The effect of sulfide on the aerobic corrosion of carbon steel in near-neutral pH saline solutions

Sherar, B.W.A.; Keech, Peter G.; Shoesmith, David W.

doi:10.1016/j.corsci.2012.09.027

Cited by 29 publications

(19 citation statements)

References 30 publications

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“…Peak shifts in the Raman spectrum observed after exposure to oxygen have been interpreted as indication of a partial further oxidation of the initially formed mackinawite to a product containing a fraction of Fe III (reaction 2). 29,51,52 From here onward, further oxidation was different depending on whether it took place in the presence or absence of a thin electrolyte film. In the presence of an electrolyte film, the iron(III) oxide hydroxide akaganeite, FeOOH, formed during exposure to air (reaction 3), which transformed by laser heating to hematite, Fe 2 O 3 (reaction 4).…”

Section: Resultsmentioning

confidence: 99%

“…The characteristic B 1g mode of the Fe sublattice changes slightly in position, which may be attributed to partial oxidation with time. 29,51,52 If the reasoning in the previous paragraph is correct, strong restructuring occurs in the S sublattice of mackinawite over time.…”

Section: Resultsmentioning

confidence: 99%

“…Collected spectra showed a good agreement with the database Raman spectrum of mackinawite, 19,50 but distinct disagreement with data from other authors was found. 29,49,51,52 Due to the lack of availability of a normal mode analysis for mackinawite, no detailed interpretation of the Raman data was possible. Recently, a study by density functional theory (DFT) became available, which reported computed vibrational spectra of mackinawite.…”

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confidence: 99%

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Raman Spectroscopy of Mackinawite FeS in Anodic Iron Sulfide Corrosion Products

Genchev

Erbe

2016

J. Electrochem. Soc.

119

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Raman spectroscopy in a confocal microscope was used to study electrochemically synthesized corrosion products from sour gas experiments. When exposed to oxygen-containing atmosphere, the initial mackinawite FeS corrosion product transformed under laser irradiation to hematite, Fe 2 O 3 . Measurements with a thin water layer on top of the corrosion products prevented the transformation, as drying was prevented. In situ Raman measurements of mackinawite formation avoided the problem of transformation completely. In situ and operando, the initially formed mackinawite showed two Raman peaks in the wavenumber range >180 cm −1 centered around 200-215 cm −1 and 285-300 cm −1 . On an empirical basis, these modes were assigned to a B 1g mode of the iron sublattice and an A 1g mode of the sulfur sublattice, respectively. A comparison with a literature assignment for aged mackinawite suggests that the aging observed involves significant changes in the sulfur sublattice. Corrosion of iron in H 2 S containing solutions is a general problem in crude oil and natural gas production, and is generally referred to as sour corrosion. Aqueous H 2 S solutions promote corrosion of steels, [1][2][3] but the exact nature and mechanisms of corrosion strongly depend on the reaction conditions. 4-7 While the process has been widely investigated for pure iron, [8][9][10][11][12] and carbon steels, [13][14][15][16][17] there is still a lack of understanding of the reaction path and electronic properties of the corrosion products. 18,19The chemistry of the corrosion products formed during H 2 Striggered corrosion is rather complex, as there are many different solids consisting only of iron and sulfur. 20 However, mackinawite has been found to be the initial, 8,21 and probably most important corrosion product, of iron in aqueous sulfide solutions as it was observed in reactions carried out over a wide range of pH and temperature. 11,19,[22][23][24] It possesses a tetragonal, layered crystal structure, [25][26][27] and can be synthesized by precipitation from solutions containing Fe 2+ and S 2− solutions, 28,29 or by reaction of sulfide solution with metallic iron. 19,21,26,30 In the field of microbially induced corrosion, sulfatereducing bacteria are known to transform sulfate compounds into iron sulfides, e.g. mackinawite. [31][32][33][34][35][36] Raman spectroscopy has become an important tool for identification of corrosion products. [37][38][39][40][41][42][43][44][45] Some major problems may still occur due to laser heating, fluorescence, or low sensitivity as a consequence of the small cross-sections of Raman scattering. However, the fact that glass and water are both very weak Raman scatterers makes this technique suitable for in situ measurements in aqueous environments. 46-48The presence of water has an additional positive effect on the process as it decreases the heating from the laser. The use of (in situ and operando) Raman spectroscopy for study corrosion process studies of iron in sulfide rich environments has been already repor...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

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Raman Spectroscopy of Mackinawite FeS in Anodic Iron Sulfide Corrosion Products

Genchev

Erbe

2016

J. Electrochem. Soc.

119

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“…The effect of any individual parameter on corrosion rate has been studied extensively [3][4][5][6]. But the conjoint effect of the above mentioned parameters and interfering effects and interactions are complex and are not very well understood.…”

Section: Introductionmentioning

confidence: 99%

Corrosion Behavior of Carbon Steel in Synthetically Produced Oil Field Seawater

Paul

Pattanayak

Guchhait

2014

International Journal of Metals

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The life of offshore steel structure in the oil production units is decided by the huge corrosive degradation due to SO42-, S2−, and Cl−, which normally present in the oil field seawater. Variation in pH and temperature further adds to the rate of degradation on steel. Corrosion behavior of mild steel is investigated through polarization, EIS, XRD, and optical and SEM microscopy. The effect of all 3 species is huge material degradation with FeSx and FeCl3 and their complex as corrosion products. EIS data match the model of Randle circuit with Warburg resistance. Addition of more corrosion species decreases impedance and increases capacitance values of the Randle circuit at the interface. The attack is found to be at the grain boundary as well as grain body with very prominent sulphide corrosion crack.

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“…In this case, the generation of sulfide by SRB could be the limiting factor, fitting in with the narrative of microbially enhanced corrosion. It is now well understood that sulfides enhance corrosion; this is thought to occur by catalysis of the surface reaction (Sherar, Keech and Shoesmith, 2013), rather than by a thermodynamic shift in the potential, providing a clear explanation of the role of SRB on the surface.…”

Section: Introductionmentioning

confidence: 99%

Mathematical modelling of electron transfer modes in electroactive microorganisms

Fischer¹

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Electroactive microorganisms (EAMs) are known to function in a variety of systems, and receive strong focus in scientific investigation; microbial fuel cells (MFCs) and microbial electrolysis cells (MECs) are two key fields utilising these microorganisms to date. Microbially influenced corrosion (MIC) and the conduction of filamentous bacteria in ocean sediments also make use of external electrical currents to enable growth in what otherwise may be an abiotic environment. With the discovery of more of these systems and a growing understanding of their relevance over the past couple of decades, research into them has been steadily increasing. Electrochemical techniques such as cyclic voltammetry and impedance analysis have been used to gain a greater understanding of the system. However, mechanistic model-based analysis has lagged behind, with the fundamentals and consequences of electron transfer still not fully understood. Mechanistic investigation is vital for the progression and furthering of related research, and for highlighting the interactions occurring within EAMs, as many processes occur at a level that cannot be resolved by experimental systems. While a number of models have described extracellular electron transfer, in particular, for MFCs, none have analysed short-range electrontransfer mechanisms on a comparative basis. This thesis uses common finiteelement and electrochemical diffusive-reactive modelling techniques to investigate electroactive organisms in highly diverse environments. One such system is a filamentous sulfide-oxidising system in ocean sediment. Filamentous bacteria grow between sulfide-rich and oxygen-rich regions, transferring electrons between selfdetermined anodic and cathodic zones. Splitting of the metabolic pathway between partners allows growth to be determined thermodynamically rather than empirically, with bacteria releasing or consuming electrons depending upon the available substrate. This modelling approach determined that the bacteria, while electroactive, cannot grow with the rates seen experimentally, and highlighted that the current conceptual picture is incomplete. A similar approach is used to investigate microbially influenced corrosion, showing that direct electrical uptake greatly exacerbates corrosion when compared to a purely chemical system, due to the shifting of the electrical potential of the metal and the subsequent increase in electrochemical rates. This model of corrosion rates in carbon steel showed the variability with changing environmental conditions and bacterial activity, ranging from ii as little as 0.05 mm/yr to a very significant 1.5 mm/yr with highly aggressive biofilms.

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The effect of sulfide on the aerobic corrosion of carbon steel in near-neutral pH saline solutions

Cited by 29 publications

References 30 publications

Raman Spectroscopy of Mackinawite FeS in Anodic Iron Sulfide Corrosion Products

Raman Spectroscopy of Mackinawite FeS in Anodic Iron Sulfide Corrosion Products

Corrosion Behavior of Carbon Steel in Synthetically Produced Oil Field Seawater

Mathematical modelling of electron transfer modes in electroactive microorganisms

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