Characterization of naturally grown oxide layers on copper with and without benzotriazole by electrochemical and photoelectrochemical measurements

Autorisation éditeur okInternational audienceThe active corrosion of ancient artefacts (bronze disease) is linked to the presence of copper chloride underneath Cu(I) oxide formed at the surface of bronze. The properties of the Cu(I) oxide determine the mechanism of formation of the corrosion layer and their knowledge would to develop efficient stabilization treatments. The aim of our work is to characterize the structure and the electronic properties of Cu(I) oxide layers formed in different conditions (atmospheric and aqueous electrolyte) under opencircuit potential, using electrochemical and photoelectrochemical methods and SEM. Photoelectrochemistry allows the characterization the semiconducting properties of the passive layer and leads to a better knowledge of the nature of the electrode/solution interface and of the electrochemical reactions occurring at the oxide surface. Atmospheric Cu(I) oxide shows mainly p-type behaviour, whereas Cu(I) oxide layers formed at open-circuit potential by immersion in a NaCl solution were shown to exhibit p-type behaviour during the first hours of immersion and simultaneous n-p behaviour for longer immersion times. In the presence of benzotriazole added to the sodium chloride solution, the photoelectrochemical measu-rements revealed modifications of the semi-conducting properties of the Cu2O layer (duplex p-n layer from short immersion times) and showed that BTA makes the oxide layer more insulating. Results will be discussed in regards to the Cu(I) oxide role on the bronze disease

Hydrogen evolution in aqueous solutions containing dissolved H2S: Evidence of direct electroactive contribution of H2S

International audienceThis paper compares the cathodic reactions occurring on steel in an oxygen-free aqueous solution containing dissolved H 2 S or dissolved CO 2. It is well admitted that the rate of the cathodic reaction is enhanced in aqueous solutions containing dissolved CO 2 , in comparison with strong acid solutions at the same pH [1-6]. In a previous paper [7], the authors have shown that this phenomenon appears only in the mass transfer limitation region, where the transport of carbonic acid is added to the transport of proton. In the case of H 2 S containing solutions, this chemical mechanism is no more sufficient to explain the cathodic polarization curves. An additional electrochemical reaction is clearly observed, with strong links with H 2 S concentration

Hydrogen evolution in aqueous solutions containing dissolved H2S: Evidence of direct electroactive contribution of H2S

International audienceThis paper compares the cathodic reactions occurring on steel in an oxygen-free aqueous solution containing dissolved H 2 S or dissolved CO 2. It is well admitted that the rate of the cathodic reaction is enhanced in aqueous solutions containing dissolved CO 2 , in comparison with strong acid solutions at the same pH [1-6]. In a previous paper [7], the authors have shown that this phenomenon appears only in the mass transfer limitation region, where the transport of carbonic acid is added to the transport of proton. In the case of H 2 S containing solutions, this chemical mechanism is no more sufficient to explain the cathodic polarization curves. An additional electrochemical reaction is clearly observed, with strong links with H 2 S concentration

Impact of Oxygen on Corrosion and Hydrogen Permeation of Pure iron in the Presence of H2S

International audienceThis paper examines the influence of oxygen traces on corrosion and hydrogen charging of steel in H 2 S containing environment. It is well known that H 2 S is the driving force for many types of steel failures such as hydrogen induced cracking (HIC), sulfide stress cracking (SSC), and stress-oriented hydrogen induced cracking (SOHIC). Since it is a huge concern for oil and gas industries, standard test methods have been developed and published as NACE technical methods (e.g. NACE TM0284 and NACE TM0177). Though it is recognized that oxygen pollution shall be avoided during H 2 S cracking tests, there is still a lack of experimental data to illustrate the potential impacts of a small oxygen pollution. The aim of the present study was to check if oxygen traces can modify corrosion mechanisms and hydrogen charging of steel in H 2 S medium. Experiments consisted in hydrogen permeation measurements through thin pure iron membrane. They were performed at corrosion potential in order to be in realistic environmental conditions. Corrosion rate was also evaluated through weight loss measurements. Analysis of test solutions was performed in order to identify reaction products between H 2 S and O 2

Corrosion of Pure iron and Hydrogen Permeation in the Presence of H 2 S with O 2 contamination

International audienceThis paper examines the influence of traces of oxygen on corrosion and hydrogen charging of steel in an H 2 S containing environment. It is well known that H 2 S promotes hydrogen entry into steels, that may result in many types of steel failures such as Hydrogen Induced Cracking (HIC), Sulfide Stress Cracking (SSC), and Stress-Oriented Hydrogen Induced Cracking (SOHIC). Since it is a huge concern for oil and gas industries, standard test methods have been developed and published as NACE technical methods (e.g. NACE TM0284 and NACE TM0177). Though it is recognized that oxygen pollution should be avoided during H 2 S cracking tests, there is still a lack of experimental data to illustrate the potential impacts of a small oxygen pollution. The aim of the present study is to check if oxygen traces can modify the mechanisms of corrosion and hydrogen charging of steel in H 2 S containing medium. Experiments consisted of hydrogen permeation measurements through a thin pure iron membrane. They were performed at free potential circuit in order to ensure more realistic environmental conditions. The corrosion rate was also evaluated and test solutions analyzed

Electrochemical study of oxygen impact on corrosion and hydrogen permeation of Armco iron in the presence of H 2 S

International audienceH 2 S corrosion of mild steel is a recurrent issue in the oil and gas industry. Many studies related to the corrosion and hydrogen permeation of steel in an H 2 S containing environment have been made during the past decades with the intent of improving the knowledge and the prevention of economic loss. Since H 2 S is also a hydrogen entry promoter, lots of studies are also dedicated to the understanding of H 2 S cracking. Although it is generally accepted to avoid oxygen contamination in such a medium, there is a lack of research concerning its effect on the corrosion and hydrogen charging of steel. In this study, the effect of oxygen on corrosion and hydrogen charging of steels in an H 2 S containing environment is studied using Electrochemical Impedance Spectroscopy (EIS). An equivalent electrical circuit has been built according to SEM observations, literature research and experimental results. Using this equivalent electrical circuit, experimental data was analyzed and the average corrosion rates were deduced and found to be in good agreement with corrosion rates obtained by weight loss measurements. Furthermore, the evolution of fitting parameters (double layer capacity, charge transfer resistance, diffusion impedance, etc.) was found to be in good agreement with the real physical meaning of such parameters in the given conditions. This research contributes to the explanation of the mechanism behind the high corrosion rate observed in an H 2 S environment polluted with traces of oxygen

EIS study of iron and steel corrosion in aqueous solutions at various concentrations of dissolved H2S : impact of oxygen contamination.

International audienceMildly acidic water containing dissolved H 2 S presents a strong risk in the cracking of low-carbon steels. Several studies on H 2 S cracking mechanisms have shown that the main driving force is linked to the ability of H 2 S to promote hydrogen entry into the bulk material. Standard test methods have been developed and published as NACE technical standards (e.g. NACE TM0284 and NACE TM0177) to aid materials selection in the oil and gas sector. Though it is recognized that oxygen pollution should be avoided during H 2 S cracking tests, there is a lack of experimental data to illustrate the effects of a small oxygen pollution. Dissolved oxygen concentrations greater than the recommended upper limit (50 parts per billion) can easily be obtained in the case of poor laboratory practices. This paper will focus on the interactions between oxygen and H 2 S on electrochemical behavior of unalloyed steel. A continuous O 2 injection at a level corresponding to 500 ppb is applied, together with H 2 S bubbling in our test solutions, for periods lasting the same order as SSC standard tests. Steel surface reaction phenomena/corrosion rates in H 2 S saturated solution, with or without oxygen pollution, are studied using electrochemical impedance spectroscopy. The evolution of corrosion rates obtained from impedance analysis was compared to two other independent methods: i/ weight loss measurements and, ii/ hydrogen permeation. Without O 2 pollution, a permeation efficiency of 100% was obtained, as expected. Permeation current density was thus found to match precisely with the corrosion current density determined by impedance analysis at different times. On the other hand, when a continuous O 2 pollution was added in the system, significantly higher corrosion rates were observed, associated with test solution acidification. At the same time, permeation efficiency was decreased by up to one order of magnitude

Temperature dependence of the electrochemical behavior of the 690 Ni-base alloy between 25 and 325 °C

International audienceThe electrochemical behavior and the chemical composition of passive films formed on the Alloy 690 at room temperature in borate buffer solution (pH = 9.0) was studied with different techniques for two surface finishings. XPS and quantum yield measurements showed the presence of Ni and Cr oxides and hydroxides for passive films formed on both the as received and the mechanically polished one, whereas the presence of mixed spinel type Ni (1-x) Fe x Cr 2 O 4 was only observed on the as received material. Additionally, Electrochemical Impedance Spectroscopy (EIS) highlighted a higher corrosion resistance for the as received alloy in comparison with the mechanically polished alloy, which was linked to the chemical composition of the oxide film. Electrochemical measurements were performed before, during, and after oxidation of the Alloy 690 of Steam Generator (SG) tube of Pressurized Water Reactor (PWR) at high temperature and high pressure in the simulated primary circuit of PWR. At high temperature, the interface becomes electrochemically active yielding the precipitation of the corrosion products which form a few tens of nm thick diffusion barrier for the released metal cations. This overlayer is built on the top of a few nm thick, Cr rich inner layer at the alloy/oxide interface which was found to behave similarly to that initially formed at ambient temperature. It is concluded that high temperature oxidation in the static condition of an autoclave at 325°C does not promote a better passivation state than the one already existing initially

Etude de la corrosion d'un acier faiblement allié en milieu confiné contenant du CO2 dissous

L'annulaire des conduites pétrolières flexibles est un espace confiné (rapport V/S de l'ordre de 0,03 mL cm-2) qui peut contenir de l'eau et du CO2. Dans cet annulaire, le pH est élevé et les vitesses de corrosion sont très faibles par rapport à la situation rencontrée en plein bain. Afin d'étudier cet effet de confinement, une cellule à couche mince, comprenant un système d apport de gaz et un dispositif de contrôle du positionnement, a été développée. La chute ohmique a été modélisée pour calculer l'impédance dans cette cellule. Les impédances mesurées lors de la corrosion d'un acier faiblement allié en milieu confiné contenant du CO2 dissous ont ensuite été analysées. La diminution des vitesses de corrosion en milieu confiné est attribuée à un blocage de la surface active de l'acier par un film de sidérite isolant. Un modèle de corrosion tenant compte de ce blocage a été développé. Les prévisions théoriques sont en bon accord avec les mesures à l'état stationnaire.PARIS-BIUSJ-Thèses (751052125) / SudocPARIS-BIUSJ-Physique recherche (751052113) / SudocSudocFranceF

Mécanismes d'oxydation, de décapage et de sur-décapage des aciers fortement alliés au silicium

Les mécanismes d'oxydation, de décapage et sur-décapage d'un acier bas carbone est d'un acier fortement allié au silicium (1,6 et 3.2 % en masse de silicium) ont été étudiés. Le suivi de l'oxydation par thermogravimétrie et la caractérisation de la calamine des aciers fortement alliés au silicium a montré un effet très marquant de passivation de la couche de silice. Les calamines des échantillons modèles sont composées de couches d'hématite, magnétite et wüstite partiellement décomposée en fer et magnétite pour l'acier bas carbone. Pour l'acier au silicium, la fayalite est présente à l'interface acier/wüstite sous forme de grains ou d'une couche interne. Le suivi du potentiel de circuit ouvert pendant le décapage et sur-décapage de ces échantillons a montré un potentiel de corrosion stable et anodique pour les oxydes de fer et une chute drastique de ce potentiel au contact de l'acide avec le métal. Le suivi du taux de dissolution totale par ICP-AES combiné avec des mesures de courant de corrosion par la méthode de Tafel a montré une contribution importante de la dissolution électrochimique par oxydation de la wüstite et la magnétite et réduction de Fe3+ issu de la dissolution chimique de l'hématite et la magnétite. La fayalite est libérée dans la solution par dissolution de la wüstite ou du métal adjacents. Après le contact acide/metal, toutes les dissolutions sont exclusivement électrochimiques par corrosion du métal et réduction de la magnétite (cas des calamines industrielles). La spectroscopie d'impédance électrochimique a été utilisée pour la première fois pour ce type d'étude. L'estimation des valeurs de capacité a montré un comportement pseudo passif pour la couche d hématite et d électrode poreuse pour la wüstite.Oxidation, pickling and over-pickling mechanisms of a low carbon steel and a high alloyed steel (1.6 and 3.2 wt.% Si) were investigated. The monitoring of oxidation with thermogravimetry and characterization of scale showed a very important passivating effect of the silica layer. Model scales are composed of layers of hematite, magnetite and partially decomposed wüstite into iron and magnetite for the low carbon steel. For the silicon steel, fayalite is present in the steel/wüstite interface as grains or an internal layer. Open circuit potential measurements during pickling and over-pickling of these samples showed a stable and anodic corrosion potential for iron oxides and a significant potential jump once the acid reaches the metal. The monitoring of the total dissolution rate with ICP-AES coupled with corrosion current measurements with the Tafel method showed an important contribution of electrochemical dissolution by oxidation of wüstite and magnetite and reduction of Fe+3 from chemical dissolution of hematite. Fayalite is liberated in the solution by dissolution of the surrounding wüstite or metal. After the contact acid/metal, all dissolutions are exclusively electrochemical by corrosion of the metal and reduction of magnetite (case for industrial scales). Electrochemical impedance spectroscopy was used for the first time for this kind of studies. The estimation of the capacitance values showed a passive like behaviour for hematite and a porous electrode one for wüstite.PARIS-JUSSIEU-Bib.électronique (751059901) / SudocSudocFranceF