obtained by analytical modeling and FEM analysis, and the mechanisms accounting for the experimental results is preliminarily illustrated.     

Morphology and phase composition of corrosion products formed at the zinc-iron interface of a galvanized steel

The corrosion products formed on the inner wall of pipes made of galvanized low carbon steel, exposed for ∼2 years to water flowing in a large household heating system, were analysed using X-ray diffraction, Mössbauer and Raman spectroscopic techniques, as well as metallographic techniques. Products grew in the form of large-sized tubercles that gradually developed causing base metal losses up to perforation of the steel pipe. Considerable differences in the phase composition were found between the products formed in contact with the steel and those constituting the outer part of tubercles. The former were mainly made of FeCO₃ (siderite), with small amounts of Zn₅(CO₃)₂(OH)₆ (hydrozincite), ZnCO₃ (smithsonite), (Fe,Zn)CO₃ mixed carbonate and CaCO₃ (calcite), the latter mainly by Fe(III) oxyhydroxide goethite. Both parts of the tubercles also contained small amounts of other ferric oxyhydroxides, γ-FeOOH (lepidocrocite) and β-FeOOH (akaganeite), and very small amounts of hematite. The procedures used proved effective for an adequate identification of both the iron-containing and iron-free compounds in the corrosion products as well as for suggesting a corrosion mechanism.     

Electrochemical polarization behavior of X70 steel in thin carbonate/bicarbonate solution layers trapped under a disbonded coating and its implication on pipeline SCC

Potentiodynamic polarization measurements were performed on X70 pipeline steel in thin carbonate/bicarbonate solution layers trapped under a disbonded coating. A conceptual model was developed to illustrate the effects of the thickness and concentration of the trapped solution layer, cathodic protection (CP) potential and stress on stress corrosion crack initiation and propagation in pipelines. It was found that the passivity of the steel depended on the solution layer thickness, and the passive current density decreased with the thinning of the solution layer. With an increasing solution concentration, the role of the solution layer thickness in the steel passivity became unapparent, which was attributed to a strong passivating ability of bicarbonate and carbonate ions. Furthermore, with the decrease of the solution layer thickness, the pitting potential was shifted negatively. However, an increase of the solution concentration enhanced the resistance of the steel to pitting. A pre-application of CP would degrade the passivity of the steel due to the hydrogen-enhanced activity of the steel. Moreover, an applied stress shifted the pitting potential negatively, and decreased the passive potential range.     

Theoretical considerations on the supposed linear relationship between concrete resistivity and corrosion rate of steel reinforcement

Traditionally, the assessment of service life of steel reinforced concrete structures has been focused on the prediction of the time required to achieve a transition from passive to active corrosion rather than to accurately estimate the subsequent corrosion rates. However, the propagation period, i.e. the time during which the reinforcing steel is actively corroding, may add significantly to the service life. Consequently, ignoring the propagation period may prove to be a conservative approach. On the other hand the prediction of the corrosion rate may result in a very complex task in view of the electrochemical nature of corrosion and the numerous parameters involved. In order to account for the various influences an essentially empirical model has been introduced in which the electrolytic resistivity of the concrete environment serves as the major parameter. This model will be discussed for carbonation‐induced corrosion based on the commonly accepted theory of aqueous corrosion. An alternative model for microcell corrosion is proposed which is based on the commonly accepted view that anodic and cathodic sites are microscopic and their locations change randomly with time. In line with this view electrolytic resistivity can be incorporated and thus may play a significant role in the kinetics of the corrosion process. For a wide range of corrosion current densities the relationship between corrosion current density, log(i_corr), and concrete resistance, log(R_con), can then be approximated by an almost ideal linear relationship. Assuming a fixed geometrical arrangement of anodic and cathodic sites on the steel surface, this linear relationship is also valid for concrete resistivity, ρ_con. However, from the theoretical treatment of the electrochemical processes underlying reinforcement corrosion it becomes evident that a linear relationship between corrosion current density and concrete resistivity does not necessarily imply that concrete resistance is dominating the overall corrosion cell resistance. In most cases a significant portion of the driving voltage of the corrosion cell will be consumed by the transfer of electrical charge involved in cathodic reactions, i.e. cathodic activation control will dominate.     

Phosphate coating on stainless steel prepared in electrolyte with silica sol: zinc segregation,post-treatment and corrosion resistance

Phosphate film is generally not compact, left with microscopic cracks or pores during the phosphating process. Silica sol is incorporated into the phosphating solution to fabricate phosphate films on stainless steel 316L by electrochemical method. It is found that at appropriate amount of silica sol (8 vol.-%), the cracks on the hopeite film are effectively filled, while they appear again when much more silica sol is added as observed by SEM images. Moreover, zinc is found simultaneously formed as detected by the energy dispersive spectroscopy and X-ray diffraction measurements. In order to improve the performances of the hopeite film, we use titania sol by dip coating to cover the hopeite film. The titania sol can improve the anticorrosion ability of the films with limited extent since its crack formation during curing. By adding polyvinyl butyral (2 wt-%) in this sol, the composite film exhibits great improvement in corrosion resistance resulting from the cracks remedy and synergy effect of zinc with titania gel.     

The determination of the corrosion rate of steel in concrete by a non-stationary method

A new equivalent circuit model of the behaviour of the steel/concrete system is proposed. The theoretical basis for calculating the elements of this model from transient potentiostatic decay curves is given. Finally, a simplified method for determining the instantaneous corrosion rate from the transient response is proposed.     

The use of pumice as a coating for the reinforcement of steel against corrosion and concrete abrasions

This study presents the results of corrosion resistance for pumice collected from pyroclastic exposure in the Van, Kayseri, Nevsehir and Osmaniye regions of Turkey. The corrosion resistance of reinforced steel (RS) and mass losses of concrete specimens were investigated. The specimens were exposed to 5 and 10% sodium sulphate solutions. Reinforced steel mass losses and compressive strengths of concrete were measured. Improvements of the compressive strength and corrosion resistance were observed for specimens with the increasing layers of coating. The corrosion rates of pumice coated specimens were lower than the control specimens. There was a close relationship between type of pumice coating and reinforcement corrosion. Corrosion ratio decreased with increasing amounts of reactive SiO₂. The alkalinity of the concrete, permeability of the concrete cover, the quality of the concrete and the corrosion environment were crucial factors in influencing the effectiveness of the concrete cover for corrosion protection of reinforced steel. All pumice concretes offered excellent resistance to corrosion, where Osmaniye pumice (OP) best increased corrosion resistance of reinforced steel.     

Effect of the exposure angle in the corrosion rate of plain carbon steel in a marine atmosphere

This investigation aims to analyse the effect of the exposure angle on the corrosion rate of mild steel. Test samples were exposed to a marine environment at 0°, 30°, 45° and 90° inclination. To determine the effects of contaminants on the protective characteristics of the rusts, Cl and SO₂ contents in the atmosphere as well as SEM-EDX analyses and polarisation curves on the weathered samples were performed. Results demonstrated that the exposure angle influences the corrosion rate, as also the morphology of the rust, but with no effect on rust composition.     

Variation of carbon steel corrosion rate with flow conditions in the presence of an inhibitive formulation

This work is an extension of studies into the mechanism of inhibition of a carbon steel by a non-toxic multicomponent inhibitor (fatty amines associated with phosphonocarboxylic acid salts) used for the treatment of water in cooling circuits. In a previous work [N. Ochoa, F. Moran, N. Pébère, B. Tribollet, Corros. Sci. 47 (2005) 593], it was shown that the properties of the protective layers formed on the metal surface were dependent on the electrode rotation rate. Moreover, two distinct surface areas were visualised on the metal surface and the ratio between the two zones was dependent on the flow conditions. The present study focuses on the measurement of the corrosion rate from impedance diagrams obtained at the corrosion potential for different electrode rotation rates. The measured polarisation resistances correspond to the anodic process. A non-monotonic variation of the corrosion current densities was observed and explained by the variation of the ratio between the two layers, which each have different intrinsic protective properties. From the polarisation curves plotted in the same conditions, the non-monotonic variation was not shown. Independently of the electrode rotation rate, the corrosion current densities remained low. This study brought an original approach to the influence of flow on the corrosion rate in the presence of inhibitors.