SVET, AFM and AES study of pitting corrosion initiated on MnS inclusions by microinjection

Vuillemin, Bruno; Philippe, X.; Oltra, R.; Vignal, V.; Coudreuse, L.; Dufour, Louis-Claude; Finot, Éric

doi:10.1016/s0010-938x(02)00222-6

Cited by 139 publications

(69 citation statements)

References 20 publications

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“…Evidence for a galvanic couple between a noble (cathodic) MnS and active (anodic) SS at the boundary has been presented by Vuillemin as well as Vignal. 22,33 In those works, MnS inclusions in SS 316 were investigated using the scanning vibrating electrode technique. Prior to local injection of HCl at the inclusion site, no current was detected over MnS inclusion.…”

Section: Discussionmentioning

confidence: 99%

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Pit Propagation at the Boundary between Manganese Sulfide Inclusions and Austenitic Stainless Steel 303 and the Role of Copper

Lillard

Kashfipour

Niu

2016

J. Electrochem. Soc.

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Pitting corrosion around manganese sulfide (MnS) inclusions in stainless steel 303 (SS 303) were investigated using in situ Atomic Force Microscopy (AFM), Scanning Kelvin Probe Force Microscopy (SKPFM) and Scanning Electron Microscopy. In situ AFM experiments in 0.1 M sodium chloride solution at voltages near the pitting potential combined with post immersion energy dispersive X-ray spectroscopy (EDS) found copper (Cu) deposition on MnS inclusions but no pitting corrosion. SKPFM images before and after Cu deposition found that Cu ennobled the inclusion. Damage evolution at MnS inclusions was imaged in real-time with AFM at an applied anodic potential. During pit propagation the MnS inclusion remained "passivated" while a trench formed in the bulk SS 303 at the MnS/SS boundary. Focused Ion Beam (FIB) cross sectioning of trenches after this immersion period found no damage to the MnS and Cu deposition on the portion of the inclusion that was inside the trench. FIB images of unexposed samples found preexisting sub-surface trenches at MnS inclusions below the plastic deformation zone at the surface. From these results a proposed mechanism of corrosion propagation at the MnS / SS boundary is described. Over the course of the past century corrosion pits in austenitic stainless steels have been associated with manganese sulfide (MnS) inclusions. An excellent review of the early work in this area has been provided by Wranglen.1 It was proposed that MnS inclusions oxidized preferentially as they were ". . . less noble then the surrounding oxide film, and then [the oxidation] spreads to the active metal below the sulfide inclusions." The model also discussed the sulfur species that may be produced during MnS oxidation including sulfide (S 2− , HS − ), sulfite (SO 3 2− ) and sulfate (SO 4 2− ). As it relates to those species, Wranglen argued that the electrochemical oxidation of sulfur to sulfite produced local acidity. To the contrary, Eklund argued that local acidity was produced from the electrochemical oxidation of sulfide to sulfate. 2More recently, Stewart and Williams, in a metastable pitting study, proposed that MnS dissolution and the corresponding "supply of sulfur to the active pit surface" was a critical step for pit stability.3 They showed that laser re-melting of the surface greatly reduced metastable activity and pitting damage. Thus, larger MnS inclusions could supply sufficient S to maintain pit stability while smaller inclusions could not. Similar conclusions were drawn by Searson and Latanison for rapidly solidified SS 303. 4 Later work by Williams focused on the formation of a critical pitting solution at the site of inclusions as the trigger for pitting corrosion.5 It was proposed that the high dissolution rate of MnS inclusions resulted in the formation of a "sulfur crust" over the inclusion that concentrated chloride underneath it by electromigration. The result was the formation of an occluded environment in which stainless steel depassivates. Early work by Webb and Alkire proposed that the sulfide ...

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Section: Discussionmentioning

confidence: 99%

“…22 In this pre-treatment the sample was prepared, polished and cleaned in the same manner. However, prior to immersion in 0.1 M NaCl the sample it was exposed at the OCP for four hours to a 1 M NaCl solution that was acidified with HCl to pH 3.…”

Section: Cu Deposition Onmentioning

confidence: 99%

Pit Propagation at the Boundary between Manganese Sulfide Inclusions and Austenitic Stainless Steel 303 and the Role of Copper

Lillard

Kashfipour

Niu

2016

J. Electrochem. Soc.

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“…It consisted of measuring the potential distribution in solution with a Luggin capillary at different positions along the electrode surface, and it was successfully applied over the passing years for mapping heterogeneities during corrosion processes [9][10][11]. The scanning-vibrating-electrode technique (SVET), first developed for in situ monitoring of the steady-state current density near individual living cells by Jaffe and Nuccitelli [12], was also well-suited for studying corroding interfaces [13][14][15][16][17]. It is based on the use of a single microelectrode which is vibrated in one or two directions across the sample surface, allowing the potential gradient to be measured accurately with a lock-in amplifier referenced to the probe-vibration frequency [5,12].…”

Section: Introductionmentioning

confidence: 99%

Local electrochemical impedance spectroscopy: A review and some recent developments

Huang

Orazem

et al. 2011

Electrochimica Acta

100

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a b s t r a c tLocal electrochemical impedance spectroscopy (LEIS), which provides a powerful tool for exploration of electrode heterogeneity, has its roots in the development of electrochemical techniques employing scanning of microelectrodes. The historical development of local impedance spectroscopy measurements is reviewed, and guidelines are presented for implementation of LEIS. The factors which control the limiting spatial resolution of the technique are identified. The mathematical foundation for the technique is reviewed, including definitions of interfacial and local Ohmic impedances on both local and global scales. Experimental results for the reduction of ferricyanide show the correspondence between local and global impedances. Simulations for a single Faradaic reaction on a disk electrode embedded in an insulator are used to show that the Ohmic contribution, traditionally considered to be a real value, can have complex character in certain frequency ranges.

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“…Microbiologically-influenced corrosion may intensify the corrosion conditions within pits [17] and pit initiation and progression may be influenced by microstructure arrangement and by internal mechanical strain issues [19]. Under anoxic conditions, smooth steel surfaces with MnS present require chlorides to drive the autocatalytic reaction [20].…”

Section: Mns`2hmentioning

confidence: 99%

A Conceptual Model for the Interaction between Carbon Content and Manganese Sulphide Inclusions in the Short-Term Seawater Corrosion of Low Carbon Steel

Melchers

Chaves

Jeffrey

2016

Metals

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Abstract:The critical role of manganese sulphide (MnS) inclusions for the initiation of the short-term growth of pitting or localized corrosion of low carbon steels has long been recognized. Classical results show that pitting probability and pitting severity increases with increased sulphide concentration for low carbon steels as a result of magnesium sulphides acting as local cathodes for initiating pitting corrosion. However, the iron carbides (cementite) in steels can also act as local cathodes for initiation of pitting corrosion. Herein it is proposed that there is competition between pits for cathodic area and that this will determine the severity of pitting and general corrosion observed in extended exposures. Preliminary experimental data for immersion exposures of up to 56 days in natural seawater of three low carbon steels show, contrary to conventional wisdom, greater pit depths for the steels with lower S content. However, the pit depth results are consistent with lower C/S ratios. This is considered to support the concept of cathodic competition between C and S. It is proposed that this offers explanations for a number of other phenomena, including the thus far unexplained apparently higher reactivity of some MnS inclusions.

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SVET, AFM and AES study of pitting corrosion initiated on MnS inclusions by microinjection

Cited by 139 publications

References 20 publications

Pit Propagation at the Boundary between Manganese Sulfide Inclusions and Austenitic Stainless Steel 303 and the Role of Copper

Pit Propagation at the Boundary between Manganese Sulfide Inclusions and Austenitic Stainless Steel 303 and the Role of Copper

Local electrochemical impedance spectroscopy: A review and some recent developments

A Conceptual Model for the Interaction between Carbon Content and Manganese Sulphide Inclusions in the Short-Term Seawater Corrosion of Low Carbon Steel

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