Near-neutral pH Stress Corrosion Cracking Research Articles

Corrosion behavior of X-70 pipe steel in near-neutral pH solution

The mechanism of near-neutral pH stress corrosion cracking (SCC) of natural gas pipelines has not been well-established since the first accident was found in the 1980s. In particular, the role of hydrogen in near-neutral pH SCC has remained unknown. In this work, cyclic voltammetry was used to comprehensively investigate the fundamentals of the electrochemical corrosion reactions occurring at the steel/solution interface in diluted, 5% CO 2/N 2-purged, near-neutral pH bicarbonate solutions. It is shown that there is no stable oxide film formed on the steel surface in near-neutral pH solution. The dissolution-based cracking mechanism does not apply for near-neutral pH SCC of pipelines. The formation of a metastable Fe(OH) 2 deposit layer shows a catalytic activity on hydrogen evolution reaction, indicating that a significant amount of hydrogen could be generated under near-neutral pH condition. The presence of corrosive anions in the soil electrolyte enhances both the anodic polarization of the steel and the cathodic hydrogen evolution reaction, resulting in an increased hydrogen evolution rate. The introduction of oxygen could form a stable oxide film on the surface of steel, resulting in the loss of the surface catalytic effect on hydrogen evolution reaction. Thus, a hydrogen-based mechanism does not apply for SCC in the presence of oxygen.

Thermodynamically modeling the interactions of hydrogen, stress and anodic dissolution at crack-tip during near-neutral pH SCC in pipelines

A thermodynamic model was developed to clarify the interactions of hydrogen, stress and anodic dissolution at crack-tip during near-neutral pH stress corrosion cracking in pipelines by comprehensively considering the electrochemical reactions occurring in the pipeline steel in deoxygenated, near-neutral pH solution. By analyzing the change of the free-energy of steel due to the presence of hydrogen and stress, it is demonstrated that a synergism of hydrogen and stress promotes the cracking of steel. The enhanced hydrogen concentration in the stressed steel significantly accelerates the crack growth. An exact expression of the hydrogen concentration factor, i.e., the dependence of anodic dissolution rate of steel at crack-tip on the hydrogen concentration, is essential at the quantitative prediction of the crack growth rate.

Application of electrochemical techniques in investigation of the role of hydrogen in near-neutral pH stress corrosion cracking of pipelines

It has been acknowledged that hydrogen plays a critical role in near-neutral pH stress corrosion cracking (SCC) of pipelines. However, the accurate mechanism for hydrogen involvement remains unknown. This work reviewed the applications of various electrochemical techniques towards understanding near-neutral pH SCC. The techniques reviewed include electrochemical hydrogen permeation, cyclic voltammetry, electrochemical impedance spectroscopy, electrochemical noise and scanning photo-electrochemical microscopy. The manner by which these techniques allow for the investigation of the hydrogen evolution mechanism, adsorption/desorption and permeation kinetics and hydrogen diffusion and accumulation in steel as well as the interactions between hydrogen, anodic dissolution and stress at crack tip in near-neutral pH environmental condition is described. It is anticipated that the advanced electrochemical measurement techniques provide essential tools to investigate the mechanistic aspects on hydrogen involvement in near-neutral pH stress corrosion cracking in pipelines.

Mechanism for hydrogen evolution reaction on pipeline steel in near-neutral pH solution

Cyclic voltammetry, hydrogen permeation tests and electrochemical impedance spectroscopy measurements were combined to study the mechanism for hydrogen evolution reaction on X-70 pipe steel in near-neutral pH solution. It is found that hydrogen evolution reaction is dominated by the reduction of water molecules, followed by either an electrochemical hydrogen recombination reaction or a hydrogen absorption reaction. The near-neutral pH environment is capable of generating catalytic surface effect on hydrogen evolution on the pipe steel. The increasing dissolution of the cathodically pre-polarized steel could be due to the enhanced activation of the steel, rather than the increasing amount of hydrogen atoms in the steel. These results provide mechanistic information to understand the near-neutral pH stress corrosion cracking of pipelines.

Fundamentals of hydrogen evolution reaction and its implications on near-neutral pH stress corrosion cracking of pipelines

In this work, electrochemical techniques were utilized to investigate the hydrogen evolution reaction on X-70 pipe steel and the hydrogen permeation through the steel in near-neutral pH environmental condition. The results demonstrate that the steel has always been in an active-dissolution state in near-neutral pH solution and there is no film formed on the steel surface. Hydrogen evolution is inhibited by anodic polarization of the steel, which is attributed to the alternation of hydrogen evolution mechanism and kinetics on the anodially polarized steel. Combined with slow strain rate tensile tests, it is found that the high susceptibility of steel to stress corrosion cracking (SCC) is always associated with a high hydrogen permeation current. A thermodynamic model was developed, by analyzing the change in free-energy of the steel in the presence and absence of hydrogen and stress, to determine the interactions of hydrogen, stress and anodic dissolution at the crack-tip. The role of hydrogen involvement in pipeline near-neutral pH SCC could be determined quantitatively by characterizing the effect of hydrogen concentration on the dissolution rate of steel and the synergism of hydrogen and stress to promote crack growth.

Analysis of electrochemical hydrogen permeation through X-65 pipeline steel and its implications on pipeline stress corrosion cracking

Electrochemical hydrogen permeation tests were performed to measure the hydrogen permeation current through the X-65 pipeline steel in the electrolytes simulating the soil conditions to initiate near-neutral pH stress corrosion cracking (SCC) in pipelines. The hydrogen permeation current was analyzed following the constant concentration model. It is shown that, AQDS, simulating the organic compound in the soil, inhibits hydrogen permeation by decreasing the sub-surface hydrogen concentration, while sulfide promotes hydrogen permeation by inhibiting the hydrogen recombination and thus increasing the sub-surface hydrogen concentration. The steel specimen is more susceptible to stress corrosion cracking in the soil solution with a higher sub-surface hydrogen concentration, indicating that hydrogen is involved in near-neutral pH SCC in pipelines. It is suggested that hydrogen promotes the cracking of the steel, accompanying with the anodic dissolution on the crack sides and at the crack tip.

Microstructural effect on near-neutral pH stress corrosion cracking resistance of pipeline steels

Microstructural effect on near-neutral pH stress corrosion cracking resistance of pipeline steels

Relationship between Yield Strength and Near-Neutral pH Stress Corrosion Cracking Resistance of Pipeline Steels—An Effect of Microstructure

Abstract In this paper the relationship between the near-neutral pH stress corrosion cracking (SCC) resistance and the yield strength of pipeline steels was investigated and an attempt was made to ...

Corrosion Fatigue and Near-Neutral pH Stress Corrosion Cracking of Pipeline Steel and the Effect of Hydrogen Sulfide

Abstract Crack advance has been studied in an X-70 pipeline steel, using the compliance technique. The electrolyte used in the study was a very dilute brine bubbled with 10% carbon dioxide (CO2). C...

Environmental aspects of near-neutral pH stress corrosion cracking of pipeline steel

The severity of four different soil environments toward the development of near-neutral pH stress corrosion cracking (SCC) of pipeline steel was evaluated using slow strain-rate testing (SSRT). These soils were collected from pipeline sites where near-neutral pH SCC has been observed. It was demonstrated in this investigation that SSRT can differentiate the severity of various soil electrolytes to near-neutral pH SCC. For different soils, the relative susceptibility was found to be determined by the pH values of the soil electrolytes in equilibrium with a given CO2/N2 gas mixture. The higher the pH value up to ∼7, the more conducive the soil electrolyte was to near-neutral pH SCC. The pH value in a soil electrolyte was found to depend on the level of CO2 in the soil solution and the initial HCO3− concentration before the introduction of CO2. For a given soil, the susceptibility depends on the actual level of CO2 in the soil electrolyte. Higher levels of CO2 lower the pH in the soil electrolyte and tend to increase the susceptibility to SCC. In laboratory tests, cathodic polarization was found to increase the susceptibility to failure, possibly by inhibiting general corrosion, which otherwise removed discrete stress-raising pits and defects from the specimen surface that acted as crack initiation sites or by increasing the extent of hydrogen-induced crack initiation or propagation. In the field, cathodic polarization is likely to prevent near-neutral pH SCC by increasing the pH at the pipe surface to values greater than 7.5. The pH was maintained near-neutral in the lab tests by continuous purging of the test solution with CO2/N2. A method is proposed for assessing the relative aggressiveness of various soil extracts to near-neutral pH SCC. Aggressive soil extracts appear to exhibit a narrower variation in pH between solutions purged with N2 and with CO2 than that for less-aggressive soil extracts purged with the same gases.

Mechanisms of High-pH and Near-Neutral-pH SCC of Underground Pipelines

This paper provides an overview of mechanisms for high-pH and near-neutral pH stress corrosion cracking of underground pipelines. Characteristics and historical information on both forms of cracking are discussed. This information is then used to support proposed mechanisms for crack initiation and growth.