0000000000049356
AUTHOR
Halina Krawiec
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 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.
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…
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…
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.
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…
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).
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…
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.
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.
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…
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.
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…
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…