Hydrogen embrittlement of the coarse grain heat affected zone of a quenched and tempered 42CrMo4 steel

The coarse grain heat affected zone (CG-HAZ) of welds produced in a quenched and tempered 42CrMo4 steel was simulated by means of a laboratory heat treatment consisting in austenitizing at 1200 °C for 20 min, oil quenching and finally applying a post weld heat treatment at 700 °C for 2 h (similar to the tempering treatment previously applied to the base steel). A tempered martensite microstructure with a prior austenite grain size of 150 μm and a hardness of 230 HV, similar to the aforementioned CG-HAZ weld region, was produced. The effect of the prior austenite grain size on the hydrogen embrittlement (HE) behaviour of the steel was studied comparing this coarse-grained microstructure with that of the fine-grained base steel, with a prior austenite grain size of 20 μm.The specimens used in this study were charged with hydrogen gas in a reactor at 19.5 MPa and 450 °C for 21 h. Cylindrical specimens were used to determine hydrogen uptake and hydrogen desorption behaviour. Smooth and notched tensile specimens tested under different displacement rates were also used to evaluate HE.Embrittlement indexes, EI, were generally quite low in the case of hydrogen pre-charged tensile tests performed on smooth tensile specimens. However, very significant embrittlement indexes were obtained with notched tensile specimens. It was observed that these indexes always increase as the applied displacement rate decreases. Moreover, hydrogen embrittlement indexes also increase with increasing prior austenite grain size. In fact, the embrittlement index related to the reduction in area, EI_(RA), reached values of over 20% and 50% for the fine and coarse grain size steels, respectively, when tested under the lowest displacement rates (0.002 mm/min).A comprehensive fractographic analysis was performed and the main operative failure micromechanisms due to the presence of internal hydrogen were determined at different test displacement rates. While microvoids coalescence (MVC) was found to be the typical ductile failure micromechanism in the absence of hydrogen in the two steels, brittle decohesion mechanisms (carbide-matrix interface decohesion, CMD, and martensitic lath interface decohesion, MLD) were observed under internal hydrogen. Intergranular fracture (IG) was also found to be operative in the case of the coarse-grained steel tested under the lowest displacement rate, in which hydrogen accumulation in the process zone ahead of the notch tip is maximal.     

Hydrogen effects on X80 pipeline steel in high-pressure natural gas/hydrogen mixtures

Blending hydrogen into existing natural gas pipelines has been proposed as a means of increasing the output of renewable energy systems such as large wind farms. X80 pipeline steel is commonly used for transporting natural gas and such steel is subjected to concurrent hydrogen invasion with mechanical loading while being exposed to hydrogen containing environments directly, resulting in hydrogen embrittlement (HE). In accordance with American Society for Testing and Materials (ASTM) standards, the mechanical properties of X80 pipeline steel have been tested in natural gas/hydrogen mixtures with 0, 5.0, 10.0, 20.0 and 50.0vol% hydrogen at the pressure of 12 MPa. Results indicate that X80 pipeline steel is susceptible to hydrogen-induced embrittlement in natural gas/hydrogen mixtures and the HE susceptibility increases with the hydrogen partial pressure. Additionally, the HE susceptibility depends on the textured microstructure caused by hot rolling, especially for the notch specimen. The design calculation by the measured fatigue data reveals that the fatigue life of the X80 steel pipeline is dramatically degraded by the added hydrogen.     

The dependence of hydrogen embrittlement on hydrogen transport in selective laser melted 304L stainless steel

The mechanical property and hydrogen transport characteristics of selective laser melting (SLM) 304L stainless steel were investigated by tensile tests and thermal desorption spectroscopy (TDS). The heat treatment affected the hydrogen embrittlement (HE) susceptibility and the treatment at 950 °C showed the larger HE effects. Cellular structures and melt-pool boundaries were dissolved at 850 and 950 °C, respectively. TDS results indicate that the hydrogen diffusivity of the as-received SLM 304L was lower than that of wrought 304L and the hydrogen diffusion activation energy increased with the recrystallisation degree, which was related to the dislocation density. Dislocations, rather than strain-induced martensite, were the main cause of HE owing to the high austenite stability of the samples. The pre-existing dislocations in the SLM 304L sample heat-treated at 950 °C for 4 h affected the hydrogen transport behaviour during sample stretching and led to severe HE.     

Hydrogen embrittlement and associated surface crack growth in fine-grained equiatomic CoCrFeMnNi high-entropy alloys with different annealing temperatures evaluated by tensile testing under in situ hydrogen charging

The effect of the annealing temperature after cold rolling on hydrogen embrittlement resistance was investigated with a face-centered cubic (FCC) equiatomic CoCrFeMnNi high-entropy alloy using tensile testing under electrochemical hydrogen charging. Decreasing annealing temperature from 800 °C to 750 °C decreased grain sizes from 3.2 to 2.1 μm, and resulted in the σ phase formation. Interestingly, the specimen annealed at 800 °C, which had coarser grains, showed a lower hydrogen embrittlement susceptibility than the specimen annealed at 750 °C, although hydrogen-assisted intergranular fracture was observed in both annealing conditions. Because the interface between the FCC matrix and σ was more susceptible to hydrogen than the grain boundary, the presence of the matrix/σ interface significantly assisted hydrogen-induced mechanical degradation. In terms of intergranular cracking, crack growth occurred via small crack initiation near a larger crack tip and subsequent crack coalescence, which has been observed in various steels and FCC alloys that contained hydrogen.     

Hydrogen embrittlement behaviors at different deformation temperatures in as-quenched low-carbon martensitic steel

The present study investigated hydrogen-related fractures at different deformation temperatures ranging from ?100 °C to 100 °C in low-carbon martensitic steel. The sensitivity to hydrogen embrittlement increased as the temperature decreased from 100 °C to 0 °C, while it decreased as the temperature decreased further below 0 °C. We characterized the fracture surface types from the morphological and crystallographic aspects and found that the fraction of hydrogen-embrittled surfaces exhibited a similar temperature dependence on the sensitivity to hydrogen embrittlement. The qualitative discussion suggested that the degree of hydrogen accumulation exhibits a peak value in the medium temperature range, which has the same tendency as the sensitivity to hydrogen embrittlement confirmed experimentally. Thus, we proposed that the effect of deformation conditions on the sensitivity to hydrogen embrittlement could be explained on the basis of the hydrogen accumulation behavior.     

Effect of the loading mode and temperature on hydrogen embrittlement behavior of 15Cr for steam turbine last stage blade steel

The hydrogen embrittlement of 15Cr martensitic stainless steel, for steam turbine last stage blades, was systematically studied by using slow strain rate tensile (SSRT) test and constant loading tensile (CLT) test at room temperature and 80 °C to simulate the service conditions. It was shown that, despite the lower hydrogen concentration absorbed during SSRT, the hydrogen-induced fracture strength of 15Cr steel for SSRT was lower than the threshold fracture strength for CLT. This was due to the remarkable enhancement in local hydrogen concentration due to the transportation of hydrogen by mobile dislocation during SSRT. In addition, although the higher hydrogen concentration was absorbed during SSRT at 80 °C, the hydrogen embrittlement susceptibility of 15Cr steel for SSRT at 80 °C was lower than that at room temperature, because the degree of local hydrogen accumulation decreased at a higher temperature.     

Hydrogen permeation in a Cr–Mo–V medium-carbon steel: Effect of the quenching medium and tempering temperature

Hydrogen permeation tests are carried out to evaluate the effect of the quenching medium and tempering temperature on the permeation parameters and density of hydrogen traps, of a Cr–Mo–V low-alloy medium-carbon steel. Three types of steel membranes are tested: 1) in the as-quenched condition, 2) tempered at 235 °C and 3) tempered at 530 °C; each one quenched in two different media: oil or brine. From the as-quenched condition, the apparent concentration of hydrogen and hydrogen flux, tend to decrease as the tempering temperature increases. The membranes in the as-quenched condition and tempered at 530 °C, show lower hydrogen diffusivity and higher density of hydrogen traps than membranes tempered at 235 °C. It is concluded that tempering at 235 °C, promotes hydrogen induced cracking, which is contrary to what has been previously determined. The cracking is related to a higher hydrogen diffusivity and lower density of hydrogen traps.     

Effect of specific microstructures on hydrogen embrittlement susceptibility of a modified AISI 4130 steel

The focus of this study is to analyze hydrogen embrittlement susceptibility of a modified AISI 4130 steel by means of incremental step loading tests. Three different microstructures with a hardness of 40 HRC were analyzed: martensite with large and small prior austenite grains and dual-phase (martensite/ferrite). According to the results, the dual-phase microstructure presented the lowest hydrogen embrittlement susceptibility and martensite with large prior austenite grains, the highest. This behavior was attributed to the lower fraction of high-angle boundaries presented by the martensite with large prior austenite grains, which led to a higher diffusible hydrogen content. Moreover, the ferrite local deformation in the dual-phase microstructure enhanced its hydrogen embrittlement resistance by lowering the stress concentration. A synergic effect of decohesion and localized plasticity was identified on the hydrogen induced fracture of the tested microstructures leading to an intergranular + quasi-cleavage fracture in the martensite and quasi-cleavage in the dual-phase microstructure.     

Damage associated with interactions between microstructural characteristics and hydrogen/methane gas mixtures of pipeline steels

There is no common standard for blended hydrogen use in the natural gas grid; hydrogen content is generally based on delivery systems and end-use applications. The need for a quantitative evaluation of hydrogen-natural gas mixtures related to the mechanical performance of materials is becoming increasingly evident to obtain long lifetime, safe, and reliable pipeline structures. This study attempts to provide experimental data on the effect of H₂ concentration in a methane/hydrogen (CH₄/H₂) gas mixture used in hydrogen transportation. The mechanical performance under various blended hydrogen concentrations was compared for three pipeline steels, API X42, X65, and X70. X65 exhibited the highest risk of hydrogen-assisted crack initiation in the CH₄/H₂ gas mixture in which brittle fractures were observed even at 1% H₂. The X42 and X70 samples exhibited a significant change in their fracture mechanism in a 30% H₂ gas mixture condition; however, their ductility remained unchanged. There was an insignificant difference in the hydrogen embrittlement indices of the three steels under 10 MPa of hydrogen gas. The coexistence of delamination along with the ferrite/pearlite interface, heterogeneous deformation in the radial direction, and abundance of nonmetallic MnS inclusions in the X65 sample may induce a high stress triaxiality at the gauge length at the beginning of the slow strain rate tensile process, thereby facilitating efficient hydrogen diffusion.     

Effects of hydrogen on the fracture toughness of CrMo and CrMoV steels quenched and tempered at different temperatures

Tempering temperatures ranging between 500 and 720 °C were applied in order to analyse the relationship between steel microstructure and the deleterious effect of hydrogen on the fracture toughness of different CrMo and CrMoV steels. The influence of hydrogen on the fracture behaviour of the steel was investigated by means of fracture toughness tests using CT specimens thermally pre-charged with hydrogen gas.First, the specimens were pre-charged with gaseous hydrogen in a pressurized reactor at 19.5 MPa and 450 °C for 21h and elasto-plastic fracture toughness tests were performed under different displacement rates. The amount of hydrogen accumulated in the steel was subsequently determined in order to justify the fracture toughness results obtained with the different steel grades. Finally, scanning electron microscopy was employed to study both the resulting steel microstructures and the fracture micromechanisms that took place during the fracture tests.According to the results, hydrogen solubility was seen to decrease with increasing tempering temperature, due to the fact that hydrogen microstructural trapping is lower in relaxed martensitic microstructures, the strong effect of the presence of vanadium carbides also being noted in this same respect. Hydrogen embrittlement was also found to be much greater in the grades tempered at the lowest temperatures (with higher yield strength). Moreover, a change in the fracture micromechanism, from ductile (microvoid coalescence, MVC), in the absence of hydrogen, to intermediate (plasticity-related hydrogen induced cracking, PRHIC) and brittle (intergranular fracture, IG), was appreciated with the increase in the embrittlement indexes.     

The influence of intergranular and interphase boundaries and δ-ferrite volume fraction on hydrogen embrittlement of high-nitrogen steel

We study the effect of grain size of austenitic and ferritic phases and volume fraction of δ-ferrite, which were obtained in different solution-treatment regimes (at 1050, 1100, 1150 and 1200 °C), on hydrogen embrittlement of high-nitrogen steel (HNS). The amount of dissolved hydrogen is similar for the specimens with different densities of interphase (γ-austenite/δ-ferrite) and intergranular (γ-austenite/γ-austenite, δ-ferrite/δ-ferrite) boundaries. Despite, the susceptibility of the specimens to hydrogen embrittlement, depth of the hydrogen-assisted surface layers, hydrogen transport during tensile tests and mechanisms of the hydrogen-induced brittle fracture all depend on grain size and ferrite content. The highest hydrogen embrittlement index I_H = 32%, the widest hydrogen-affected layer and a pronounced solid-solution hardening by hydrogen atoms is typical of the specimens with the lowest fraction of the boundaries. Even though fast hydrogen transport via coarse ferritic grains provides longer diffusion paths during H-changing, the width of the H-affected surface layer in the dual-phase structure of the HNS specimens is mainly determined by the hydrogen diffusivity in austenite. In tension, hydrogen transport with dislocations increases with the decrease in density of boundaries due to the longer dislocation free path, but stress-assisted diffusion transport does not depend on grain size and ferrite fraction. The contribution from intergranular fracture increases with an increase in the density of intergranular and interphase boundaries.     

Effects of grain size and dislocation density on the susceptibility to high-pressure hydrogen environment embrittlement of high-strength low-alloy steels

The tensile properties of several high-strength low-alloy steels in a 45 MPa hydrogen atmosphere at ambient temperature were examined with respect to the effects of grain size and dislocation density on hydrogen environment embrittlement. Grain size was measured using an optical microscope and dislocation density was determined by X-ray diffractometry. Both grain refinement and a reduction in dislocation density are effective in reducing the susceptibility to embrittlement. The steel that has high dislocation density or large grain size inclines to show a smooth intergranular fracture surface. Given only the grain size and dislocation density, a simple approximation of the embrittlement property of high-strength steel could be obtained. This method could be useful in selecting candidate materials in advance of the mechanical tests in high-pressure hydrogen gas.     

Simulation and optimization of hydrogen production by steam reforming of natural gas for refining and petrochemical demands in Lebanon

Steam reforming of natural gas produces the majority of the world's hydrogen (H₂) and it is considered as a cost-effective method from a product yield and energy consumption point of view. In this work, we present a simulation and an optimization study of an industrial natural gas steam reforming process by using Aspen HYSYS and MATLAB software. All the parameters were optimized to successfully run a complete process including the hydrogen production zone units (reformer reactor, high temperature gas shift reactor HTS and low temperature gas shift reactor LTS) and the purification zone units (absorber and methanator). Optimum production of hydrogen (87,404 MT/year) was obtained by fixing the temperatures in the reformer and the gas shift reactors (HTS & LTS) at 900 °C, 500 °C and 200 °C respectively while maintaining a pressure of 7 atm, and a steam to carbon ratio (S/C) of 4. Moreover, ~99% of the undesired CO₂ and CO gases were removed in the purification zone and a reduction of energy consumption of 77.5% was reached in the heating and cooling units of the process.     

Hydrogen embrittlement suscetibility on X-120 microalloyed steel as function of tempering temperature

This research work is focused on the hydrogen embrittlement (HE) effect on mechanical properties of X-120 microalloyed steel and to determine the hydrogen permeability parameters after tempering treatment at 200, 400, and 600 °C for 10 min. Stress-strain curves were obtained in as-received and tempered conditions, and permeability tests were carried out to determine the HE susceptibility. The results showed a microstructure composed of martensite-bainite, acicular-ferrite and retained austenite with no appreciable change on its morphology after tempering treatment. However, the microalloyed steel showed a decrease in its mechanical properties after charging conditions as tempering temperature increases. Fractography analysis revealed a decohesion and dislocation emission mechanism of HE which induce nucleation and crack growth. The index embrittlement (%EI) was related to the reduction in effective diffusion (D_eff) and increment of apparent concentration (C_app) due to the increment of irreversible traps as a function of the type of precipitates presented in tempering stages.     

Characterization of the cold ductility degradation after aging in centrifugally cast 20Cr32Ni+Nb alloy tube

The mechanical properties (yield stress, ultimate tensile stress and elongation) of alloy 20Cr32Ni + Nb subject to isochronal aging at temperatures between 670 and 820 °C for 200 h were investigated using samples extracted from a centrifugally cast tube. The results confirm the occurrence of embrittlement in the aged samples, with maximum embrittlement observed around 770 °C without significant gain in strength.     

Eliminating reversible hydrogen embrittlement in high-strength martensitic steel by an electric current pulse

Hydrogen embrittlement has been a great issue in ultrahigh-strength automotive steel applications. Few studies on solving hydrogen embrittlement have been conducted in terms of removing hydrogen, and most studies focus on improving the resistance to hydrogen embrittlement through microalloying. In this study, an electric pulse was used to solve hydrogen embrittlement by removing hydrogen at 120 Hz (frequency), 180 μs (duration), and 200 A (current intensity). The temperature of the samples reached 105 °C under these parameters. Compared with the samples heat treated at the same temperature, the precharged samples processed by electric pulses had a lower hydrogen content and less ductility loss. Moreover, electric pulse processing can also reduce the approximate equilibrium concentration of hydrogen compared with heat treatment. This is due to the introduction of electrical free energy, which reduces the barrier to hydrogen diffusion, and pulsed electric current also accelerates the hydrogen diffusion.     

Effects of hydrogen pressure and prior austenite grain size on the hydrogen embrittlement characteristics of a press-hardened martensitic steel

The effects of hydrogen gas pressure and prior austenite grain size (PAGS) on the susceptibility of a 22MnB5 press-hardened martensitic steel (PHS) to hydrogen embrittlement were studied. The hydrogen test apparatus at NIST-Boulder was modified for tensile testing of plate-type and sheet-type specimens in gaseous hydrogen. This modification made it possible to evaluate the slow strain rate tensile (SSRT) properties of the PHS with three different PAGS at various hydrogen pressures (0.21 MPa–5.5 MPa). SSRT testing in gaseous hydrogen resulted in significant reductions of both the tensile strength and ductility, as compared to those measured in air. In addition, the presence of gaseous hydrogen resulted in a transition in fracture morphology from the near-45° slant fracture to a more brittle fracture along a plane perpendicular to the tensile axis. The hydrogen-affected fracture zones were connected to the sheet specimen free surfaces, signifying the effect of external hydrogen. The fracture surfaces of the hydrogen-embrittled specimens contained relatively flat, “cleavage-like” facets, the size of which depended on the PAGS or packet size. The PHS having the largest PAGS represented generally larger secondary cracks and straighter crack paths in addition to a greater area fraction of the “cleavage-like” facets, likely indicative of a lower frequency of crack deflections. Compared to the largest PAGS condition, the two PHS with smaller PAGS were more resistant to the hydrogen-induced fracture especially at relatively low hydrogen gas pressures (<0.52 MPa). In contrast, with an increase in hydrogen pressure, all PHS specimens exhibited significant decreases in tensile strength and ductility. The positive effect of refining martensitic microstructure, at the low hydrogen pressures, is likely associated with improved toughness of the smaller grain-sized specimens.     

The performance of green carbon as a backbone for hydrogen storage materials

We investigate the use of carbonized bamboo, which has an organic porous structure, as a hydrogen storage material. Bamboo samples were thermally treated at 800, 900, 1000, and 1100 °C for 24 h. The pore size and hydrogen storage capacity of each sample were measured by N₂ and H₂ gas sorption up to 1.13 bar at 77 K. The maximum hydrogen storage was exhibited by the sample treated at 900 °C, which reached 1.35 wt% at 1.13 bar/77 K. The results showed that the bamboo, one of the green carbons, has the potential to be used as an environmental-friendly carbon backbone for hybrid hydrogen storage materials.     

Hydrogen embrittlement characteristics of hot-stamped 22MnB5 steel

Hydrogen embrittlement (HE) characteristics of 22MnB5 steel (U-bent specimen) manufactured using hot-stamping process at various temperatures were experimentally and numerically investigated. Steel resistance to HE was examined through delayed failure tests under static and cyclic loading during hydrogen charging. First, the low cyclic loading caused severe HE, in which a clear difference in the extent of HE was obtained depending on the hot-stamped sample, which directly affected the microstructural characteristics and stress–strain distribution. The hot-stamped samples with large martensite phase showed low resistance to HE compared with those with small martensite phase because of the high concentration of hydrogen trapped in the phase boundaries. Moreover, the dual phase (ferrite and martensite) of the hot-stamped samples reduced their resistance to HE, which is caused by the hydrogen trapped in the laminar-shaped pearlite phase. The resistance to HE was improved by low-temperature heating at 200 °C for 1 h because of the generation of ε-carbides as trap sites as they render the hydrogen non-diffusible. Furthermore, the internal strain in the U-bent sample could accelerate HE because of the high concentration of hydrogen. These results were verified by experimental and numerical analyses. Thus, the hydrogen trapping mechanism was proposed as a valid mechanism for HE in 22MnB5.     

Hydrogen storage – Industrial prospectives

The topic of this paper is to give an historical and technical overview of hydrogen storage vessels and to detail the specific issues and constraints of hydrogen energy uses. Hydrogen, as an industrial gas, is stored either as a compressed or as a refrigerated liquefied gas. Since the beginning of the last century, hydrogen is stored in seamless steel cylinders. At the end of the 60 s, tubes also made of seamless steels were used; specific attention was paid to hydrogen embrittlement in the 70 s. Aluminum cylinders were also used for hydrogen storage since the end of the 60 s, but their cost was higher compared to steel cylinders and smaller water capacity. To further increase the service pressure of hydrogen tanks or to slightly decrease the weight, metallic cylinders can be hoop-wrapped. Then, with specific developments for space or military applications, fully-wrapped tanks started to be developed in the 80 s. Because of their low weight, they started to be used in for portable applications: for vehicles (on-board storages of natural gas), for leisure applications (paint-ball) etc… These fully-wrapped composite tanks, named types III and IV are now developed for hydrogen energy storage; the requested pressure is very high (from 700 to 850 bar) leads to specific issues which are discussed. Each technology is described in term of materials, manufacturing technologies and approval tests. The specific issues due to very high pressure are depicted.