Numerical modelling of the electrochemical behaviour of 316L stainless steel based upon static and dynamic experimental microcapillary-based techniques

Microcapillary-based techniques allow the selection and interrogation of single metallurgical sites and are therefore becoming increasingly popular to investigate the electrochemical behaviour of metallic phases and non-metallic heterogeneities in alloys. This study has been carried out to assess the differences between current measurements made using a 'closed' microcapillary system (the electrochemical microcell technique) with current measurements derived from a flowing 'open' microcapillary droplet cell (the scanning droplet cell). The experimental results were compared with calculations derived from a model system adopting a finite element approach. The corrosion system consists of fou…

Influence of an elastic stress on the conductivity of passive films

Abstract The electrochemical impedance was measured over a large range of frequency and under straining condition in sodium chloride solution. The Mott-Schottky analysis, performed at high frequency, appears as very useful method to study the effect of an elastic stress on the capacitance values. The results obtained indicate that the semi-conductive properties of passive films formed on a type 316 L stainless steel (SS) are not markedly modified by an elastic stress when applied after ageing. In contrast, passive films formed in the presence of elastic stress have a higher donor and acceptor concentration than those formed in a stress-free state, suggesting that the passive film conductivi…

Impact of Superfinish Turning on Surface Integrity of Pure Copper

Abstract The presented study deals with comprehension of relationships between machining cutting conditions and physical-chemical properties linked with surface integrity. A multi-physics model is presented to calculate residual stress, temperature and dislocation fields in the machined material. This model includes both thermal-mechanical, structural evolution and dynamic recristallisation approaches. The model was applied to pure copper after superfinish turning. Good agreement was found between numerical values and experimental ones. This paper also presents a work on the impact of mechanical and microstructural changes induced by machining on the electrochemical behaviour and corrosion …

Analysis of laser shock waves and resulting surface deformations in an Al-Cu-Li aluminium alloy

Abstract Laser shock processing is now a recognized surface treatment for improving fatigue or corrosion behaviour of metallic materials through the generation of a compressive stress field. In turn, the analysis of shock wave propagation is of primary importance to predict numerically morphological and mechanical surface modifications. Considering experimental and numerical analyses of shock wave propagation, and surface deformations induced by single impacts, a 2050 aluminum alloy having different microstructures was investigated under laser-shock loading. In a first step, the evolution of shock wave attenuation and elastic precursor amplitude was correctly reproduced by finite element si…

Relationships between strain, microstructure and oxide growth at the nano- and microscale

In the present article, the relationships between oxidation processes, surface strains and the microstructure of duplex stainless steels were investigated. Specimens were oxidized at 500 °C under secondary vacuum for 1 h to form a thin oxide film (thickness in the range of 20-50 nm). Such specimens were considered as the model system for developing novel methods of analysis in understanding the behavior of passive films. The interfacial strain field after oxidation was measured experimentally at the microscale using the point grid method. On the other hand, the chemical composition of the oxide film was determined at the submicroscopic scale by means of local scanning Auger spectroscopy (wi…

Influence of friction on the local mechanical and electrochemical behaviour of duplex stainless steels.

International audience; The electrochemical behaviour of ferritic and austenitic phases in duplex stainless steel (UNS S32304) and the modifications induced by straining during sliding were studied by potentiodynamic polarisation curves determined at the microscale in a 1MNaCl (pH 3) solution, using an electrochemical microcell. The mechanical properties and stress state of each phase were determined by microhardness and X-ray microdiffraction measurements, before and after straining. The results show that sliding generates elastic straining of the ferrite and plastic deformation of the austenite. The electrochemical behaviour of these phases is dramatically altered, inducing a reduction of…

Numerical Studies of the Diffusion Processes and First Step Oxidation in Nickel-Oxygen Systems by Variable Charge Molecular Dynamics

Variable charge molecular dynamic simulations have been performed to study the diffusion mechanisms of oxygen atoms (O) in nickel (Ni) in the temperature range 950-1600 K and the very first steps of oxidation of monocrystalline nickel surfaces at 300 K and 950 K. The oxygen diffusivity can be well described by an Arrhenius law over the temperature range considered. The oxygen diffusion coefficient has been analysed and values of Ea = 1.99 eV for the activation energy and D0 = 39 cm2.s-1 for the pre-exponential factor were obtained. The first steps growth of the oxide layer show that after the dissociative chemisorption of the oxygen molecules on nickel surface, the oxidation leads to an isl…

Grain size, stress and surface roughness

In this article, we report molecular dynamics (MD) simulations on the formation of roughness at the surface of strained polycrystalline aluminum samples at 300 K. The computed roughness increases as a function of applied strain but does not follow a linear law for all applied strains. A linear relationship with a small slope is obtained in the elastic domain. Then, the roughness increases rapidly with the applied strain in the plastic domain studied. Moreover, the surface roughness increases as a function of grain size (between 5 and 20 nm) in the plastic domain (<6%).

Experimental and Numerical Analysis of the Distribution of Residual Stresses Induced by Laser Shock Peening in a 2050-T8 Aluminium Alloy

Laser shock peening (LSP) is an innovative surface treatment technique successfully applied to improving fatigue performance of metallic material. The specific characteristic of (LSP) is the generation of a low work-hardening and a deep compressive residual stresses mechanically produced by a laser-induced shock wave propagating in the material. The aim of this study is to analyse the residual stress distribution induced by laser peening in 2050-T8 aluminium alloy experimentally by the X-ray diffraction technique (method sin2Y) and numerically, by a finite element numerical modelling. A specific focus was put on the residual stress distribution along the surface of the impacted material.

Impact des conditions d'usinage sur la zone du matériau affectée par le procédé

Colloque avec actes et comité de lecture. Internationale.; International audience; Les procédés d'usinage peuvent créer des contraintes résiduelles à la surface des pièces usinées et ainsi modifier la microstructure et la texture de la matière proche de la surface. De tels changements sont importants pour l'étude du comportement des pièces au cours du temps. Il est alors nécessaire de quantifier les contraintes résiduelles, les composantes de texture et de déterminer la microstructure induite par l'usinage pour comprendre et prédire le comportement des surfaces considérées. Dans cette étude, le matériau cuivre pur a été choisi et considéré comme un "système modèle". En tournage, l'influence…

Corrosion behaviour of galvanized steel studied by electrochemical microprobes applied on low-angle cross sections

Abstract The combined use of the microcapillary cell (MEC) and scanning vibrating electrode technique (SVET) and low-angle cross sections was employed to elucidate the role of each coating region on the protection of the cut-edge corrosion of galvanized steels. Different compounds are involved in the blocking action of the corrosion products: Zincite (ZnO) on the steel substrate, hydrozincite (Zn5(OH)6(CO3)2) at the coating/steel interface, and Simonkolleite (Zn5(OH)8Cl2) and ZnO on the different coating regions in different proportions. The coating surface is also active at the initial stage and during long-term protection and thus, must be considered in experimental simulation of the cut-…

Influence of plastic deformation on the microstructure and corrosion behaviour of Ti–10Mo–4Zr and Ti–6Al–4V alloys in the Ringer’s solution at 37°C

Abstract The influence of plastic deformation on the microstructure and passivity of Ti–6Al–4V and Ti–10Mo–4Zr is studied. The content of titanium-based compounds in the passive film formed on the alloys increases under straining. In the region where necking occurs, the β-phase content drops in Ti–6Al–4V. The grain orientation spread increases with increasing strain. The quality index of EBSD maps is affected on Ti–10Mo–4Zr (dislocation structures along preferential orientations). The corrosion behaviour is investigated in the Ringer’s solution (37 °C). Results obtained in the anodic and cathodic domains are discussed considering changes described previously.

Influence of the Electrochemical Parameters on the Properties of Electroplated Au-Cu Alloys

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…

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

International audience; 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 was discussed.

Use of the electrochemical microcell technique and the SVET for monitoring pitting corrosion at MnS inclusions

The purpose of this paper is to report on use of the electrochemical microcell technique and the scanning vibrating electrode technique for monitoring pitting corrosion on the same stainless steel microstructure. First, the electrochemical behaviour of sites containing a single inclusion was investigated in order to the determine both the successive steps occurring during the inclusions activation and some key-parameters such as the onset potential for MnS dissolution and the pitting potential. Then, the local current distribution around a pitting site was monitored at open circuit potential in order to locate anodic and cathodic regions and to obtain informations on the galvanic coupling b…

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

International audience; The surface roughening of nanocrystalline aluminum 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 samples surface was 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.

Local electrochemical impedance spectroscopy study of the influence of ageing in air and laser shock processing on the micro-electrochemical behaviour of AA2050-T8 aluminium alloy

International audience; In the present paper, the micro-electrochemical behaviour of AA2050-T8 in 0.1 M NaCl was first studied after polishing by means of local electrochemical impedance spectroscopy and field-emission scanning electron microscopy/electron dispersive spectroscopy (FE-SEM/EDS). The influence of ageing in air and LSP was then investigated. Ageing in air for three months led to an increase in the charge transfer resistance. This was clearly observed in sites surrounding constituent particles where the charge transfer resistance was in the order of 1 MΩ cm2 (instead of 10-3 MΩ cm2 after polishing). Increased passivity around particles was confirmed from FE-SEM/EDS analysis. On …

Role of plastic deformation and microstructure in the micro-electrochemical behaviour of Ti–6Al–4V in sodium chloride solution

Abstract The role of alloying elements and the influence of plastic deformation on the micro-electrochemical behaviour and the pitting corrosion susceptibility of TiAl6V4 have been investigated in 10 g/L NaCl using the electrochemical microcell technique. Local electrochemical measurements have revealed that both the increase of surface roughness and the increase of dislocation density have impact on the electrochemical behaviour of TiAl6V4 after plastic deformation. It has been shown the surface roughness induced by slip band emergence is the predominant parameter responsible for the increase of the cathodic current. It has also been shown that cathodic reactions occur preferentially at su…

Friction Model for Tool/Work Material Contact Applied to Surface Integrity Prediction in Orthogonal Cutting Simulation

Abstract Tribological behavior at both tool/chip and tool/work material interfaces should be highly considered while simulating the machining process. In fact, it is no longer accurate to suppose one independent constant friction coefficient at the tool/chip interface, since in reality it depends on the applied contact conditions, including the sliding velocity and pressure. The contact conditions at both above mentioned interfaces may affect the thermal and mechanical phenomena and consequently the surface integrity predictions. In this article, the influence of contact conditions (sliding velocity) on the tribological behavior of uncoated tungsten carbide tool against OFHC copper work mat…

Study of the mechanical effects on passivity breakdown by local probe techniques

This paper aims at demonstrating that a relationship exists between surface stress and pitting corrosion. The surface stress field generated by polishing was first calculated using a thermo-mechanical model and a finite element code. Pitting corrosion tests performed at the microscale along the austenite/ferrite interface using the electrochemical microcell technique were then analyzed considering the microstructure and the residual surface stress field. Mechano-chemical criteria are proposed leading to an enhancement of pitting corrosion of duplex steels.

Stress/strain effects on electrochemical activity: Metallurgical/mechanical/interactions and surface reactivity

Abstract Tribocorrosion is of complex nature as it involves multiscale interactions between mechanical, (electro-)chemical, physical, and material factors. The influence of mechanical stresses/strains on the surface reactivity of metallic alloys is described here. The electrochemical behavior and the corrosion resistance of engineering alloys are discussed in the presence of compressive and tensile stresses through different examples. The role of physical (formation of steps, roughness, microcracks), metallurgical (dislocations, crystallographic texture, and grain size), and chemical (passive film composition) changes induced by plastic deformation on electrochemical behavior and corrosion …

Influence of the microstructure and laser shock processing (LSP) on the corrosion behaviour of the AA2050-T8 aluminium alloy

International audience; The corrosion behaviour of AA2050-T8 was studied after polishing and after laser shock processing (LSP) treatment using the electrochemical microcell technique and the SVET. After polishing, pitting at constituent particles and intergranular corrosion were observed. By contrast, no intergranular corrosion developed after LSP. Microcell measurements revealed that LSP increases the pitting potential. SVET measurements revealed that local anodic currents are systematically lower on LSP-treated surfaces than on polished ones. The current density on the LSP-treated surface remains constant around 50 μA cm−2 up to 123 min after immersion, while on the polished surface it r…

The use of the Pearson’s correlation coefficients to identify mechanical-physical-chemical parameters controlling the tribocorrosion of metallic alloy

Abstract Tribocorrosion is of complex nature as it involves multiscale interactions between mechanical, (electro-)chemical, physical, and material factors. A methodology based on the use of the Pearson’s correlation matrix and local techniques is described here to analyze interactions between these factors. The most influent experimental parameters selected for tribocorrosion tests on the surface/subsurface characteristics and on the corrosion parameters are identified. Correlations between surface/subsurface and corrosion parameters are also analyzed to propose criteria and to understand basic mechanisms of tribocorrosion. This methodology is particularly useful in the case of multiphase m…

Influence of the dissolution of MnS inclusions under free corrosion and potentiostatic conditions on the composition of passive films and the electrochemical behaviour of stainless steels

Abstract The influence of the dissolution of MnS inclusions at the OCP value and 400 mV versus SCE on the chemical composition of passive films and the electrochemical behaviour of resulfurized austenitic stainless steel was studied in 1 M NaClO 4 , pH 3, solution using SIMS, XPS, electrochemical impedance spectroscopy and the electrochemical microcell technique. The electrochemical dissolution (at 400 mV versus SCE) of inclusions occurred uniformly along the interface and this process was almost complete after 25 min immersion. A small amount of sulfur was detected on the matrix that exhibited a wide passive range. By contrast, the dissolution process under free corrosion was not uniform a…

Corrosion behaviour of heavily deformed pearlitic and brass-coated pearlitic steels in sodium chloride solutions

Abstract The influence of plastic deformation and galvanic coupling on the microstructure and corrosion behaviour of pearlitic steel and brass-coated pearlitic steel was investigated in sodium chloride solution at 25 °C. Microstructural changes were quantified using scanning electron microscopy coupled with EBSD. Chemical and electrochemical modifications were evaluated using XPS, ZRA, the electrochemical microcell technique and the weight loss method. From these experiments, the influence of microstructural changes on the electrochemical parameters and the corrosion rate was discussed.

Atomic Structure and Mechanical Behaviour of Passive Film Formed on Stainless Steels

Influence de la composition chimique du film passif et des contraintes résiduelles sur le comportement micro-électrochimique des aciers inoxydables duplex en milieux contenant des ions chlorure

Le comportement micro-electrochimique d’aciers inoxydables duplex a ete determine dans des milieux contenant des chlorures, a l’aide de la technique de la microcellule electrochimique (capillaires de 30 µ m). Les resultats obtenus ont ete analyses en considerant la composition chimique du film passif. Des relations quantitatives entre les parametres electrochimiques et la distribution en chrome et fer dans la couche passive ont ete trouvees. Comme les deux phases ont des proprietes mecaniques differentes, un champ de contraintes residuelles heterogene est genere a la surface de l’alliage. Une methode thermo-mecanique basee sur la simulation numerique par elements finis a ete utilisee pour c…

Determination of elastoplastic properties of TiO2 thin films deposited on dual phase stainless steel using nanoindentation tests

International audience; In recent years, the extraction of mechanical behaviour of thin films by nanoindentation using sharp indenter geometry has been extensively studied. This work investigates the mechanical properties of TiO2 thin film (1 µm thickness) deposited by spin coating on dual phase Duplex stainless steel and glass substrates. Experiments are carried out with different sharp triangular pyramids (a Cube corner and a Berkovich indenter) using a commercial Nano Indenter® XP apparatus. The substrate effect has been counteracted and an inverse method proposed in literature for bulk material has been adapted to assess the elastoplastic parameters of the tested thin film directly from…

Passive properties of lean duplex stainless steels after long-term ageing in air studied using EBSD, AES, XPS and local electrochemical impedance spectroscopy

Abstract Passivity of duplex stainless steel was studied after long-term ageing in air using local electrochemical impedance spectroscopy, AES, XPS and EBSD. After mechanical polishing, the passive film was homogeneous and had a capacitive behaviour described by the CPE. After long-term ageing, a small thickening was detected and O2−/OH− was significantly higher in the austenite than in the ferrite. Austenite behaved as a blocking electrode whereas two capacitive loops were observed in the ferrite (low value of O2−/OH). The loop at high frequencies was related with the oxygen reduction and the loop at low frequencies was connected with the passive film.

Corrosion Behaviour of Ti6Al4V and TiMo10Zr4 Alloys in the Ringer’s Solution: Effect of pH and Plastic Strain

The corrosion behaviour of titanium alloys is not well understood – especially the role of the microstructure and plastic strain. In this paper, the influence of the microstructure and plastic strain on the corrosion resistance of TiMo10Zr4 and Ti6Al4V alloys was studied in the Ringer’s solution at 37 °C. Measurements were performed for different pH values and in aerated and de-aerated solutions using potentiodynamic polarization techniques. Results obtained on the two alloys were compared. It was shown that in the absence of plastic strain TiMo10Zr4 shows better corrosion resistance than Ti6Al4V (especially for pH = 8). By contrast, the current density in the passive range measured after 8…

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 pres…

Influence of residual stress, surface roughness and crystallographic texture induced by machining on the corrosion behaviour of copper in salt-fog atmosphere

International audience; The influence of quadratic stress, crystallographic texture, lubrication and surface roughness generated by superfinish turning on the corrosion behaviour of pure copper was quantified in salt-fog atmosphere. This was done using statistical analysis (Pearson's correlation matrix). Three compounds were found after corrosion tests: atacamite/paratacamite and a black layer (mixture of the lubricant and the salt atmosphere). Surface characteristics were classified according to their decreasing influence on the formation of atacamite/paratacamite as follows: surface roughness and quadratic stress. Lubrication and the crystallographic texture have the lowest influence on c…

A physical-based constitutive model for surface integrity prediction in machining of OFHC copper

International audience; Due to the rising interest in predicting machined surface integrity and sustainability, various models for metal cutting simulation have been developed. However, their accuracy depends deeply on the physical description of the machining process. This study aims to develop an orthogonal cutting model for surface integrity prediction, which includes a physical-based constitutive model of Oxygen Free High Conductivity (OFHC) copper. This constitutive model incorporates the effects of the state of stress and microstructure on the work material behavior, as well as a dislocation density-based model for surface integrity prediction. The coefficients of the constitutive mod…

Parametric study of laser welding of copper to austenitic stainless steel

Abstract Welding of copper to stainless steel is challenging because of sharp difference in thermophysical properties of materials and the presence of miscibility gap in Fe-Cu system. The parametric study of continuous Yb:YAG laser welding between copper and austenitic stainless steel 316L has been performed. The influence of laser power, welding speed and beam offset from joint line on weld composition, microstructure and tensile properties was studied. The corrosion behaviour of the welds was evaluated in 0.1M NaCl with the potentiostatic pulse testing method, salt fog and immersion tests. In function of copper dilution in the melted zone, different types of microstructure were observed: …

Numerical modelling of the electrochemical behaviour of 316 stainless steel based upon static and dynamic experimental microcapillary-based techniques: effect of electrolyte flow and capillary size

objective of this work was to determine the parameters that affect the mass transport and the distribution of species in microcapillaries close to the specimen surface. Local experiments were carried out under static and flow conditions on type 316L stainless steel in 1.7 M NaCl, pH = 3, by means of the electrochemical microcell and the scanning droplet cell technique. The polarisation behaviour of pure iron (used as a model system) in an aqueous environment was calculated adopting a finite element approach and was compared to the experimental results. The corrosion system consists of three parallel electrochemical reactions: the oxygen reduction reaction (ORR), the hydrogen evolution react…

Influence of applied strain on the microstructural corrosion of AlMg2 as-cast aluminium alloy in sodium chloride solution

International audience; The corrosion behavior of ISO AlMg2 (AA5052) was studied at the microscale using the Electrochemical Microcell Technique. The influence of plastic deformation on the corrosion resistance of this alloy was also examined. After polishing, pitting at small copper-enriched precipitates and structural etching were observed. After deformation, numerous slip bands were found in grains. After 5.5% plastic strain, the global electrochemical behavior of samples was significantly affected. Pitting potential was decreased in sites containing slip bands or in sites with large strain gradients (measured using microgauges deposited by lithography).

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…

Local electrochemical impedance measurements on inclusion-containing stainless steels using microcapillary-based techniques

MnS inclusions are good precursor sites for pitting corrosion of stainless steel. The objective of this paper was to quantify the passive properties of resulfurized stainless steel after immersion in chloride media. This was done by combining microcapillary techniques with electrochemical impedance spectroscopy and numerical analysis (specific equivalent circuit). It was shown that sulfur species produced in the electrolyte during the dissolution of inclusions react with the native passive film to CrS and FeSO 4 . Local electrochemical impedance spectroscopy measurements provided data describing the behaviour of the affected matrix at the microscale. For example, the value of the charge tra…

Diffusion of oxygen in nickel: A variable charge molecular dynamics study

Abstract Variable charge molecular dynamics have been performed to study the diffusion mechanisms of oxygen atoms (O) in nickel (Ni) in the temperature range 950 K–1600 K. It is observed that oxygen does not diffuse via jumps of oxygen through interstitial sites but via a vacancy diffusion mechanism. The oxygen diffusivity can be well described by an Arrhenius law over the temperature range considered. The oxygen diffusion coefficient has been analysed and indicates a value of E a = 1.99 eV for the activation energy and D 0 = 39.2 cm 2 s − 1 for the pre-exponential factor. Our numerical results were compared with a compilation of experimental and theoretical studies, and exhibit a good agre…

Phenomenological Model for Gold-Copper Electrodeposition: Application to Thick Coatings

Pure gold-copper alloys are known to be difficult to electrodeposit because of a strong variation in composition after a few microns have been deposited. Commissariat al’Energie Atomique (CEA) stud...

Influence of Plastic Deformation on the Corrosion Behaviour of As-Cast AlMg2 and AlCu4Mg1 Aluminium Alloys in NaCl Solution

The influence of plastic deformation on the corrosion behavior of as-cast AlMg2 and AlCu4Mg1 aluminum alloys was studied at the microscale using the Electrochemical Microcell Technique and surface microgauges. It was shown that large strain gradients develop locally. The corrosion behavior of both alloys was affected by plastic deformation. The most active sites contain large strain gradients in AlMg2 and cracks with damage in the matrix in AlCu4Mg1.

Finite element analysis of laser shock peening of 2050-T8 aluminum alloy

Laser shock processing is a recently developed surface treatment designed to improve the mechanical properties and fatigue performance of materials, by inducing a deep compressive residual stress field. The purpose of this work is to investigate the residual stress distribution induced by laser shock processing in a 2050-T8 aeronautical aluminium alloy with both X-ray diffraction measurements and 3D finite element simulation. The method of X-ray diffraction is extensively used to characterize the crystallographic texture and the residual stress crystalline materials at different scales (macroscopic, mesoscopic and microscopic).Shock loading and materials’ dynamic response are experimentally…

Recent advances in local probe techniques in corrosion research – Analysis of the role of stress on pitting sensitivity

Local probe techniques have been largely applied to predict the spatial distribution of the electrochemical reactions and to quantify the corrosion rate. These local probe techniques are now being developed to capture the temporal information, in-situ and in real-time. Nevertheless only few works have been devoted to investigate with these local probes the role of stress on pitting sensitivity on passive materials. In this paper, a part of the most recent studies based on combination of local electrochemical measurements with finite element mapping of surface stress gradients are reported illustrating the role of inclusions under straining and the mechanical effect of surface preparation on…

Influence of cutting process mechanics on surface integrity and electrochemical behavior of OFHC copper

The authors gratefully acknowledge the support received from IC ARTS and CEA Valduc; International audience; Superfinishing machining has a particular impact on cutting mechanics, surface integrity and local electrochemical behavior. In fact, material removal during this process induces geometrical, mechanical and micro-structural modifications in the machined surface and sub-surface. However, a conventional 3D cutting process is still complex to study in terms of analytical/numerical modeling and experimental process monitoring. So, researchers are wondering if a less intricate configuration such as orthogonal cutting would be able to provide information about surface integrity as close as…

Quenched molecular dynamics studies on the extraction energy of aluminum atoms

The extraction energy of an aluminum atom is calculated at 0 K as a function of coordination number and defect depth for three surface orientations [(100), (110) and (111)]. For each orientation, atoms are selected and extracted one by one. A linear relationship is obtained between the extraction energy of surface atoms and their coordination numbers (with slight variations due to the geometrical configuration of the atoms). However, the study of the influence of the defect depth on the extraction energy highlights the role played by intrinsic stress on the extraction energy. Copyright © 2008 John Wiley & Sons, Ltd.

Oxidation of nanocrystalline aluminum by variable charge molecular dynamics

International audience; We investigate the oxidation of nanocrystalline aluminum surfaces using molecular dynamics (MD) simulations with the variable charge model that allows charge dynamically transfer among atoms. The interaction potential between atoms is described by the electrostatic plus (Es+) potential model, which is composed of an embedded atom method potential and an electrostatic term. The simulations were performed from 300 to 750K on polycrystalline samples with a mean grain size of 5 nanometers. We mainly focused on the effect of the temperature parameter on the oxidation kinetic. The results show that, beyond a first linear regime, the kinetics follow a direct logarithmic law…

Mechanical properties and corrosion behaviour after scratch and tribological tests of electrodeposited Co-Mo/TiO2 nano-composite coatings

International audience; The micro-mechanical (Young’s modulus and hardness) and tribological properties, as well as the scratch resistance of Co-Mo/TiO2 nano-composite coatings were investigated. The coating was found to be harder and stiffer than the substrate (pure cobalt). Low residual stresses were also derived from Stoney’s equation (type I stress). The corrosion behaviour after tribological and scratch tests was studied in Ringer’s solution. Dry sliding of the coating against an alumina ball at the load of 1 N or 2 N over the same distance had nearly no influence onthe anodic branch of the polarisation curves. By contrast, the current density in the cathodic branch (oxygen reduction r…

The use of local electrochemical probes and surface analysis methods to study the electrochemical behaviour and pitting corrosion of stainless steels

Abstract In this paper, the electrochemical microcell technique is combined with ex situ (SIMS and XPS) and in situ (SVET) techniques to study the electrochemical behaviour and pitting corrosion of inclusion-contaning stainless steels. Dissolution of metallurgical heterogeneities, depassivation and pitting mechanisms are first discussed in 1 M NaClO4, pH 3, and 1 M NaCl, pH 3, by considering the chemical composition and morphology of inclusions. The influence of the chemical composition of passive films on the electrochemical reactions and the microgalvanic coupling processes occurring at the corrosion potential is also investigated on the same specimen microstructure.

Study of the Hydrogen Embrittlement Sensitivity of an X4CrNiMo 16.5.1 Stainless Steel and the Associated Electron Beam Weld

X4CrNiMo 16.5.1 steel (commercial name APX4) is a low carbon martensitic stainless steel known for its remarkable mechanical characteristics and its good resistance to corrosion. The use of APX4 in the manufacture of high pressure gas vessels requires a thorough understanding of its resistance to Hydrogen Embrittlement (HE) as the gas can contain traces of hydrogen, and martensitic steels, and their welds, are generally very sensitive to HE. This paper deals with the first part of this study, involving the characterization of the microstructure and the mechanical properties of each zone of the electron beam weld (melted zone and four different heat affected zones), and the investigation of …

Ultra-low density metallic foams synthesized by contact glow discharge electrolysis (CGDE) for laser experiments★

International audience; The goal of this work is to realize metallic foams synthesized by contact glow discharge electrolysis with specific characteristics. In this paper, we show the results of our studies, consisting in investigating parameters that influence the foams characteristics. Thus, the morphology of metallic foams is examined through scanning electron microscopy (SEM) observations with the acid nature. Moreover, the evolution of the mass and the volume of metallic foams with two experimental parameters (overvoltage and gold concentration) is also investigated. The acid nature affects the foams microscopic structure highlighted by the SEM observations, but for now no valid explan…

Influence of the passive film properties and residual stresses on the micro-electrochemical behavior of duplex stainless steels

In the present paper, the chemical composition of passive films formed on both phases of two types of duplex stainless steels (UNS S31803 and UNS S32304) is determined at the micro-scale using Auger electron spectroscopy (AES). Samples were either mechanically polished (down to diamond pastes) or electrochemically etched in acidic solutions. The micro-electrochemical behavior of samples was then determined in sodium chloride media by means of the electrochemical micro-cell technique (capillary diameters of 30 μm). The results obtained were analyzed considering the passive film chemical composition. Quantitative relationships between electrochemical parameters and the distribution of chromiu…

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…

Vers une approche multi-échelle et pluridisciplinaire pour l'étude et la prédiction des processus de corrosion localisée : Aspects expérimentaux et numériques.

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The use of microcapillary techniques to study the corrosion resistance of AZ91 magnesium alloy at the microscale

Abstract The AZ91 alloy is composed of Mg 17 (Al, Zn) 12 precipitates, an eutectic phase around these precipitates, AlMn intermetallic particles and an α-Mg solid solution (matrix). The corrosion behaviour of AZ91 was investigated at the microscale by means of the electrochemical microcell technique, which uses extremely small capillaries (diameters between 5 and 10 μm). Experiments were conducted in 0.1 M NaClO 4 at 25 °C. The β-Mg 17 (Al, Zn) 12 precipitates were found to have the highest corrosion resistance, whereas the eutectic phase was very active (pitting potential of approximately −1400 mV vs. Ag/AgCl). The α-Mg solid solution displayed better corrosion resistance than the eutectic…

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

PurposeThe 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/approachTwo 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 …

Influence of the chemical dissolution of MnS inclusions on the composition of passive films and the local electrochemical behaviour of stainless steels

Abstract Immersion of stainless steel containing MnS inclusions in aqueous electrolytes leads to the chemical dissolution of these heterogeneities. Chemical dissolution of MnS inclusions in 1M NaCl, pH=3 was studied using in-situ AFM and the dissolution rate of MnS was estimated between 0.04 and 0.19 μm 3 /min. The local electrochemical measurements reveal that the chemical dissolution of MnS inclusions promotes pitting corrosion. Similary, chemical dissolution of MnS inclusions in IM NaClO 4 , pH=3 solution modified the surface close to the inclusions by the presence of FeSO 4 in the passive film.

A Methodology to Deduce the Microstructural Spatial Deformation of Polycrystalline Structures: Application to the Alloy 600

Studying the corrosion of the alloy 600, under water pressure, is of high importance to understand the ageing process of pressurized water reactors. Today, the impact of the oxide growth on the mechanical properties of nickel alloys is a challenge. The surface analysis and the quantification of the local deformation are key factors to deduce the surface damage of the substrate produced by corrosion. Here, we introduce a new methodology to determine the deformation distribution of the alloy 600 by using polycrystalline samples. The method is based on nanopads disposed on the surface samples, which allow a mapping, at the microscopic scale, of the spatial deformation. We applied to the sample…

Understanding sigma-phase precipitation in a stabilized austenitic stainless steel (316Nb) through complementary CALPHAD-based and experimental investigations

Abstract Sigma-phase precipitation in a 316Nb “stabilized” austenitic stainless steel was studied through complementary CALPHAD-based and dedicated experimental investigations. Thermokinetic calculations performed using Thermo-Calc (with the DICTRA module) and MatCalc software showed that the sigma phase (σ) precipitated directly at γ-austenite grain boundaries (GB) via a common solid-state reaction when carbon and nitrogen contents fell below a critical threshold. Residual δ ferrite was found to be more susceptible to σ-phase precipitation; this type of precipitation occurred via two mechanisms that depended on the concentration profiles of δ-ferrite stabilizing elements induced by previou…

A Mechanical–Electrochemical Approach for the Determination of Precursor Sites for Pitting Corrosion at the Microscale

International audience; 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 observe…

Influence of the grain orientation spread on the pitting corrosion resistance of duplex stainless steels using electron backscatter diffraction and critical pitting temperature test at the microscale

Abstract The corrosion behavior of UNS S32202 duplex stainless steel was studied by combining electron backscatter diffraction (EBSD) measurements and critical pitting temperature tests at the microscale. The grain orientation spread (GOS) value was determined in grains of both phases from EBSD data. It was shown that austenitic sites containing extremely small ferrite grains having a GOS value greater than 1.3° were precursor sites for pitting in 4 M NaCl. The critical pitting temperature range was 45–90 °C. All the other sites of both phases remained passive up to 100 °C.

Influence of Centerline Intermetallic Stringers on Pitting Corrosion Resistance of Superduplex Stainless Steel

Superduplex stainless steel UNS S32750 / EN 1.4410 is commonly used in marine environment, petrochemical, oil and gas, chemical and desalination industries, requiring materials with superior corrosion and mechanical properties. Very few residual intermetallic particles may be present under the form of centerline stringers whose effects on corrosion properties are not well documented. A previous study demonstrated the negligible influence of the intermetallic phases in centerline stringers (typically < 0.1% over thickness) on the hydrogen embrittlement susceptibility of superduplex stainless steel [1]. The present study aims at highlighting the impact of centerline intermetallic stringers on…

Influence of long-term ageing in solution containing chloride ions on the passivity and the corrosion resistance of duplex stainless steels

Abstract The influence of long-term ageing in NaCl on the passivity and the electrochemical behavior of UNS S32304 is studied. The passive film thickness, the Cr/Fe ratio and the chloride content were significantly increased after ageing. The chloride distribution depends on residual stresses, sample microstructure and surface preparation. Local electrochemical measurements revealed that pitting potentials are between 250–550 mV vs. SCE after electropolishing. The higher the chloride content, the lower the local pitting potential. It was also shown that the presence of chloride was balanced by the enrichment in chromium after ageing. Then no pitting potential could be measured.

The use of linear regression methods and Pearson’s correlation matrix to identify mechanical–physical–chemical parameters controlling the micro-electrochemical behaviour of machined copper

Abstract Machining introduces residual stresses at the specimen surface and modifies the microstructure and the texture in a small volume close to the surface. Such changes are important in controlling the corrosion behaviour of machined workpieces in the presence of an aggressive environment. In the present paper, the relationships between cutting parameters and the surface and subsurface characteristics of machined copper were first quantified experimentally using a complete plan of L 8 (2 3 ) and a linear regression method. The influence of surface characteristics on the local polarisation curves of machined surfaces was then investigated. The shear-type crystallographic orientation gene…

On the optimization of the cutting conditions for an improved corrosion resistance of OFHC copper

International audience; Machining has a particular impact on the surface integrity and on corrosion resistance of components. In fact, material removal induces geometrical, mechanical and micro-structural modifications in the machined surface and sub-surface that alter the electrochemical behavior of the material, and so the aging process. In this study, oxygen free high conductivity copper (OFHC) has machined under orthogonal cutting conditions using uncoated cemented carbide tools. Then, the corrosion resistance in 0.1 M NaCl salt fog atmosphere of the machined samples is analyzed. Finally, the optimal cutting conditions, including the tool geometry, for an improved corrosion resistance a…

Comparison of local electrochemical impedance measurements derived frombi-electrode and microcapillary techniques

Abstract In the present paper, local electrochemical impedance spectra were obtained on a 316L stainless steel from two configurations: a dual microelectrode (bi-electrode) and microcapillaries. With the bi-electrode, the local impedance measurements were made from the ratio of the applied voltage to the local current density calculated from the application of the ohm's law. With the use of microelectrochemical cells, the specimen surface area in contact with the electrolyte is limited by the use of glass microcapillaries and the local impedance was defined from the ratio of the local potential to the local current restricted to the analysed surface area. Differences and similarities observ…

Local analysis of the mechanical behaviour of inclusions-containing stainless steels under straining conditions

Abstract A numerical method is described for determining the surface stress distribution under straining conditions from the real microstructure of materials containing local heterogeneities. The method is applied to resulfurized steels with a high density of MnS and oxide inclusions. The results are compared to those obtained from surface observations.

Mechanical properties and corrosion behaviour of low carbon martensitic stainless steel after machining

The influence of different combinations of cutting conditions on the mechanical behaviour (microhardness), the microstructure and the corrosion behaviour in NaCl solution (using the electrochemical microcell technique and pulse potentiodynamic testing) of a low carbon martensitic stainless steel (grade X4CrNiMo16.5.1 stainless steel) after tempering treatment was studied. Microhardness was increased on the machined surface. In addition, the electrochemical experiments have shown that the machined materials have a heterogeneous electrochemical behaviour. Significant effect of machining on pitting corrosion was noticed. The pitting potential was found to decrease as the microhardness increase…

Strain mapping near a triple junction in strained Ni-based alloy using EBSD and biaxial nanogauges

A key element for analyzing the crack initiation in strained polycrystalline alloys is the local quantification of the surface strain distribution according to the grain texture. Using electron backscattered diffraction, the local microstructure was determined to both localize a triple junction and deduce the local Schmid factors. Kernel average misorientation (KAM) was also used to map the areas of defect concentration. The maximum principal strain and the in-plane shear strain were quantified using the biaxial nanogauge. Distortions of the array of nanodots used as spot markers were analyzed near the triple junction. The crystallographic orientation and the surface strain were then invest…

Influence of the microstructure on the corrosion behaviour of low-carbon martensitic stainless steel after tempering treatment

Abstract The microstructure of grade X4CrNiMo16.5.1 stainless steel was studied at different scales. The chemical composition of the native passive film formed on the different phases was then determined at the microscale. The degree of homogeneity of the native passive film is discussed. Subsequently, the susceptibility to pitting corrosion of X4CrNiMo16.5.1 was quantified using the electrochemical microcell technique. The nature of precursor sites and the morphology of pits were investigated by combining scanning electron microscopy with Electron BackScatter Diffraction and potentiostatic pulse tests. The role of the microstructure and the cold-worked layer generated by polishing in pitti…

Experimental and numerical assessment of subsurface plastic deformation induced by OFHC copper machining

Strain distributions in the machined surface and subsurface of OFHC copper workpieces were determined experimentally and through numerical simulations. An experimental setup, comprising a double frame camera and a pulsed laser, was developed to measure the displacement fields using the digital image correlation (DIC) technique; strain distributions were then calculated. A numerical orthogonal cutting model was also developed and applied in order to predict such distributions. Comparison between simulated and measured results enabled an understanding of the fundamental mechanisms of plastic deformation of the machined surface of OFHC copper.; International audience; Strain distributions in t…

Influence of Post-machining Thermal Treatment on the Corrosion Behaviour of Copper

Abstract In this paper, the influence of a post-machining thermal treatment (PMTT) on the corrosion behaviour of copper was investigated in a salt fog atmosphere. The corrosion behaviour was affected by the presence of a high density of grain boundaries generated during machining or dislocations formed during PMTT under certain conditions. The obtained results showed that it is possible to find PMTT conditions to cancel changes induced by machining and that the critical factor leading to a sharp increase of the percentage of oxidized surface seems to be the density of dislocations near the machined surface.

Orthogonal cutting simulation of OFHC copper using a new constitutive model considering the state of stress and the microstructure effects

International audience; This work aims to develop an orthogonal cutting model for surface integrity prediction, which incorporates a new constitutive model of Oxygen Free High Conductivity (OFHC) copper. It accounts for the effects of the state of stress on the flow stress evolution up to fracture. Moreover, since surface integrity parameters are sensitive to the microstructure of the work material, this constitutive model highlights also the recrystallization effects on the flow stress. Orthogonal cutting model is validated using experimental designed cutting tests. More accurate predictions were obtained using this new constitutive model comparing to the classical Johnson-Cook model.

Mapping the 3D-surface strain field of patterned tensile stainless steels using atomic force microscopy.

Abstract The quantification of microstructural strains at the surface of materials is of major importance for understanding the reactivity of solids. The present paper aims at demonstrating the potentialities of the atomic force microscopy (AFM) for mapping the three-dimensional surface strain field on patterned tensile specimens. Electron beam (e-beam) lithography has been used to deposit 16×16 arrays of gold-squared pads. Monitoring the evolution of such a pattern under applied strain allows to quantify the triaxial strains both at the micro-(plastic) domain and nanoscale (elastic) domain vs. applied strain. The proposed method was applied to stainless steels after 4.5% plastic strain.

A variable charge molecular dynamics study of the initial stage of nickel oxidation

Abstract The oxidation of nickel single crystals is investigated by using variable charge molecular dynamics. The simulations are performed on three nickel low-index surfaces ((1 0 0), (1 1 0) and (1 1 1)) at temperatures between 300 K and 950 K. The results show that the shape of the oxidation kinetics is independent of the crystallographic orientation and the temperature under the present conditions. The oxide thin film grows according to an island growth mode, this initial stage of oxidation can be divided in three steps: (i) the dissociative chemisorption step (ii) the oxide island nucleation and (iii) the lateral growth of the island. The first step is slowdown/speedup by the surface o…

Numerical Simulations on the Growth of Thin Oxide Films on Aluminum Substrates

We investigated the oxidation of nanocrystalline aluminum surfaces by using variable charge molecular dynamics at 600 K under three oxygen pressures: 1, 10 and 20 atm. The interaction potential was described by the electrostatic plus (Es+) model that allows dynamical charge transfer among atoms. We mainly focused on the effect of the oxygen pressure on the oxidation kinetic, the chemical composition and the microstructure of the oxide films formed. The results show that oxidation kinetics as well as chemical composition and microstructure depend on the applied oxygen pressure. The oxide film thickness tends to a limiting value equal to ~3 nm. Finally, we obtained a partially crystalline oxi…

Synthesis of 3D dendritic gold nanostructures assisted by a templated growth process: Application at the detection of traces of molecules

International audience; Complex architectures like 3D gold dendritic nanostructures were synthesized by an in situ templated growth method using a thin film of a block copolymer [polystyrene-b-poly(4-vinylpyridine)] deposited onto silicon substrates. The overall study has demonstrated the strong link between the morphology, size, and distribution of the structures and the synthetic physicochemical parameters, such as pH, reaction temperature, concentration, and nature of reactants. A nonequilibirum state of the medium has been required to create a fractal growth of the gold structures onto a prepatterned gold-seeded surface and has led to a better control of the structures' surface coverage…

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 oxid…