Characterization of corrosion of X70 pipeline steel in thin electrolyte layer under disbonded coating by scanning Kelvin probe

Scanning Kelvin probe technique was used to characterize the electrochemical corrosion behavior of X70 steel in a thin layer of near-neutral pH and high pH solutions, respectively. Results demonstrate that passivity can be developed on steel in the near-neutral pH solution layer as thin as 60 μm, which is attributed to the fact that Fe²⁺ concentration in aqueous phase could reach saturation in the thin solution layer. The solubility of FeCO₃ is reached to drop out of solution as a precipitate. With the increase of solution layer thickness, it becomes more difficult for Fe²⁺ concentration to reach saturation. Consequently, the passivity cannot be maintained, and the steel shows an active dissolution state. Anodic dissolution rate of steel increases with the immersion time. The electrochemical polarization behavior of X70 steel in high pH solution is approximately independent of the solution layer thickness and immersion time. In thin solution layer, diffusion and reduction of oxygen dominate the cathodic process, as demonstrated by the presence of cathodic limiting diffusive current. In the bulk solution, the absence of limiting diffusive current density in cathodic polarization curve indicates that the main cathodic reaction is reduction of H₂CO₃ and , and the formed film is thus mainly FeCO₃.     

Micro-electrochemical characterization of corrosion of pre-cracked X70 pipeline steel in a concentrated carbonate/bicarbonate solution

The electrochemical corrosion behavior of a stressed, pre-cracked X70 pipeline steel was studied in a bicarbonate/carbonate solution by electrochemical and micro-electrochemical measurements, numerical calculation and surface analysis technique. The effects of stress and potential on passivity, corrosion and electrochemical behavior of the steel at crack-tip were mechanistically determined. It was found that the passive film formed at crack-tip was less stable than that formed in the region ahead of the crack. Moreover, the crack-tip is more susceptible to pitting corrosion than other region of the specimen. The applied stress enhances the anodic dissolution of the steel. In particular, the stress concentration at crack-tip further increases the local anodic dissolution rate. The enhancement of the anodic dissolution of the steel at crack-tip is also resulted from the formation of a galvanic couple, i.e., the crack-tip as an anode and the surrounding region as a cathode.     

Effects of alternating current on corrosion of a coated pipeline steel in a chloride-containing carbonate/bicarbonate solution

In this work, the alternating current (AC)-induced corrosion of a coated pipeline steel was studied in a chloride-containing, concentrated carbonate/bicarbonate solution, which simulated the trapped high pH electrolyte under coating, by potentiodynamic polarization measurements, immersion tests and surface characterization technique. It was found that an application of AC resulted in a negative shift of corrosion potential of the steel, caused an oscillation of anodic current density, and degraded the steel passivity developed in the solution. With the increase of AC current density, the corrosion rate of the steel increased. At a low AC current density, a uniform corrosion occurred, while at a high AC current density, pitting corrosion occurred extensively on the steel electrode surface. At individual applied AC, there was a higher electrochemical dissolution activity of the coated steel electrode containing a 1 mm defect than that of the electrode containing a 10 mm defect.     

Effect of AC on stress corrosion cracking behavior and mechanism of X80 pipeline steel in carbonate/bicarbonate solution

The influence of various AC current densities on stress corrosion cracking behavior and mechanism of X80 pipeline steel was investigated in carbonate/bicarbonate solution by polarization curves and slow strain rate tensile tests. With the increasing AC current density, the SCC susceptibility of the steel increases, especially at high AC current density. A significant difference in the SCC behavior and mechanism is found for the steels with or without AC application. In the absence of AC, the fracture mode is intergranular and the mechanism is attributed to anodic dissolution. Under AC application, the cracks propagation is transgranular, and the mechanism is mixed controlled by both anodic dissolution and hydrogen embrittlement.     

Effect of cathodic protection on corrosion of pipeline steel under disbonded coating

In this work, a test rig was developed to study the effect of cathodic protection (CP) on corrosion of X70 pipeline steel in the crevice area under disbonded coating through the measurements of local potential, solution pH and dissolved oxygen concentration. Results demonstrated that, in the early stage of corrosion of steel, CP cannot reach the crevice bottom to protect steel from corrosion due to the geometrical limitation. Corrosion of steel occurs preferentially inside crevice due to a separation of anodic and cathodic reaction with the depletion of dissolved oxygen in the crevice solution. The main role of CP in mitigation of sequential corrosion of steel in crevice under disbonded coating is to enhance the local solution alkalinity. With the increase of distance from the open holiday, a high cathodic polarization is required to achieve appropriate CP level at crevice bottom. A potential difference always exists between the open holiday area and inside crevice, reducing the CP effectiveness.     

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.     

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.     

SCC initiation for X65 pipeline steel in the “high” pH carbonate/bicarbonate solution

The initiation of stress corrosion cracking (SCC) was studied using scanning electron microscope observations of linearly increasing stress test specimens. SCC initiation from the following surfaces was studied: (i) initiation from the commercial pipe surface covered by the Zn coating, (ii) initiation from a mechanically polished surface with a deformed layer, and (iii) initiation from an electro-polished surface. SCC initiation involved different features for these surfaces as follows. (i) For the Zn coated commercial pipe surface, a crack in the Zn coating led to the dissolution of the deformed layer and when the deformed layer was penetrated, intergranular SCC initiation became possible. (ii) For a mechanically polished surface with a deformed layer, cracks in the surface oxide concentrated the anodic dissolution to such an extent that there was transgranular SCC in the deformed layer. SCC was intergranular when the deformed layer had been penetrated. Transgranular stress corrosion cracks were stopped at ferrite grain boundaries (GBs) oriented perpendicular to the SCC propagation direction. (iii) For an electro-polished surface, the surface oxide film was cracked at many locations, but intergranular SCC only propagated into the steel when the oxide crack corresponded to a GB. An oxide crack away from a GB is expected to be healed. The observed SCC initiation mechanism was not associated with simple preferential chemical attack of the ferrite GBs.     

Characterization of corrosion of X65 pipeline steel under disbonded coating by scanning Kelvin probe

Corrosion of X65 pipeline steel under a disbonded coating was studied by scanning Kelvin probe measurements. Three types of specimen were designed and prepared to investigate the effects of immersion time, oxygen concentration and wet-dry cycle on Kelvin potential profile and thus corrosion behavior of the steel. Kelvin potential measured on “intact” area is shifted negatively with time, indicating an increasing water uptake under the “intact” coating. With the increase of the amount of solution, it is expected that the electrolyte concentration and electrochemical reaction rate change, resulting in a significant decrease of interfacial potential. Moreover, there is a more negative Kelvin potential on disbonded area than that on “intact” area. The negative shift of Kelvin potential is attributed to corrosion reaction of steel occurring under the disbonded coating. Due to the narrow geometry of coating disbondment, an oxygen concentration difference exists along the depth of the disbondment. The corrosion behavior under disbonded coating strongly depends on the oxygen partial pressure and local geometry. With continuous purging of nitrogen and removing of oxygen, Kelvin potential tends to be identical throughout the disbonded area. During wet-dry cycle, the thickness of solution layer trapped under disbonded coating decreases due to evaporation of water. With the decrease of solution layer thickness, the measured Kelvin potential decreases, indicating that the effect associated with the reduction of oxygen solubility in the concentrated solution during drying of electrolyte is favored over that related to the enhanced oxygen diffusion and reduction. There exists a critical thickness of solution layer, below which the oxygen solubility is sufficiently low to support the electrochemical corrosion reaction of steel.     

Local environment under simulated disbonded coating on steel pipelines in soil solution

Taking advantage of microelectrode technique, the local potential and pH in a crevice simulating disbonded coating on X70 pipeline steel were investigated as a function of cathodic protection (CP) in a near neutral pH soil bulk solution bubbled with 5% CO₂/N₂ gas. The experimental potential–pH (E–pH) diagrams were established for the steel in the crevice. Stress corrosion cracking (SCC) susceptibility of the steel in the local environment in the crevice was analyzed based on the experimental E–pH diagrams. The results showed that the local steel potential in the deep of the crevice was independent on CP potential applied at the opening. Due to the effect of the atmospheric CO₂, a near-neutral pH local environment promoting near-neutral pH SCC (also known as transgranular SCC, TGSCC) might be harbored in the crevice even with normal CP at the opening. During CP interruption, the steel potential decay and CO₂ absorption (pH decrease) might shift E–pH points into a susceptibility region of near-neutral pH SCC.     

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.     

Local additional potential model for effect of strain rate on SCC of pipeline steel in an acidic soil solution

Stress corrosion cracking (SCC) behavior of X70 pipeline steel in an acidic soil solution was investigated by slow strain rate test, surface characterization, potentiodynamic polarization curve measurement and electrochemical hydrogen permeation technique. A local additional potential model (LAPM) was developed to illustrate the critical role of strain rate in SCC of the steel. According to LAPM, both density and mobility of local active spots on the steel surface, i.e., dislocation emergence point, increase linearly with strain rate. Generation of such active spots introduces an additional negative potential locally, affecting the electrochemical reaction and, consequently, the susceptibility of the steel to SCC. It is found that a maximum of the SCC susceptibility occurs at strain rate of 10⁻⁶ s⁻¹, which is associated with an enhanced hydrogen evolution due to the local additional potential (LAP) effect. When strain rate is sufficiently high to exceed 10⁻⁶ s⁻¹, the mobility of the dislocation emergence points is so fast that the reactive species in solution cannot combine with them for cathodic reaction, resulting in a decrease of the SCC susceptibility. Similarly, a maximum of hydrogen permeation current observed at the strain rate of 10⁻⁶ s⁻¹ is also attributed to the effect of strain rate on the density and mobility of dislocations in the steel. Diffusion of hydrogen atoms in a strained steel is through both body diffusion and dislocation diffusion, with the latter enhanced by an increasing strain rate. When strain rate is so high that the dislocation mobility is sufficiently fast, hydrogen atoms become incapable of catching up with the dislocations. As a result, the hydrogen diffusion is dominated by the body diffusion mode.     

Micro-electrochemical characterization of corrosion of welded X70 pipeline steel in near-neutral pH solution

The local corrosion behavior of welded X70 pipeline steel in near-neutral pH solution was studied by micro-electrochemical measurements, including scanning vibrating electrode and local electrochemical impedance spectroscopy. The microstructure of the welded steel was observed by optical microscopy and scanning electron microscopy. It is demonstrated that the microstructure of weld metal consists of acicular ferrite and grain boundary ferrite, while that of heat-affected zone is a mixture of acicular ferrite, bainitic ferrite and a few martensite/austenite microconstituents. The microstructure of base steel is typically ferrite and pearlite. Electrochemical corrosion mechanism of welded X70 steel does not experience change upon hydrogen-charging, or stressing, or both. Hydrogen-charging is capable of enhancing the local anodic dissolution of the steel. The resistance of corrosion product layer decreases with hydrogen-charging, and heat-affected zone has the largest dissolution current upon hydrogen-charging. The increase of applied stress enhanced the anodic dissolution of welded X70 steel, especially the heat-affected zone, in near-neutral pH solution. Maximum current is observed in heat-affected zone, and increases with the increase of applied stresses. The total synergistic effect of hydrogen-charging (10 mA/cm²) and applied stress (550 MPa) on anodic dissolution of welded X70 steel in near-neutral pH solution is determined to be within the range of 5.7 and 6.5, with a maximum value encountering in heat-affected zone.     

Stress corrosion cracking behavior of X70 pipe steel in an acidic soil environment

Stress corrosion cracking (SCC) behavior of X70 pipe steel was investigated in an extracted acidic soil solution by slow strain rate test (SSRT), potentiodynamic polarization curve measurements and surface analysis technique. The SCC process and mechanism of X70 steel in the acidic soil solution is mixed-controlled by both anodic dissolution and the hydrogen involvement. With the different applied potentials, the dominance of SCC process changes. At a relatively less negative potential, the steel SCC is based primarily on the anodic dissolution mechanism. When the applied potential is shifted negatively, hydrogen is involved in the cracking process, resulting in a transgranular cracking mode. With the further negative shift of applied potential, the SCC of the steel follows completely a hydrogen-based mechanism, with a river-bed shaped brittle feature of the fracture surface. Heat treatment alters the microstructure of the steel, resulting in a change of SCC susceptibility. In particular, the quenched steel with a bainite microstructure has a high susceptibility to SCC in the acidic soil, while the as-received steel with a ferrite matrix have a low SCC susceptibility.     

Electrochemical corrosion of X65 pipe steel in oil/water emulsion

The electrochemical corrosion behavior of X65 pipeline steel in the simulated oil/water emulsion was investigated under controlled hydrodynamic and electrochemical conditions by rotating disk electrode technique. Results demonstrated that mass-transfer of oxygen plays a significant role in the cathodic process of steel in both oil-free and oil-containing solutions. Electrode rotation accelerates the oxygen diffusion and thus the cathodic reduction. The higher limiting diffusive current density measured in oil-containing solution is due to the elevated solubility of oxygen in oil/water emulsion. The anodic current density decreases with the increase of electrode rotating speed, which is attributed to the accelerated oxygen diffusion and reduction, enhancing the steel oxidation. Addition of oil decreases the anodic dissolution of steel due to the formation of a layer of oily phase on steel surface, increasing the reaction activation energy. The steel electrode becomes more active at the elevated temperature, indicating that the enhanced formation of oxide scale is not sufficiently enough to offset the effect resulting from the enhanced anodic dissolution reaction kinetics. The corrosion reaction mechanism is changed upon oil addition, and the interfacial reaction is activation-controlled, rather than mass-transfer controlled. When sand particles are added in oil/water emulsion, there is a significant increase of corrosion of the steel. The presence of sands in the flowing slurry would impact and damage the oxide film and oily film formed on the steel surface, exposing the bare steel to the corrosive solution.     

Failure mechanisms of high strength steels in bicarbonate solutions under anodic polarization

High strength steels used in prestressing concrete structures are not exempt from the effects induced by corrosion on the normal concrete reinforcement. Carbonation of surrounding concrete or mortar is not unlikely for prestressing tendons and strands. Moreover, these steels undergo to brittle fracture as a consequence of stress corrosion cracking phenomena. To evaluate if concrete carbonation can promote this kind of failure, constant load tests in bicarbonate aqueous solutions under anodic polarization were carried out on high strength steel wires. Microscopic examination pointed out that the wires exhibited a brittle fracture mode, while its natural feature is ductile, as indicated by air testing. Failure mechanism was evaluated by a fracture mechanic approach. Cracks initiation was attributed to an anodic dissolution mechanism, while its propagation, interpreted by means of the surface mobility theory, was related to interaction between hydrogen atoms and magnetite at a crack tip.     

Effects of hydrogen on the fracture toughness of a X70 pipeline steel

Effects of hydrogen on the fracture toughness of a X70 pipeline steel were investigated in the cases of hydrogen pre-charging and dynamic hydrogen charging in 0.5 mol/L H₂SO₄ solution under slow strain rate tensile testing. Under the hydrogen pre-charging, the fracture toughness decreased in a linear relationship with the hydrogen concentration as the hydrogen concentration was more than 1 ppm in weight. The fracture surfaces were characteristic of dimples. Under the dynamic hydrogen charging, the fracture toughness for hydrogen-induced cracking decreased linearly with logarithm of the hydrogen concentration without stress. The hydrogen-induced fracture had the appearance of cleavage facets.     

Comparative studies on the corrosion properties of a Fe-Mn-Al-Si steel and an interstitial-free steel

Recent developments in a group of super ductile Fe-Mn-Al-Si steels with high-manganese content demands for more research in the corrosion behavior of such steels. The corrosion properties of the Fe-Mn-Al-Si steel was studied in acidic (0.1 M H₂SO₄), alkaline (0.1 M NaOH) and chloride-containing (3.5% NaCl) environments, using immersion and polarization experiments and compared with that of interstitial-free (IF) steel. In acidic solution, the Fe-Mn-Al-Si steel exhibited significantly lower corrosion resistance than that of IF steel. Though the Fe-Mn-Al-Si steel showed lower corrosion resistance as compared to IF steel in chloride solution, the difference was not as substantial as observed in acidic medium. However, in alkaline solution, the Fe-Mn-Al-Si steel showed no significant difference in the corrosion resistance in comparison with that of IF steel, and moreover exhibited substantially high corrosion resistance than in acidic and chloride solution. The post-corrosion characterization studies showed higher corrosion attack of the Fe-Mn-Al-Si steel exposed to acidic solution as compared to that in alkaline and chloride solutions, which is consistent with the corrosion measurement data.     

Interpretation of the corrosion process of a galvannealed coating layer on dual-phase steel

The dissolution process of a galvannealed coating layer on dual-phase steel was examined by correlating a stripping test, metallographic observations and a polarisation test in an acidified chloride solution. The galvannealed coating layer was composed of several Fe–Zn intermetallic phases, namely the gamma, delta, and zeta phases, from the substrate. The dissolution began from the outermost zeta phase and proceeded to the gamma and then the delta phase. The dissolution rates for each intermetallic phase and galvanic couples were measured and estimated through a polarisation test, and the gamma phase in the gamma-substrate galvanic couple exhibited the highest corrosion rate.