Stress corrosion cracking of X65 pipeline steel in fuel grade ethanol environments

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Goodman, Lindsey R.
Singh, Preet M.
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In recent years, the demand for alternatives to fossil fuels has risen dramatically, and ethanol fuel has become an important liquid fuel alternative globally. The most efficient mode of transportation of petroleum-based fuel is via pipelines, and due to the 300% increase in ethanol use in the U.S. in the past decade, a similar method of conveyance must be adopted for ethanol. Low-carbon, low-alloy pipeline steels like X52, X60, and X65 comprise the existing fuel transmission pipeline infrastructure. However, similar carbon steels, used in the ethanol processing and production industry, were found to exhibit stress corrosion cracking (SCC) in ethanol service. Prior work has shown that contaminants absorbed by the ethanol during distillation, processing or transport could be the possible determinants of SCC susceptibility; 200 proof ethanol alone was shown not to cause SCC in laboratory studies. To ensure the safety and integrity of the pipeline system, it was necessary to perform a mechanistic study of SCC of pipeline steel in fuel grade ethanol (FGE). The objective of this work was to determine the environmental factors relating to SCC of X65 steel in fuel grade ethanol (FGE) environments. To accomplish this, a systematic study was done to test effects of FGE feedstock and common contaminants and constituents such as water, chloride, dissolved oxygen, and organic acids on SCC behavior of an X65 pipeline steel. Slow strain rate tests (SSRT) were employed to evaluate and compare specific constituents' effects on crack density, morphology, and severity of SCC of X65 in FGE. SCC did not occur in commercial FGE environments, regardless of the ethanol feedstock. In both FGE and simulated fuel grade ethanol (SFGE), SCC of carbon steel was found to occur at low water contents (below 5 vol%) when chloride was present above a specific threshold quantity. Cl- threshold for SCC varied from 10ppm in FGE to approximately 1 ppm in SFGE. SCC of carbon steel was inhibited when oxygen was removed from solution via N2 purge or pHe was increased by addition of NaOH. During SSRT, in-situ¬ electrochemical measurements showed a significant role of film rupture in the SCC mechanism. Analysis of repassivation kinetics in mechanical scratch tests revealed a large initial anodic dissolution current spike in SCC-causing environments, followed by repassivation indicated by current transient decay. In the deaerated environments, repassivation did not occur, while in alkaline SFGE repassivation was significantly more rapid than in SCC-inducing SFGE. Composition and morphology of the passive film on X65 during static exposure tests was studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Results showed stability of an air-formed native oxide under static immersion in neutral (pHe = 5.4) SFGE, and dissolution of the film when pHe was decreased to 4.3. XPS spectra indicated changes in film composition at high pHe (near 13) and in environments lacking sufficient water. In light of all results, a film-rupture anodic-dissolution mechanism is proposed in which local plastic strains facilitates local breakdown of the air-formed oxide film, causing iron to dissolve anodically. During crack propagation anodic dissolution occurs at the crack tip while crack walls repassivate preserving crack geometry and local stress concentration at the tip. It is also proposed that SCC can be mitigated by use of alkaline inhibitors that speed repassivation and promotes formation of a more protective Fe(OH)3 film.
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