O2 contamination in SSC / HIC test environments. Impact on test results and discussion on acceptable limits for high H 2 S content

International audienceIt is a well admitted fact that oxygen contamination shall be avoided during H 2 S cracking tests of low alloy steels. In the 2016 revisions of NACE TM0177 and NACE TM0284 documents, quantitative limits of O 2 contamination were included with thresholds at 10 and 50 ppb of dissolved oxygen depending on the considered mechanical properties of the tested grade. However, the scientific basis of these values are not well established and there is still a lack of experimental data to illustrate the potential impacts of an oxygen pollution. In addition, while the revised test methods explicitly address initial contamination of the test solution before H 2 S introduction, they do not consider a continuous oxygen supply during testing. Yet, continuous contamination is extremely difficult to be completely eliminated. In order to better understand the impact of O 2 contamination on H 2 S cracking, a 3-years Joint Industrial Project was launched at the end of 2015. The objectives were to evaluate if O 2 contamination can affect H 2 S cracking test results. A range of steel grades covering different types of O&G applications for High H 2 S content were used. SSC (uniaxial tensile tests as well as 4 point-bend) and HIC tests were conducted, with well controlled and continuous O 2 contamination. Three levels of O 2 partial pressures in the gas feed corresponding to 300 ppb, 50 ppb and less than 10 ppb dissolved O 2 were used. In parallel to the standard qualification tests, hydrogen permeation and weight-loss corrosion experiments were performed with the same test matrix, covering all regions of the SSC severity diagram. This paper aims at sharing the main results of this project for high H 2 S content

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 and hydrogen permeation of low alloy steel in H2S-containing environments : the effect of test buffer solution chemistry

International audienceH 2 S-containing (sour) service environments present a considerable risk of hydrogen induced cracking (HIC) and sulfide stress cracking (SSC) to steel line pipe, pressure vessel and tubular components during upstream oil and gas production, through the ability of H 2 S to corrode and promote hydrogen entry into the material bulk via a cathodic reaction process. Materials selection for sour service is made via standard test methods such as NACE TM0284 and NACE TM0177. A commonly used test solution (NACE TM0177 solution A) comprises sodium chloride (5.0%) + acetic acid (0.5%), to work in a range between pH 2.8-4.0. When pH stability is essential over long testing periods, solutions that are buffered by acetic acid with sodium acetate are proposed. NACE TM0177 solution B (5.0% NaCl + 0.4% sodium acetate + 2.5% acetic acid) presents an initial pH of 3.4-3.6, specified not to exceed pH 4.0 over the testing duration. Newer, alternative solutions from the high-strength line pipe (HLP) research committee from the Iron and Steel Institute of Japan (ISIJ) propose higher acetic acid/acetate concentrations for enhanced buffering capacity. This may offer practical testing advantages, although material corrosion rates and hydrogen uptake are possibly affected. In this conference proceeding, we report on the corrosion and hydrogen uptake performance of a sour-grade X65 steel exposed to NACE Solutions A and B, and an HLP solution (at the same pH as NACE B solution, i.e. pH 3.5) under continuous H 2 S purging (0.1 MPa, T = 24°C) over 720 hours. Electrochemical methods measure electrochemical impedance at the entry face of, and hydrogen permeation across, the X65 membrane. Overall, the differences we note are linked to the different weak acid/conjugate base concentration. Keywords Hydrogen permeation, acetic acid, hydrogen sulfide, X65 steel

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

Impact of oxygen on corrosion of pure iron and on hydrogen charging in H2S Medium

Ce travail de thèse a porté sur l’impact de traces d’oxygène sur la corrosion de fer pur ou d’acier en milieu H 2 S, ainsi que sur le chargement en hydrogène. Trois axes de recherche ont été suivis.Une première partie est consacrée à la chimie de la réaction H 2 S+O 2 . Nous avons d’abord identifié dans la littérature les chemins réactionnels possibles de la réaction H2S+O2 , et les méthodes d’analyse des espèces S-O en solution. Nous avons ensuite utilisé des méthodes thermodynamiques pour prédire les espèces les plus stables, qui ont été validées par des essais expérimentaux. Il ressort de cette analyse que les principaux produits solubles de la réaction H2S+O2 sont les ions sulfate, thiosulfate etsulfite, ainsi que les ions H + . La décroissance continue du pH de la solution d’essai dans un système corrosif en milieu H2S peut être un indicateur d’une pollution par l’oxygène.La seconde partie utilise des méthodes électrochimiques pour étudier les phénomènes de corrosion et de formation de dépôts en présence ou en absence d’oxygène. La vitesse de corrosion est systématiquement plus grande en présence de O2 . Un modèle d’impédance a été developpé pour l’étude de l’évolution de l’interface métal/électrolyte, et ce modèle est en accord avec la littérature et est validé par l’évaluation de la vitesse de corrosion par perte de masse.Enfin, la troisième partie est consacrée au chargement en hydrogène dans le fer pur ou dans un acier pétrolier de type X65. En absence de pollution par l’oxygène, on observe des rendements très proches de 100 % entre le courant de perméation et le courant de corrosion estimé à partir des mesures d’impédance, et ce sur plusieurs semaines. En présence d’O2 , ce rendement est systématiquement beaucoup plus faible. Par ailleurs, quelques tests menés sur l’acier pétrolier montrent également un effet important de l’oxygène sur le caractère plus ou moins protecteur du dépôt, qui n’avait pas été observé sur système modèle utilisant du fer purThe work in this thesis presents the effect of trace concentrations of oxygen (O2 ) on corrosion and hydrogen uptake of pure iron/steel in H2S-media. Three main avenues of research were conducted.The first part is concerned with the reaction chemistry between dissolved H2S and O2. A literature review is presented, identifying a number of reaction pathways associated with the dissolved H2S and O2 reaction as well as analytical methods used to measure the resulting S-O reaction products. Subsequently, thermodynamic calculations allow for the prediction of the most stable species indissolved H2S -O2 solutions, later confirmed using spectroscopic and chromatographic methods. Such techniques reveal that the principal soluble reaction products are sulfate, thiosulfate and sulfite anions,as well as hydronium ions. From pH monitoring, a continuous rise in acidity of an H2S solution can be an indication of O2 ingress.Secondly, electrochemical methods are used to explore corrosion phenomena and deposit formation in the presence and absence of O2 pollution. Corrosion rates in the presence of O2 are reproducibly much higher if compared against those in the system lacking O2 . An electrochemical impedance spectroscopy model has been developed to study the evolution of the metal / electrolyte interface over time, which is validated using weight loss corrosion rate measurements, and represents impedance data reported in the literature on similar systems.Finally, the third part is devoted to hydrogen uptake in pure iron and petroleum industry sour-grade steel (X65). In the absence of O2 pollution, permeation efficiency yields close to 100% are observed between the permeation current and the corrosion current estimated from the impedance measurements over a period of several weeks. In the presence of O2 , however, this yield is reproducibly far lower. Moreover, some tests conducted on X65 also show a significant effect of O2 on the quite protective nature of the deposit, not observed on the model system using pure iro

Impact de l’oxygène et de l’H2S sur la corrosion du fer pur et sur le chargement en hydrogène

The work in this thesis presents the effect of trace concentrations of oxygen (O2 ) on corrosion and hydrogen uptake of pure iron/steel in H2S-media. Three main avenues of research were conducted.The first part is concerned with the reaction chemistry between dissolved H2S and O2. A literature review is presented, identifying a number of reaction pathways associated with the dissolved H2S and O2 reaction as well as analytical methods used to measure the resulting S-O reaction products. Subsequently, thermodynamic calculations allow for the prediction of the most stable species indissolved H2S -O2 solutions, later confirmed using spectroscopic and chromatographic methods. Such techniques reveal that the principal soluble reaction products are sulfate, thiosulfate and sulfite anions,as well as hydronium ions. From pH monitoring, a continuous rise in acidity of an H2S solution can be an indication of O2 ingress.Secondly, electrochemical methods are used to explore corrosion phenomena and deposit formation in the presence and absence of O2 pollution. Corrosion rates in the presence of O2 are reproducibly much higher if compared against those in the system lacking O2 . An electrochemical impedance spectroscopy model has been developed to study the evolution of the metal / electrolyte interface over time, which is validated using weight loss corrosion rate measurements, and represents impedance data reported in the literature on similar systems.Finally, the third part is devoted to hydrogen uptake in pure iron and petroleum industry sour-grade steel (X65). In the absence of O2 pollution, permeation efficiency yields close to 100% are observed between the permeation current and the corrosion current estimated from the impedance measurements over a period of several weeks. In the presence of O2 , however, this yield is reproducibly far lower. Moreover, some tests conducted on X65 also show a significant effect of O2 on the quite protective nature of the deposit, not observed on the model system using pure ironCe travail de thèse a porté sur l’impact de traces d’oxygène sur la corrosion de fer pur ou d’acier en milieu H 2 S, ainsi que sur le chargement en hydrogène. Trois axes de recherche ont été suivis.Une première partie est consacrée à la chimie de la réaction H 2 S+O 2 . Nous avons d’abord identifié dans la littérature les chemins réactionnels possibles de la réaction H2S+O2 , et les méthodes d’analyse des espèces S-O en solution. Nous avons ensuite utilisé des méthodes thermodynamiques pour prédire les espèces les plus stables, qui ont été validées par des essais expérimentaux. Il ressort de cette analyse que les principaux produits solubles de la réaction H2S+O2 sont les ions sulfate, thiosulfate etsulfite, ainsi que les ions H + . La décroissance continue du pH de la solution d’essai dans un système corrosif en milieu H2S peut être un indicateur d’une pollution par l’oxygène.La seconde partie utilise des méthodes électrochimiques pour étudier les phénomènes de corrosion et de formation de dépôts en présence ou en absence d’oxygène. La vitesse de corrosion est systématiquement plus grande en présence de O2 . Un modèle d’impédance a été developpé pour l’étude de l’évolution de l’interface métal/électrolyte, et ce modèle est en accord avec la littérature et est validé par l’évaluation de la vitesse de corrosion par perte de masse.Enfin, la troisième partie est consacrée au chargement en hydrogène dans le fer pur ou dans un acier pétrolier de type X65. En absence de pollution par l’oxygène, on observe des rendements très proches de 100 % entre le courant de perméation et le courant de corrosion estimé à partir des mesures d’impédance, et ce sur plusieurs semaines. En présence d’O2 , ce rendement est systématiquement beaucoup plus faible. Par ailleurs, quelques tests menés sur l’acier pétrolier montrent également un effet important de l’oxygène sur le caractère plus ou moins protecteur du dépôt, qui n’avait pas été observé sur système modèle utilisant du fer pu

Electrochemical impedance spectroscopy of iron corrosion in H 2 S solutions

International audienceCorrosion of iron exposed to H2S saturated solution at pH 4 was studied by electrochemical impedance spectroscopy, weight loss coupons and surface analysis. Hydrogen permeation was also used as indirect means of evaluating the intensity of the proton reduction reaction leading to hydrogen entry into the metal. Since corrosion in this type of test solution results in the rapid build-up of a conductive and highly porous iron sulfide scale, a specific contribution of the film has to be considered. An impedance model was thus proposed. The faradaic anodic impedance consists of a two-step reaction with charge transfer and adsorption – desorption. An additional contribution, associated with the conductive and highly porous iron sulfide film was added in parallel. This contribution, mostly visible in the 2 low frequency domain, presents a 45° tail associated with a porous electrode behavior. This model was well adapted to describe impedance diagrams measured at various exposure times, up to 620 hours. Charge transfer resistance determined from impedance analysis allowed calculating the evolution with time of the corrosion current density. A very good correlation was found between this corrosion current density and the hydrogen permeation current density. As expected in our experimental conditions, a permeation efficiency close to 100 % is demonstrated. Corrosion rate of 490 µm/year was measured by weight-loss specimens, confirming the validity of the impedance analysis, which resulted in a calculated corrosion rate of 530 µm/year

Ion pairing controls rheological properties of “processionary” polyelectrolyte hydrogels

International audienceWe demonstrated recently that polyelectrolytes with cationic moieties along the chain and a single anionic head are able to form physical hydrogels due to the reversible nature of the head-to-body ionic bond. Here we generate a variety of such polyelectrolytes with various cationic moieties and counterion combinations starting from a common polymeric platform. We show that the rheological properties (shear modulus, critical strain) of the final hydrogels can be modulated over three orders of magnitude depending on the cation/anion pair. Our data fit remarkably well within a scaling model involving a supramolecular head-to-tail single file between cross-links, akin to the behaviour of pine-processionary caterpillar. This model allows the quantitative measure of the amount of counterion condensation from standard rheology procedure