Effect of membrane thickness on hydrogen permeation in steels during wet H2S exposure

International audienceThe permeation of hydrogen in steel in the presence of acid gases is not a simple phenomenon as the steel may contain trapping sites and also because the permeation may be governed by surface reactions associated with corrosion. Recently, hydrogen permeation experiments carried out at the corrosion potential have shown a constant flux for various membrane thicknesses in the range 0.05-0.8 mm. These results revealed the difficulty to express the flux for thicker steel membrane (i.e. pipe) from laboratory studies on thin membranes, as the classical rule (flux proportional to the inverse of the membrane thickness) is not always applicable and not conservative. This paper presents new permeation results, obtained on steel membranes up to 10 mm thick. The transition between thin and thick membranes is clearly established, and is in the millimeter range in sour conditions. The necessity to adopt a new interpretative framework to link permeation measurements and hydrogen cracking mechanisms is reinforced. For thin membranes, the permeation flux is constant and governed only by the charging flux crossing the entry face. This surface mechanism is probably correlated with surface cracking mode, like SSC

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

Reversible catastrophic oxidation of a 38Fe-34Ni-25Cr alloy induced by sodium sulphate at low oxygen potential atmospheres

International audienceThe chromia-forming nickel-based alloy Haynes (R) HR-120 was oxidised with and without Na2SO4 deposit in a CO/H-2/CO2 (45/45/10%vol.) simulated process atmosphere at 900 degrees C for 96 h. During the first hours of oxidation, samples covered by sodium sulphate exhibit higher oxidation rate than non-covered ones. However, after 24 h both sulphate-covered and uncovered specimens follow the same linear kinetics. In this very low oxygen partial pressure environment (10(-18) atm), the presence of Na2SO4 promotes the growth of localized iron-rich oxide nodules leading to the observed accelerated oxidation. The development of these nodules is discussed to be the result of the chromia dissolution induced by a basic fluxing mechanism. As soon as the salt is evaporated, slower kinetics are observed and the nodules disappear. In these specific conditions, the oxidation could be considered as a self-healing process

Hydrogen charging in low alloy steels exposed to H 2 S: impact of CO 2 or N 2 in the gas mixture

International audienceThis paper examines the influence of CO 2 / H 2 S ratio on hydrogen charging in low alloy steels. Hydrogen flux through the steel surface is the driving force for sulfide stress cracking (SSC). The impact of H 2 S and pH on SSC severity is extremely well documented, and these two parameters are used in the SSC severity diagram of ISO 15156-2 [1]. However, the CO 2 / H 2 S ratio is not considered in standard SSC testing procedures, even though it has a strong impact on corrosion. Indeed, according to several authors, competitive adsorption between HS-and HCO 3-on the steel surface could modify the charging flux, thus the SSC risks. The goal of the present study was to check if hydrogen charging is influenced by other parameters than the sole pH and P H2S. Experiments consisted in hydrogen permeation measurements through HSLA steel thin membranes. They were performed under cathodic charging in order to avoid corrosion products precipitation. Charging solutions with different H 2 S concentrations with or without CO 2 were used, in order to examine the individual contributions to the charging flux, and hence to evaluate a possible impact on SSC risks

Contribution of acoustic emission to the understanding of sulfide stress cracking of low alloy steels

cited By 17International audienceThe acoustic emission technique was applied to standard tests devoted to evaluate sulfide stress cracking susceptibility of steels for oil and gas industry. The mapping of the density of AE signals vs. their location on the specimen gauge length as a function of time allowed early detection of cracking, and gave meaningful information on incubation times and propagation rates. Sulfide stress cracking initiation was correlated with the presence of critical surface defects. A mechanism involving plastic strain and/or metal dissolution was proposed to account for crack propagation. © 2011 Elsevier Ltd

Acoustic emission monitoring of wet H2S cracking of linepipe steels: Application to hydrogen-induced cracking and stress-oriented hydrogen-induced cracking

cited By 9International audienceAcoustic emission (AE) was used for monitoring steel cracking during exposure to wet hydrogen sulfide (H2S) environments. A method for filtering AE data related to hydrogen-induced cracking (HIC) was presented and applied for several case studies. In a series of tests on unstressed sweet service steels, evolution of AE indicated three successive HIC phases. An initial incubation period corresponded to hydrogen entry in the steel, during which no cracking occurred. Then two cracking phases were detected. The first was associated with decohesion of weak steel interphases. The second was identified as crack propagation under high internal hydrogen pressure. Crack propagation decreased and eventually ceased over time. Analysis of AE data was then used to evaluate the extent of HIC after sour exposure. Correlation was found when appropriate data filtering was applied. AE analysis was also applied to sour service steels under an applied load. The first steel exhibited HIC AE signals. Its fracture surface was typical of a stress-oriented hydrogen-induced cracking (SOHIC) mode of failure, in good agreement with AE results. For the second steel, which also failed during the test, no AE related to HIC was detected. Fracture surface was typical of sulfide stress cracking (SSC), also in good agreement with AE findings. © 2011, NACE International

High-temperature oxidation evaluation usingcrystal microbalance

High-temperature oxidising environments are frequently encountered but the limited number of in situ techniques that can be implemented has hindered the monitoring possibilities and a better comprehension of the oxidation phenomenon. In this paper, the high-temperature oxidation behaviours of three alloys (AISI 316L, AISI 310 and HAYNES\uae HR-120\uae) were studied by using crystal microbalances. Two types of crystal were tested: quartz or gallium orthophosphate crystals. First the behaviour of thin sputtered deposited alloys on quartz slides was studied at 400 and 700\ub0C under air oxidising conditions and compared to bulk samples. Kinetics measurements were performed on the three alloy films deposited on the resonators at 400 or 700\ub0C: it was possible to measure very small mass variations associated with thin oxide formation between 5 and 180 nm of thickness. The crystal microbalance technique gives promising perspectives in understanding the high-temperature corrosion and scaling mechanisms and also for in situ monitoring

Improving pH Prediction for High Pressure and High Temperature Applications in Oil and Gas Production

International audiencepH prediction represents a crucial step before selecting materials for use in sour oil and gas wells as regards weight loss corrosion and H 2 S cracking. Among the numerous parameters which determine the equilibrium pH, important ones are CO 2 and H 2 S partial pressures (P CO2 and P H2S respectively), the total pressure, the ionic strength and the chemical composition of the solution, and the temperature. Most models used by oil and gas operators present a too narrow range of validity for these parameters, which makes them inappropriate for high pressure and high temperature (HPHT) fields or for CO 2 reinjection. This paper presents modeling improvements which allows extending the prediction validity in temperature and pressure to respectively 200 °C and 1,000 bar of total pressure, and for an ionic strength up to 5 mol.kg-1. These improvements take into account the fugacities in gas phase of CO 2 and H 2 S as determined by the Soreide and Whitson formalism. The influence of water and CH 4 pressure is also taken into account up to several hundred bars. Activity coefficients in the water phase are calculated using the Pitzer model. The consistency of the model is verified by comparison with experimental measurements of pH under high pressure. It is then applied to oil and gas applications at high pressure and high temperature. The impact of the new calculation method is discussed both for pH evaluation and also for H 2 S activity, with strong implications for the evaluation of SSC risks

pH prediction in concentrated aqueous solutions under high pressure of acid gases and high temperature

International audienceAn extended model for pH prediction in oil and gas environments has been developed. Accurate pH calculations for high pressure and high temperature applications depends mainly on CO2 and H2S partial pressures, the ionic strength, the chemical composition of the solution, and the temperature. Accounting for the non-ideal behaviors of liquid and gas phases allows pH calculations up to 200 °C, 2000 bar total pressure, and ionic strengths up to 5 mol.L-1. The results are consistent with experimental measurements and with other models reported in the literature