Vincent Vignal

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

As pitting is a random phenomenon, it is difficult to predict where a pit will appear on the surface and consequently the use of local probes is rendered difficult. In this work, a new method to study pitting corrosion on a MnS inclusion on 316L stainless steel is proposed. It consists in modifying locally the chemistry in its vicinity by injecting with a microcapillary an aggressive solution of NaCl, H2SO4 or HCl. Once a pit appears, scanning vibrating electrode technique (SVET) is used to follow the current fluctuations over and around the pit when the metal is polarized at a passive potential. In another series of experiments the effect of local activation of MnS inclusion was studied ex-situ using Auger electron spectroscopy (AES) and atomic force microscopy. It is observed that a single pit can be initiated only when hydrochloric acid is injected, whereas sulphuric acid only partially dissolved the inclusion. On another hand, the surface morphology is not affected when a sodium chloride solution is injected. A significant enrichment in sulphur is detected around the inclusion by AES, and micropits are observed in the metal at the edge of the inclusion after HCl activation. Anodic zones are detected by SVET around the inclusion, whereas a cathodic current flows from the inclusion. The anodic current is clearly ascribed to the breakdown of passivity induced by adsorbed sulphur coming from the MnS dissolution, whereas various assumptions can be proposed for the origin of the cathodic current.

Analogy between the effects of a mechanical and chemical perturbation on the conductivity of passive films

Abstract In order to study the passivity breakdown of a type 316L stainless steel, the electrochemical impedance and surface stresses were measured under straining conditions. The Mott–Schottky analysis, performed at high frequency, appears as very useful method to study, below the apparent yield strength, the effects of a mechanical stress on the capacitance values. The results obtained in sodium chloride media indicate that the semiconducting properties of passive films formed in a tensile stress field reflect a higher vacancies concentration than those formed in a stress-free state, suggesting that the passive film conductivity is increased. It was also shown that the Mott–Schottky plots drop in the presence of tensile surface stresses, indicating that the passive film composition may be different from that formed in the presence of compressive surface stresses. A comparison between the effects of mechanical stresses and those of chloride is proposed.

Influence of the Chemical Dissolution of MnS Inclusions on the Electrochemical Behavior of Stainless Steels

Immersion of stainless steel containing a well-controlled density of MnS inclusions in 1 M NaCI, pH 3 leads to the chemical dissolution of these heterogeneities. This process was studied using in situ atomic force microscopy and the dissolution rate of MnS inclusions was estimated between 0.01 and 0.19 μm 3 /min. The effects of MnS dissolution on the chemical composition and the local electrochemical behavior of the specimen surface were investigated using secondary ion mass spectroscopy, X-ray photoemission spectroscopy, and the electrochemical microcell technique. It was shown that stable CrS and unstable FeSO 4 were formed. The size of the areas around MnS inclusions affected by the presence of sulfur-containing species depends on the immersion time and the composition of the native film. The local electrochemical measurements reveal that the chemical dissolution of MnS inclusions promotes pitting corrosion in the surrounding grains at moderate applied potentials for short immersion time and general corrosion of the whole specimen surface for long immersion time.

A mechanical-electrochemical approach for the determination of precursor sites for pitting corrosion at the microscale

The influence of metallurgical defects and residual surface stresses generated by polishing on the pitting susceptibility of duplex stainless steels was studied by combining macro- and microelectrochemical measurements with thermal-mechanical simulation and metallography tests. It has been shown that pits initiate in both phases at metallurgical point defects (such as oxide inclusions in the ferrite and dislocation lines in the austenite). By contrast, the surface stress state was the driving force for pit initiation along the austenite/ferrite interface. Experiments at the macroscale revealed that this process represents about 40% of the total number of pits observed. It has been demonstrated that the local stress gradient was the key-parameter in pit initiation and that the local average stress was the parameter governing the transition from metastable to stable pitting.

Macroscopic and Local Electrochemical Studies of Austempered Ductile Iron in Perchlorate Solutions

The corrosion behavior of austempered ductile iron (ADI) in alkaline environment has been investigated at the microscale by means of the electrochemical microcell technique, surface analysis methods, and at the macroscale using classical electrochemical techniques. Local electrochemical investigations have revealed that the matrix (ausferrite), far from spheres, undergoes passivation in 1 M NaClO 4 , pH 10 solution within a wide potential range, from the corrosion potential (of about -280 mV/SCE) until 800 mV/SCE. Surface observations combined with local electrochemical analysis have shown that corrosion of ADI first occurs in the close vicinity of some graphite spheres and then around oxide inclusions. The oxidized regions are richer in oxygen than the matrix located far from spheres. X-ray photoelectron spectroscopy analysis has revealed that the electrochemical dissolution of ADI in 1 M NaClO 4 , pH 10, leads to the formation of corrosion products containing mainly iron oxides and hydroxide.

Laser shock processing with two different laser sources on 2050‐T8 aluminum alloy

Purpose – The purpose of this paper is to conduct a comparative study of the surface modifications induced by two different lasers on a 2050‐T8 aluminum alloy, with a specific consideration of residual stress and work‐hardening levels.Design/methodology/approach – Two lasers have been used for Laser shock peening (LSP) treatment in water‐confined regime: a Continuum Powerlite Plus laser, operating at 0.532 mm with 9 ns laser pulses, and near 1.5mm spot diameters; a new generation Gaia‐R Thales laser delivering 10 J‐10 ns impacts, with 4‐6mm homogeneous laser spots at 1.06 mm. Surface deformation, work‐hardening levels and residual stresses were analyzed for both LSP conditions. Residual stresses were compared with numerical simulations using a 3D finite element (FE) model, starting with the validation of surface deformations induced by a single laser impact.Findings – Similar surface deformations and work‐hardening levels, but relatively lower residual stresses were obtained with the new large 4‐6 mm impa...

High spatial resolution strain measurements at the surface of duplex stainless steels

The determination of local strain fields at the surface of materials is of major importance for understanding their reactivity. In the present paper, lithography is used to fabricate grid points at the microscale and to map strain gradients within grains and between grains. This method was applied to duplex stainless steels which exhibit heterogeneous strain distributions under straining conditions. The influence of various parameters (the specimen microstructure, the density of slip bands, the number of systems activated and the grid geometry) on the strain value is discussed.

Formation of surface roughness on nanocrystalline aluminium samples under straining by molecular dynamics studies

The surface roughening of nanocrystalline aluminium samples was investigated by molecular dynamics simulations. Attention was focused on the fact that roughness increases with the grain size and the strain. The elastic–plastic transition was found at around 3.5% strain and a reverse Hall–Petch effect was observed under straining conditions. Then, different strain distributions in grains and grain boundaries at the sample surface were highlighted, yielding to the formation of local roughness. Finally, a linear relationship between the magnitude of roughness and the out-of-plane strain component was found.

Kinetics of Sigma Phase Precipitation in Niobium-Stabilized Austenitic Stainless Steel and Effect on the Mechanical Properties

Stabilized austenitic stainless steels are widely used in nuclear and oil industries. The 316 Nb steel grade presented in this study holds a small amount of delta ferrite in the austenitic matrix which tends to transform into sigma phase during prolonged exposures in the temperature range of 600-1000°C. Sigma phase is promoted by ferritic elements such as chromium, molybdenum, niobium and silicon. Time-Temperature-Transformation (TTT) diagram of the δ-ferrite evolution is established thanks to DSC experiments and quantitative metallographic analysis. It is observed that the highest sigma phase formation rate occurs between 800 and 900°C, and that the transformation of ferrite begins after a few minutes of exposure in this temperature range. The microstructure of transformed δ-ferrite is mostly dominated by the eutectoid mixture σ + γ2. Tensile tests were performed for three different cooling conditions: a significant embrittlement attributed to the δ-ferrite transformation is measured by a ductility loss for the lowest cooling rate.

Influence of surface preparation and microstructure on the passivity and corrosion behaviour of duplex stainless steels

The influence of various surface preparation methods (mechanical polishing, electropolishing and etching) on the passivity and the corrosion behaviour of a duplex stainless steel (UNS S32202) was studied using Auger spectroscopy and the electrochemical microcell technique. From surface analyses, the thickness and chemical compositions (ratios Cr/Fe and O2−/OH−, distribution of chloride and nitrogen) were determined. The corrosion behaviour of samples was investigated from local polarization curves. The presence of oxidation peaks and stable pitting was discussed considering the specimen microstructure and the properties of the passive film.