A mechanistic study on the hydrogen trapping property and the subsequent electrochemical corrosion behavior of quenched and tempered steel

The hydrogen-facilitated anodic dissolution of steel is an interesting experimental phenomenon, but the persistent gaps in this knowledge area are great. The changes in the Tafel slopes and the reaction rates of steel that has been cathodically charged with hydrogen are interpreted mainly in the context of hydrogen trapping and de-trapping behaviors of steel using a variety of electrochemical methods. This study reveals that the increase in the anodic current density and the decrease in the polarization resistance are attributed primarily to the hydrogen-induced lattice expansion. Based on the Tafel-slope change, the oxidation of hydrogen cation partly contributed to the increase in the total anodic current density together with the dominant anodic reaction of the steel dissolution. The electrochemical permeation measurements showed much slower effusion kinetics of the hydrogen that has been trapped at the ε-carbide particles, and the trapping and de-trapping behavior at the fine particles are one of the controlling factors of the hydrogen-enhanced anodic dissolution of steel. From an engineering aspect, it is believed that the current study will provide an important insight into future perspectives on stress corrosion cracking failure occurring in various high-strength steels.     

Electrochemical hydrogen discharge of high-strength low alloy steel for high-pressure gaseous hydrogen storage tank: Effect of discharging temperature

Hydrogen discharge technique of high-strength low alloy steel for high-pressure gaseous hydrogen storage tank was developed by using an electrochemical technique. The electrochemical hydrogen discharge of high-strength low alloy steel were investigated in a deaerated borate buffer solution (0.3 M H₃BO₃ + 0.074 M N₂B₄O₇, pH = 8.4). By applying a potential of +630 mV_SCE which is higher than the hydrogen equilibrium potentials and lower than the pitting potential, the oxidation reaction of metal (Fe → Fe²⁺ + 2e⁻) is limited and oxidation reaction of the hydrogen (H₂ + 2OH⁻ → 2H₂O + 2e⁻) was induced simultaneously. Thus, the pre-charged hydrogen inside the specimen was eliminated effectively without any damage to the specimen. The electrochemical hydrogen discharge method was performed at 25 °C, 50 °C and 75 °C. The efficiency of hydrogen discharge was accelerated with increasing temperature because the exchange current density of hydrogen is increased with temperature.     

The stability of hydrogen evolution activity and corrosion behavior of NiCu coatings with long-term electrolysis in alkaline solution

In this study, NiCu composite coating was electrochemically deposited on a copper electrode (Cu/NiCu) and tested for hydrogen evolution reaction (HER) in 1 M KOH solution for long-term electrolysis with the help of cathodic current–potential curves and electrochemical impedance spectroscopy (EIS) techniques. The bulk and surface composition of the coating was determined using atomic absorption spectroscopy (AAS) and energy dispersive X-ray (EDX) analysis. The surface morphology was investigated by scanning electron microscopy (SEM). The effect of electrolysis on the corrosion behavior of the Cu/NiCu electrode was also reported. It was found that the NiCu coating had a compact and porous structure with good time stability. The HER activity of the coating was stable over 120 h electrolysis and the HER mechanism was not modified during the operation. The corrosion tests showed that the corrosion resistance of the Cu/NiCu electrode changed when a cathodic current was applied to the electrolysis system.     

Effect of minor nickel alloying with zinc on the electrochemical and corrosion behavior of zinc in alkaline solution

The electrochemical and corrosion behavior of pure zinc and Zn-0.5Ni alloy in strong alkaline solution (7 M KOH) was investigated by Tafel plot, potentiodynamic, potentiostatic and electrochemical impedance spectroscopy (EIS) methods, and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Measurements were conducted under different experimental conditions. The results of both Tafel plot extrapolation and the electrochemical impedance spectroscopy (EIS) measurements exhibited the same trend, which the cathodic and anodic processes on the alloy surface are less significant compared with those on the pure zinc. The results revealed that, the shift in steady state of open-circuit potential (E_corr) to more negative potential in the case of the studied alloy compared with that of pure zinc has a positive effect on both charge efficiency and self-discharge.The anodic potentiodynamic measurements demonstrated that the polarization curves exhibited active/passive transition. The active dissolution of both pure zinc and its alloy increases with increasing temperature and scan rate. The activation energy (E_a) value of active region and peak current (I_AI) of the two studied electrodes in the investigated alkaline solution is calculated and compared. In the case of alloy, the results obtained at certain positive potential (+425 mV vs. SCE), exhibited high current density indicating that the most passive layer was destroyed. This indicates that the addition of small amount from Ni to Zn promotes the electrochemical reaction (in the passive region), acting as so-called self catalysis. Accordingly, one can conclude that, the electrochemical behavior of the investigated alloy in strong alkaline solution contributes to suppression of hydrogen gas evolution and increases the corrosion resistance. In addition, reactivation of the alloy surface takes place in the passive region.     

Hydrogen embrittlement behavior in the nugget zone of friction stir welded X100 pipeline steel

Hydrogen-induced damage is an inevitable challenge in pipeline safety applications, especially, the fusion welded joints owing to microstructure heterogeneity caused by welding process. In this work, X100 pipeline steel was subjected to friction stir welding (FSW) at rotation rates of 300–600 rpm under water cooling, and the relationship among the microstructure, hydrogen diffusivity, and hydrogen embrittlement (HE) behavior of the nugget zone (NZ) were studied. The NZ at 600 rpm had the highest effective hydrogen diffusion coefficient (D_eff) of 2.1 × 10^?10 m²/s because of the highest dislocation density and lowest ratio of effective grain boundary. The D_eff decreased with decreasing rotation rate due to the decrease of dislocation density and the increase of ratio of effective grain boundary, and the lowest D_eff of 1.32 × 10^?10 m²/s was obtained at 300 rpm. After hydrogen charging, the tensile strength of all specimens decreased slightly, while the elongation decreased significantly. As the rotation rate decreased, the elongation loss was obviously inhibited, and ultimately a lowest elongation loss of 31.8% was obtained at 300 rpm. The abovementioned excellent mechanical properties were attributed to the fine ferrite/martensite structure, low D_eff, and strong {111}//ND texture dramatically inhibiting hydrogen-induced cracking initiation and propagation.     

Hydrogen generation during the corrosion of carbon steel in crotonic acid and using some organic surfactants to control hydrogen evolution

The purpose of this paper is to describe and evaluate the corrosion of carbon steel in crotonic acid for hydrogen production and using polysorbate 20 (NS), dioctyl sodium sulfosuccinate (AS) and benzalkonium chloride (CS) to control hydrogen evolution. Measurements were conducted in tested solutions using hydrogen evolution and electrochemical impedance spectroscopy (EIS) measurements and complemented by scan electron microscope (SEM) and energy dispersive X-ray (EDX) investigations. It is shown that the hydrogen generation rate obtained during the corrosion of carbon steel in crotonic acid increased with increase in acid concentration, temperature and immersion time. The addition of organic surfactants inhibits the hydrogen generation rate. The inhibition occurs through adsorption of organic surfactants on the metal surface. Adsorption processes followed the Langmuir isotherm. The order of effectiveness of the surfactants was AS > NS > CS. The values of activation energy (E_a) and heat of adsorption (Q_ads) were calculated and discussed.     

Microstructure and electrochemical corrosion behavior of a Pb-1 wt%Sn alloy for lead-acid battery components

The aim of this study was to evaluate the effect of solidification cooling rates on the as-cast microstructural morphologies of a Pb-1 wt%Sn alloy, and to correlate the resulting microstructure with the corresponding electrochemical corrosion resistance in a 0.5 M H₂SO₄ solution at 25 °C. Cylindrical low-carbon steel and insulating molds were employed permitting the two extremes of a significant range of solidification cooling rates to be experimentally examined. Electrochemical impedance spectroscopy (EIS) diagrams, potentiodynamic polarization curves and an equivalent circuit analysis were used to evaluate the electrochemical corrosion response of Pb-1 wt%Sn alloy samples. It was found that lower cooling rates are associated with coarse cellular arrays which result in better corrosion resistance than fine cells which are related to high cooling rates. The experimental results have shown that that the pre-programming of microstructure cell size of Pb-Sn alloys can be used as an alternative way to produce as-cast components of lead-acid batteries with higher corrosion resistance.     

Effects of vanadium precipitates on hydrogen trapping efficiency and hydrogen induced cracking resistance in X80 pipeline steel

In this study, the number and size distribution of vanadium precipitates and their effects on hydrogen trapping efficiency and hydrogen-induced cracking (HIC) susceptibility were investigated in X80 pipeline steel. The results showed that as the vanadium content increased, the number of nanoscale vanadium precipitates clearly increased. Furthermore, the amount of hydrogen atoms trapped by vanadium precipitates gradually increased and the hydrogen diffusion coefficient decreased from 4.74 × 10^?6 cm² s^?1 in the vanadium-free V0 steel to 8.48 × 10^?7 cm² s^?1 in the V4 steel with 0.16% V, according to hydrogen permeation results. It also reduced the possibility of hydrogen atoms diffusing into the sites of harmful defects such as large-size oxides and elongated MnS inclusions, where cracks were caused more easily. In addition, the V3 steel with 0.12% V, containing the largest number of vanadium carbide particles of less than 60 nm, had the lowest HIC susceptibility.     

Analysis of electrochemical hydrogen permeation through X-65 pipeline steel and its implications on pipeline stress corrosion cracking

Electrochemical hydrogen permeation tests were performed to measure the hydrogen permeation current through the X-65 pipeline steel in the electrolytes simulating the soil conditions to initiate near-neutral pH stress corrosion cracking (SCC) in pipelines. The hydrogen permeation current was analyzed following the constant concentration model. It is shown that, AQDS, simulating the organic compound in the soil, inhibits hydrogen permeation by decreasing the sub-surface hydrogen concentration, while sulfide promotes hydrogen permeation by inhibiting the hydrogen recombination and thus increasing the sub-surface hydrogen concentration. The steel specimen is more susceptible to stress corrosion cracking in the soil solution with a higher sub-surface hydrogen concentration, indicating that hydrogen is involved in near-neutral pH SCC in pipelines. It is suggested that hydrogen promotes the cracking of the steel, accompanying with the anodic dissolution on the crack sides and at the crack tip.     

Influence of microstructure on hydrogen trapping and diffusion in a pre-deformed TRIP steel

Austenitic steels are known to exhibit a low hydrogen diffusion coefficient and hence a good resistance to hydrogen embrittlement. Therefore, it is an experimental challenge to investigate their hydrogen diffusion properties. In this study, the electrochemical permeation technique is used to determine the hydrogen diffusion coefficients in different pre-deformed states (φ = 0, 0.32, 0.39, 0.49) of the high-alloy austenitic TRIP steel X3CrMnNiMoN17-8-4 in a temperature range of 323 K–353 K. In combination with microstructural analysis, a correlation between phase transformation from γ-austenite to α′-martensite and dislocation density is shown. As a result of the lattice transformation from fcc to bcc, the diffusion rate of hydrogen is significantly increased (D_{app, φ = 0} = 3.6 × 10^?12 cm² s^?1, D_{app, φ = 0.32} = 1.6 × 10^?11 cm² s^?1at 323 K). With higher degrees of deformation, the dislocation density also increased in the martensite islands, resulting in a degressive growth of the diffusion coefficient (D_{app, φ = 0.39} = 5.3 × 10^?11 cm² s^?1, D_{app, φ = 0.49} = 1.1 × 10^?10 cm² s^?1at 323 K). Moreover, detailed calculations are performed to describe the way of hydrogen trapping and to give a possible mechanism of diffusion.     

The effect of 3D silver nanodome size on hydrogen evolution activity in alkaline solution

Three-dimensional (3D) Ag nanodomes (AgNDs) having different sizes (400, 800, 1200 and 1600 nm) were fabricated using combination of nanosphere lithography and soft lithography. The surface structures of 3D assembled latex particles, nanovoids and metal nanodomes (ND) were examined using scanning electron microscopy (SEM). Their heights and widths analyses were performed with the help of atomic force microscopy (AFM). The effect of diameter of the NDs on their hydrogen evolution activity was examined in 6 M KOH solution at 298 K using electrochemical techniques. Their activities were compared with the activity of bulk Ag electrode. The preparation of 3D-AgNDs having various diameters and examination of their size effects on the water splitting activity have not been studied yet and are being reported firstly. It was found that very well-structured and very uniformly distributed NDs can be fabricated using this procedure. AgNDs exhibit higher hydrogen evolution activity with respect to bulk Ag. Their hydrogen evolution activity depends on their diameters; 1200 nm NDs were the best among them. The current density at ?1.40 V(Ag/AgCl) which is proportional to the rate of hydrogen releasing reaction increases from 0.70 mA cm^?2 to 44.13 mA cm^?2 at this ND electrode with respect to the bulk Ag electrode. At the same 3D-AgNDs electrode and potential, the resistance against the HER reduces from 148.7 Ω cm² to 1.12 Ω cm² (99.6%) by comparing with the bulk Ag electrode. The average surface roughness factors of bulk Ag, 400 nm, 800 nm, 1200 nm and 1600 nm AgNDs are 8, 123, 100, 291 and 176, respectively. The superior hydrogen evolution performance of this electrode is related to its well-structured surface and large real surface area.     

Influence of cerium (III) ions on corrosion and hydrogen evolution of carbon steel in acid solutions

This paper intended to investigate the influence of rare earth Ce(III) ions on the corrosion behavior of carbon steel in two acid solutions (0.5 M HCl and 0.25 M H₂SO₄) in order to control the rate of hydrogen evolution in those systems. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) tests were used for corrosion rate and electrochemical impedance evaluation. SEM was used to examine the sample surfaces immersed in acid solutions containing the optimal threshold Ce(III) concentration (0.1 mM). All results reveal that the corrosion resistance of carbon steel in HCl is superior to that in H₂SO₄ due to the higher rate of hydrogen production in the latter. A model for the corrosion process mechanism and inhibition by Ce(III) salt for carbon steel in the two tested media is proposed.     

Hydrogen embrittlement of super duplex stainless steel in acid solution

Super duplex stainless steel (SDSS) is a good choice of material when resistance to harsh environments is needed. Despite the material’s excellent corrosion resistance and high strength, a number of in-service failures have been recorded. The root cause of these failures was environmentally induced cracking initiated at manufacturing and in-service metallurgical defects. In this study the hydrogen embrittlement of pre-strained super duplex stainless steel specimens was investigated after 48 h cathodic charging in 0.1 M H₂SO₄. The metallurgical changes that resulted from four levels of cold work (4, 8, 12, and 16% plastic strain) were considered and their effect on the embrittlement of the SDSS alloy was investigated. After hydrogen charging, the specimens were pulled immediately to failure and the mechanical properties evaluated. The obtaining fracture morphology was investigated using low and high magnification microscopy. Experimental results indicated that charging the super duplex stainless steel alloy with hydrogen caused varying degrees of embrittlement depending on cold work level. Increasing cold work resulted in a reduction of the elongation to failure. Microscopic investigation confirmed the significant effect of cold work on the hydrogen embrittlement susceptibility of the super duplex stainless steel alloy investigated.     

Absorption of hydrogen in tensile strained iron and high-carbon steel studied by electrochemical permeation and desorption techniques

Absorption of hydrogen in gradually tensile strained Armco iron and high-carbon steel, cathodically charged in 0.1 M NaOH solution, was studied using the electrochemical permeation and desorption techniques. Measurements of hydrogen permeation through specimens in the form of a membrane allowed determining the lattice diffusivity and concentration of hydrogen (diffusible hydrogen). The lattice diffusivity of hydrogen in iron (D = 6.2 × 10⁻⁵ cm²/s) was about 280 times higher than that in high-carbon steel (D = 2.2 × 10⁻⁷ cm²/s). In turn, a detailed analysis of the desorption rate of hydrogen from previously hydrogen charged and strained, cylindrical specimens made it possible to characterize hydrogen reversibly attached to traps. This trapped hydrogen made nearly a whole and a majority (from 70% to 85%, depending on strain) of the reversibly absorbed hydrogen in iron and high-carbon steel, respectively. In both studied materials, the amount of the trapped hydrogen strongly increased with strain. Moreover, in contrast to the diffusible hydrogen, evenly distributed in the charged specimen, the trapped hydrogen was mainly located within a subsurface region of the specimen. The estimated thickness of this subsurface region in iron was about 0.44 mm, whereas that in high-carbon steel was only about 0.017 mm. Consequently, the subsurface concentration of hydrogen in high-carbon steel was extremely high. It may be one of the reasons for more intensive hydrogen embrittlement of high-carbon (high-strength) steels in comparison with that of iron.     

Hydrogen production by electrolysis of a phosphate solution on a stainless steel cathode

The catalytic properties of phosphate species, already shown on the reduction reaction in anaerobic corrosion of steels, are exploited here for hydrogen production. Phosphate species work as a homogeneous catalyst that enhances the cathodic current at mild pH values. A voltammetric study of the hydrogen evolution reaction is performed using phosphate solutions at different concentrations on 316L stainless steel and platinum rotating disk electrodes. Then, hydrogen is produced in an electrolytic cell using a phosphate solution as the catholyte. Results show that 316L stainless steel electrodes have a stable behaviour as cathodes in the electrolysis of phosphate solutions. Phosphate (1 M, pH 4.0/5.0) as the catholyte can equal the performance of a KOH 25%w solution with the advantage of working at mild pH values. The use of phosphate and other weak acids as catalysts of the hydrogen evolution reaction could be a promising technology in the development of electrolysis units that work at mild pH values with low-cost electrodes and construction materials.     

Effect of electrotransport treatment on susceptibility of high-strength low alloy steel to hydrogen embrittlement

Electrotransport theory is defined as mass transportation of solute such as hydrogen in metal under the influence of an electrostatic force field. In this study, electrotransport treatment was applied to remove the accumulated hydrogen inside of the high-strength low alloy steel. The effectiveness of the electrotransport treatment was evaluated by hydrogen concentration measurement, slow strain rate test, and fracture surface analysis. The efficiency of electrotransport treatment is improved with increasing applied current and time, and the highest efficiency was obtained as 88.7% at 450 A for 40 min. The ultimate tensile strength and elongation of specimen after electrotransport treatment was enhanced dramatically in comparison with that of specimen under hydrogen charging condition. The brittle fracture mode was observed on the hydrogen charged specimen, but a clear ductile fracture mode was observed on the specimen after electrotransport treatment. These results confirm that the electrotransport treatment is effective to remove the accumulated hydrogen inside of the high-strength low alloy steel.     

The effect of annealing on the electrochemical properties of Zr0.5Ti0.5Mn0.5V0.3Co0.2Ni1.1 alloy electrodes

The annealing treatment was found to result in the improvement in the cyclic stability but the degradation of discharge capacity, activation and high-rate dischargeability for Zr_0.5Ti_0.5Mn_0.5V_0.3Co_0.2Ni_1.1 alloy electrode. A lower discharge potential in the annealed alloy electrode was found owing to a more homogeneous alloy, which is consistent with the pressure–composition isotherms (P–C–T) measurement. We found that the annealed alloy also had lower and flatter pressure plateaus, and larger pressure hysteresis. At high discharge rates, the hydrogen diffusion in the bulk of the alloy was the rate-determining step. The diffusion coefficients for hydrogen in the annealed and as-cast alloys were calculated to be 1.4×10⁻¹² cm² s⁻¹ and 4.3×10⁻¹² cm² s⁻¹, respectively. The lowering of high-rate discharge capacity can be ascribed to the reason that the hydrogen diffusion coefficient is lower due to homogeneous microstructure in the annealed alloy.     

FE simulation of hydrogen diffusion in duplex stainless steel

ABAQUS FE simulations of hydrogen diffusion in duplex stainless steel have been performed. Three models with different ferrite–austenite configurations have been applied and the hydrogen diffusion and the hydrogen coefficient have been evaluated as a function of austenite phase size and shape and the calculated diffusion coefficients compared to literature. Hydrogen concentration due to stress and plastic strain close to an embedded flaw has also been evaluated. An important observation is that the simulations show that when the austenite phases are saturated with hydrogen there is no large difference in the overall diffusion rate between the small and large phased models, i.e. no influence of tortuosity is observed. The work clearly demonstrates that both microstructure and flaws will influence the hydrogen diffusion and the hydrogen concentration and hence, must be taken into account when evaluating the susceptibility of hydrogen stress cracking in duplex stainless steels.     

Propagation behaviour of general and localised corrosion of carbon steel in simulated groundwater under aerobic conditions

Abstract

Carbon steel is one of the candidate overpack materials for geological disposal of high-level radioactive waste in Japan. Corrosion of carbon steel is classified into two types: general corrosion and localised corrosion. In this study, propagation of general and localised corrosion (pitting corrosion and crevice corrosion) were investigated by immersion tests of carbon steel under the aerobic conditions. The results of the immersion tests showed that the corrosion growth rate was strongly dependent on the environmental conditions and type of steel. However, the upper limit of the pitting factor, the ratio between the maximum corrosion depth and the average corrosion depth, was determined approximately using only average corrosion depth. Based on the experimental and literature data, an empirical model that predicts the maximum corrosion depth of an overpack from average corrosion depth was developed by applying the extreme value statistical analysis using the Gumbel distribution function.