0000000000171007
AUTHOR
B. Vuillemin
Study of the Chemical Conversion of Aluminum Alloys by Coupling CFDE and EQCM
The ability of the channel flow double electrode (CFDE) technique and electrochemical quartz crystal microbalance (EQCM) for studying in situ chromate phosphate conversion coating on 5182 aluminum alloys was explored. It was first demonstrated that aqueous Cr(VI) can be analyzed quantitatively with the CFDE technique by reduction into Cr(III) on a graphite electrode. Samples used for EQCM were quartz plated by physical vapor deposition using a 5182 alloy target, allowing thin layers of aluminum alloys with a similar chemical composition to be obtained. EQCM was adapted in order to account for the hydrodynamic conditions in an industrial process, by placing the quartz in a flow cell. In orde…
Investigation of self-healing mechanism on galvanized steels cut edges by coupling SVET and numerical modeling
Local cathodic inhibition has been observed on the cut-edge of galvanized steel immersed in 0.03 M NaCl solution using the scanning vibrating electrode technique. The current distribution results indicate that cathodic inhibition occurs in a limited spatial zone located between the cathodic sites on the steel and the anodic sites on the exposed zinc surface. The experimental current distributions are compared with the results of numerical simulations that show the specific diagnostic features for the detection of cathodic inhibition from scanning vibrating electrode technique (SVET) data so as to distinguish the zero current regions from experimental artifacts due to the lateral resolution …
Numerical modelling of the galvanic coupling in aluminium alloys: A discussion on the application of local probe techniques
Abstract A discussion is proposed on the determination of the input values and the experimental validation of finite element modelling of the galvanic coupling in aluminium alloys by local probe techniques such as the Scanning Vibrating Electrode Technique (SVET) and the microcapillary electrochemical cell (microcell). Polarization curves obtained by the microcell were introduced as input conditions in the model based on Laplace or Nernst–Planck equation. SVET measurements were performed to determine the coupling current distribution on an Al/Al4%Cu bimetallic system. Agreement was found between simulated and experimental current distributions depending on the input conditions and the solve…
Application of total internal reflexion fluorescence microscopy for studying pH changes in an occluded electrochemical cell: Development of a waveguide sensor
A device for pH mapping derived from optical sensors similar to total internal reflection fluorescence microscopy (TIRFM) has been developed for future possible applications in the field of localized corrosion. The sensing principle is the increase of the fluorescent yield of the fluorescein with the pH of the medium. The basic principle of this sensor is based on the excitation of a fluorescent silica polymer film of nanometre dimensions, deposited by sol–gel method on a waveguiding layer. The total internal reflexion conditions creates an evanescent wave which interacts with the molecules trapped in the silica layer. A conventional microscope located above the sample collects the fluoresc…
Relation between grain size and hydrogen diffusion coefficient in an industrial Pd–23% Ag alloy
Abstract The diffusion mechanism of hydrogen in an industrial cold worked Pd–23% Ag alloy is investigated according to its grain size. The microstructural parameters are determined by X-ray diffraction analysis and the diffusion parameters are determined using the galvanostatic electrochemical permeation technique. Two diffusion mechanisms are displayed. For apparent grain size below 40 nm the hydrogen atoms diffuse in the grain boundaries. For grain size above 100 nm, an intergranular diffusion mechanism occurs. For intermediate grain size both mechanisms coexist. Furthermore, the diffusion in the grain boundaries is not faster than the diffusion in the bulk, as generally observed for pure…
Corrosion in amine solvents used for the removal of acid gases
International audience; Processes using amine solvents for the removal of CO 2 have long been used for the treatment of natural gas. More recently, developments in the field of post-combustion CO 2 capture have gained considerable interest for greenhouse gas mitigation. Even though the nature of the amine is different for both applications, the process flow diagrams are very similar. The raw gas is contacted with the amine solvent in an absorber column, and the CO 2 is absorbed by the solvent. The rich solvent containing the CO 2 then circulates to a regenerator, where the temperature is increased to strip the CO 2. The lean solvent then returns to the absorber for a new cycle. For these pr…
Effect of the surrounding aeration on microcapillary electrochemical cell experiments
In the microelectrochemical capillary cell technique a silicone rubber gasket is used to avoid any electrolyte leakage between the pulled glass capillary and the working electrode (the metallic tested material). In this study, it is demonstrated that the oxygen reduction reaction (ORR) is strongly affected by the use of the silicone rubber. Experiments under a surrounding argon gas shielding of the pulled capillary in contact with the metallic surface have been performed showing a large effect on the ORR. Considering the high permeation rate of oxygen through silicone, the decrease of the reaction rate observed experimentally was validated by FEM modelling assuming that the air/silicone/wat…
Passivity Breakdown: Development and Application of Local Chemical and Electrochemical Probe Methods
Abstract The most identified classes of phenomena at the origin of the passivity breakdown and the electrochemical and chemical factors controlling the induced localized corrosion are summarized before introducing the scientific concepts at the origin of the design of the local probe techniques used in recent advances in understanding localized corrosion processes. Examples concerning the surface reactivity of aluminium alloys are presented to support a final discussion on the needs for experimental developments with capabilities to support modelling.
Predictive Model for Cut-Edge Corrosion of Galvanized Steels
A numerical model for the electrochemical behavior of cut-edge of galvanized steels is proposed. Some experimental data of current densities above cut-edge immersed in a 0.03M NaCl solution have been measured, using a scanning vibrating electrode technique, and compared with some simulated ones. A good fit has been obtained. The model geometry has been modified by decreasing the electrolyte thickness in order to tend towards an atmospheric corrosion case; such situation that is not easily accessible by electrochemical studies. Three regions can be distinguished according to the efficiency of the galvanic coupling to protect steel.
Impedance characterization of the electrochemical environment under a polymer film artificially delaminated
International audience; Knowledge of the electrical conductivity of the zone under a delaminated paint film is one necessary input parameter for the simulation of electrochemically driven underpaint corrosion. In this work, a microelectrode array system has been developed, tested, and applied to measure the spatial distribution of resistivity in the delaminated zone along the metal/polymer interface. The experimental device consists of a linear array of six 100 m diameter stainless steel microelectrodes (100 m in diameter) embedded in a steel substrate. A polymer coatingwas applied and an artificial "delaminated zone"was created using the laser-induced decohesion technique. The electrochemi…
Inhibition Probing on a Cut-Edge Electrode Machined from a Primer-Coated 2024-T3 Alloy
Conventional corrosion protection of 2024-T3 alloys (AA2024T3) in aeronautic structures combines conversion coating with chromate-inhibited primer protected by a top-coat. In some cases this protection can break down after mechanical damage to the paint systems inducing a risk of localized corrosion if the release of inhibitors trapped in the primer does not reach a critical level. There is a need for developing computational models combining the inhibitor release and transport within and from the coating system andthecorrosioninhibitionprocess,toassistinthedesignofnewmultifunctionalcoatingsystems.Theinfluenceonthecorrosioninhibition of various parameters such inhibitor release rate, defect…
Électrochimie et corrosion à l'échelle des microstructures
Resume. Dans ce chapitre, on montre que le role de la microstructure sur les processus de corrosion localisee, par exemple la sensibilite d’un precipite par rapport au reste de la matrice, peut etre evalue et simule en tenant compte des processus de couplage galvanique et de transport des especes chimiques, grâce a l’evolution recente d’un ensemble de methodes d’analyses chimiques, electrochimiques et electriques dont la resolution spatiale est adaptee a l’echelle micronique qui caracterise la microstructure des alliages metalliques. Il est possible de disposer, a cette echelle, d’informations comme la difference de potentiel de surface intrinseque a la coexistence d’une phase et de sa matr…
Protective mechanisms occurring on zinc coated steel cut-edges in immersion conditions
Abstract Electrochemical processes occurring on the cut-edge of a galvanized steel immersed in NaCl solutions were studied using numerical simulations, and in situ current and pH profiles measured over the cut-edge. These results clearly demonstrate that only the steel surface remote from the zinc coating is cathodically active, oxygen reduction being strongly inhibited in the vicinity of zinc. This trend was confirmed by local polarization curves recorded on these distinct areas. Ex-situ AES and SEM analysis and cathodic polarization curves in solutions containing Zn 2+ ions led to conclude that this cathodic inhibition was related to the fast nucleation of a dense Zn(OH) 2 film on the ste…
Bipolar electrolysis for tritium recovery from weakly active tritiated water
Abstract Detritiation facilities produce low activity tritiated water from which tritium cannot be recovered. Bipolar electrolysis, based on the electrochemical permeation of hydrogen and its isotopes through Pd–Ag alloy membranes, allows tritiated water enrichment together with negligible gaseous tritium release. Our purpose is to enrich water from 500 Ci/l (1.85×1013 Bq/l) to more than 2000 Ci/l (7.40×1013 Bq/l). We first describe the principle of bipolar electrolysis and its application to isotopic enrichment. The experimental part of this work consists of the determination of the isotopic separation factors. From these experimental values, we simulated the working of an operational cell…
Modeling bimetallic corrosion under thin electrolyte films
A finite element model (FEM) was developed to calculate the potential distribution in the electrolyte in the case of bimetallic corrosion between iron and zinc electrodes, taking into account mass transport of oxygen in the solution. This model was first compared with experimental results obtained by scanning vibrating electrode technique (SVET) on a galvanized steel cut-edge in immersion conditions in a 0.03 M NaCl electrolyte. A good agreement was obtained between the calculated and experimental current densities. The model predicted the evolution of the galvanic coupling as function of the electrolyte thickness and for various iron–zinc surface area ratios. Different coupling regimes wer…
Cut-edge corrosion of a Zn–55Al-coated steel: A comparison between sulphate and chloride solutions
Abstract Ex situ observations and in situ measurements of current and pH distributions over cut-edge coated steels revealed that Zn–55Al coatings are sacrificial only in chloride solutions, because of an activation of both Zn- and Al-rich phases present in the coating. In sulphate solutions, an efficient cathodic protection occurs only for short times of immersion, because only Zn-rich phases are active in this medium. The low solubility and strong acidification induced by Al(OH)SO4 allows only short distance cathodic protection, but cannot prevent red rust precipitation on the steel surface.
Effect of Aeration on the Microelectrochemical Characterization of Al[sub 2]Cu Intermetallic Phases
Local probing of the galvanic coupling between micrometer-sized Al 2 Cu phases and the surrounding aluminum-based matrix of a specially heat-treated 2011 alloy is investigated using a microcapillary electrochemical cell. The aging of an isolated Al 2 Cu particle, i.e., selective dissolution of aluminum, is controlled by the aeration condition at the tip of the capillary due to the nature of the silicon membrane used as a gasket. The local electrochemical behavior of an isolated particle after aging confirms the mass transport control of the oxygen reduction on the galvanic coupling of the particle with the surrounding matrix.
An electrochemical quartz crystal microbalance study of lithium insertion into thin films of tungsten trioxide I. Modeling of the ionic insertion mechanism
A theoretical description of the mechanism of lithium insertion into amorphous thin films of tungsten trioxide (a-WO3) prepared by thermal vacuum evaporation of WO3 powder is presented. The model developed is based on the experimental results obtained by chronoamperometry and ac impedance spectroscopy associated with electrochemical quartz crystal microbalance (EQCM). The electrode mass change and the current flowing through the electrochemical cell during cathodic polarization are simulta neously recorded. As expected, it can be observed that the insertion process is associated with a gain of mass of the inserted electrode at long times (t > 1 s). On the other hand at short times (t < 1 s)…
Corrosion in alkanolamine used for acid gas removal: From natural gas processing to CO2 capture
The aim of this paper is to review some of the parameters influencing the corrosivity of alkanolamine solvents used for natural gas purification or for CO2 capture. In the light of literature data and of new experimental results, the influences of temperature and of acid gas loading are discussed. These two parameters appear to have a strong impact on corrosion rates of carbon steel, with extrapolated corrosion rates of several tens of mm/year for the highest temperature and acid gas loading condition.
Detector-electrode for alpha spectrometry in water sample, numerical and early feasibility investigation toward thermocompression bonding assembly process
International audience; This study focuses on the feasibility of a detector-electrode for direct alpha measurement in aqueous samples. Such a device could be made by adding a boron doped diamond electrode on top of a standard silicon detector, with bonding and insulating layers. The impact of these different layers has been investigated by Monte-Carlo simulation (MCNP6), to find a compromise between alpha detection of the silicon, electrode and shielding properties of the diamond. The assembly process involving thermocompression between both substrates was successfully achieved under a clean room conditions.
Reliability of numerical models for simulating galvanic corrosion processes
International audience; Maturity of numerical simulation represents an important issue in the development of predictive models of galvanic corrosion. As widely used in electrochemical engineering, a coupled electrochemical-transport-reaction (CETR) model is recommended to simulate the current distribution above a galvanic corrosion cell made of the cut-edge of a galvanized steel sheet. Nevertheless, simulating current density distributions obtained experimentally by scanning vibrating electrode technique (SVET) above such a galvanic cell appears to be more accurate using an electrostatic model considering a homogeneous conductivity. In this case, the absence of concentration gradients next …
In situ investigation of sacrificial behaviour of hot dipped AlSi coating in sulphate and chloride solutions
Abstract The electrochemical behaviour of the cut-edge of hot-dipped aluminium–silicon-based alloy coated steel is studied in immersed conditions in sulphate and in chloride media. Preliminary studies performed on steel-pure Al bi-electrode demonstrate that a significant galvanic current can develop at short times (t
Influence of the Chemical Composition and Electronic Structure of Passive Films Grown on 316L SS on Their Transient Electrochemical Behavior
Modifications of the passive film formed on 316L stainless steel (SS) in acidic media were performed under dc or ac polarization. The effects of these ageing treatments on the chemical composition and the electronic structure of the passive film were studied. Chemical analysis with angle resolved X-ray photoelectron spectroscopy revealed that ageing induces a net enrichment in chromium oxide in the inner part of the passive film and an increase of the thickness of the inner oxide. Semiconducting behavior of the passive films was revealed by a Mott-Schottky analysis. The passive film was considered as a dielectric with different trapping levels lying in the bandgap. The observed n- or p-type…
Influence of magnesium content on the corrosion resistance of the cut-edges of Zn–Mg-coated steel
Abstract The ability of Zn–Mg coatings (with magnesium content between 5.8 and 15.5 wt.%) to protect steel sheets has been evaluated with local electrochemical techniques (scanning vibrating electrode technique, microcapillary electrochemical cell) and rotating disk electrode, and compared with the corrosion protection afforded by a pure zinc coating. From immersion tests of coated steel cut-edges, it is observed that alloying zinc with magnesium leads to a decrease of the galvanic current between the coating and the steel surface, and to an improvement of the steel corrosion resistance after a drying period, due to the presence of magnesium in the corrosion products.
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…
Corrosion in alcanolamines for natural gas treatment - High temperature experiments in lean and rich conditions
International audience; In the oil and gas industry, acid gas removal is required for the treatment of natural gas. New applications were also recently pushed forward for CO 2 capture from the flue gas of power plants. For both applications, the most widespread industrial processes use absorption-desorption by an alcanolamine solvent. In such amine units for acid gas removal, corrosion represents an important operational concern. Influent parameters governing corrosion are temperature and acid gas loading, amine nature, and the presence of degradation by-products. Some of these parameters were studied with corrosion experiments in autoclave. Test temperature was between 110°C and 120°C, i.e…
An electrochemical quartz crystal microbalance study of lithium insertion into thin films of tungsten trioxide II. Experimental results and comparison with model calculations
Abstract Lithium insertion into amorphous thin films of tungsten trioxide (a-WO 3 ) prepared by thermal vacuum evaporation of WO 3 powder has been studied experimentally by chronoamperometry, cyclic voltammetry and ac impedance spectroscopy associated with electrochemical quartz crystal microbalance (EQCM). During cathodic polarization of the electrode and at short times two antagonistic processes occur. One is a non faradaic process and is associated with the expulsion of anions from the electrode surface under the effect of the electric field built in the electrolyte when a potential difference is imposed between the electrodes. The other one is the faradaic insertion of non-solvated lith…
3 Probing and Modelling of Galvanic Coupling Phenomena in Localized Corrosion
The basic driving force of localized corrosion or corrosion protection in numerous cases is the galvanic coupling of which the dimensional aspect is fixed by a combination of scales regarding interfacial processes or properties. At the electrolyte–metal interface, it is necessary to consider the microstructure (including all real-time modification induced for example by applied stresses), the possible chemical changes at the surface of the material, and the electrolyte conductivity contribution, among others factors.
In-situ characterisation of organosilane films formation on aluminium alloys by electrochemical quartz crystal microbalance and in-situ ellipsometry
Abstract Organosilane pre-treatments have been studied intensively during the last years in order to replace hexavalent chromium conversion treatments. The aim of this study is to follow in-situ the formation of this organosilane layer in solution. Two in-situ techniques, spectroscopic ellipsometry and electrochemical quartz crystal microbalance, were used to investigate the mechanism and the kinetics of this protective film formation. In-situ measurements highlight that the organosilane film observed after the drying process is not formed into the solution, but during the emersion and drying step. Hence, it has been possible to characterise the presence of a very thin organosilane layer in…
Modeling of Growth and Dissolution of Nanotubular Titania in Fluoride-Containing Electrolytes
In this paper, model calculations of diffusion processes and pH profiles inside TiO 2 nanotubes are performed in order to explore key factors in the growth mechanism of this system in aqueous electrolytes. An electrochemical steady state featured by an equivalent rate between oxide growth and dissolution is reached for a given current efficiency. Electrochemical oxide growth is found to be exclusively located at the pore bottom, whereas chemical oxide dissolution is uniformly distributed over the whole nanotube. It can be deduced from the results that electrolyte resistance or diffusion processes in the electrolyte inside the tubes are not limiting.
Consideration of the formation of solids and gases in steady state modelling of crevice corrosion propagation
Abstract One of the challenges in the simulation of crevice corrosion propagation is the rigorous treatment of non-aqueous species (gas or solids), since the appearance of a new phase in a crevice will automatically have an impact on its geometry. This paper presents a simple approach, where heterogeneous reactions are considered in a post-processing step, by determining the conditions of potential, external chemistry (pH, chloride, …) or geometry under which gas or solid phases could appear in the crevice. Thus, as function of these conditions, stability diagrams for the different phases that are liable to appear in an actively propagating crevice can be constructed. Such diagrams (e.g. di…