Effects of CH4 and CO on hydrogen embrittlement susceptibility of X80 pipeline steel in hydrogen blended natural gas

The slow strain rate tensile experiments are carried out to investigate the tensile properties of X80 pipeline steel in hydrogen blended natural gas environments with different H₂/CH₄/CO contents. Mechanical properties and fracture morphologies are further analyzed. The results show that the hydrogen embrittlement susceptibility of X80 steel can be inhibited by the presence of CH₄/CO, and the inhibition mechanisms are discussed. When the CH₄ contents increase above 20 vol%, the inhibition on hydrogen embrittlement of X80 steel is stabilized. By comparison, the inhibitory effect of CO is more significant.     

Effect of low partial hydrogen in a mixture with methane on the mechanical properties of X70 pipeline steel

In this study, the effect of a low partial hydrogen in a mixture with natural gas on the tensile, notched tensile properties, and fracture toughness of pipeline steel X70 is investigated. An artificial HE aging is simulated by exposing the tested sample to the mixture gas condition for 720 h. In addition, a series of tests is conducted in ambient air and 10 MPa of 100% He and H₂. Overall, 10 MPa of 100% H₂ significantly degrades the mechanical properties of an X70 pipeline steel. However, it is observed that the 10 MPa gas mixture with 1% H₂ does not affect the mechanical properties when tested with a smooth tensile specimen. In the notched tensile test, a significant reduction in loss in the area is observed when tested with a notched specimen with a notch radius of 0.083 mm. It is also confirmed that a 10-MPa gas mixture with 1% H₂ causes a remarkable reduction in the toughness. The influence of the exposure time to 1% hydrogen in a mixture with natural gas was found to be minor.     

Comparative study of embrittlement of quenched and tempered steels in hydrogen environments

The study of steels which guarantee safety and reliability throughout their service life in hydrogen-rich environments has increased considerably in recent years. Their mechanical behavior in terms of hydrogen embrittlement is of utmost importance. This work aims to assess the effects of hydrogen on the tensile properties of quenched and tempered 42CrMo4 steels. Tensile tests were performed on smooth and notched specimens under different conditions: pre-charged in high pressure hydrogen gas, electrochemically pre-charged, and in-situ hydrogen charged in an acid aqueous medium. The influence of the charging methodology on the corresponding embrittlement indexes was assessed. The role of other test variables, such as the applied current density, the electrolyte composition, and the displacement rate was also studied. An important reduction of the strength was detected when notched specimens were subjected to in-situ charging. When the same tests were performed on smooth tensile specimens, the deformation results were reduced. This behavior is related to significant changes in the operative failure micromechanisms, from ductile (microvoids coalescence) in absence of hydrogen or under low hydrogen contents, to brittle (decohesion of martensite lath interfaces) under the most stringent conditions.     

Influence of hydrogen pressure on fatigue properties of X80 pipeline steel

The low-cycle fatigue and fatigue crack growth (FCG) properties of X80 pipeline steel in hydrogen atmosphere were determined to investigate the variation of hydrogen pressure and its influence on fatigue life. The test environment was switched to a hydrogen atmosphere after 1000, 3000, or 5000 cycles of pre-fatigue testing in a nitrogen atmosphere. Notch tensile tests were conducted in nitrogen and hydrogen atmospheres after the specimens were pre-fatigued for 3000 or 5000 cycles. The results showed that the cycles to failure of X80 decreased exponentially with increasing hydrogen pressure. When the displacement amplitude (DA) values remained steady (below 3000 cycles), the X80 steels showed no noticeable deterioration in the fatigue properties with or without hydrogen. When the DA values increased (above 5000 cycles), cracks propagated slowly and fatigue properties were strongly reduced in the hydrogen atmosphere, but not in nitrogen. Hydrogen-accelerated crack growth dominates the reduction of fatigue life below 0.6 MPa of hydrogen pressure. Hydrogen-accelerated crack initiation plays a more important role than FCG in the reduction of fatigue life with increasing hydrogen pressure.     

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.     

Materials aspects associated with the addition of up to 20 mol% hydrogen into an existing natural gas distribution network

The introduction of hydrogen into the UK natural gas main has been reviewed in terms of how materials within the gas distribution network may be affected by contact with up to 80% Natural Gas (NG)/20 mol% hydrogen blend at up to 2 barg. A range of metallic, polymeric and elastomeric materials in the gas distribution network (GDN) were assessed via a combination of literature review and targeted practical test programmes.The work considered:? The effect of hydrogen on metallic materials identified in the network.? The effect of hydrogen on polymeric materials identified in the network.? The effect of hydrogen exposure on polyethylene pipeline joining and repair techniques (squeeze-off, and socket and saddle electrofusion joints)The experimental work involved soaking materials, under pressure conditions representative of the network, in 100% hydrogen, 20% hydrogen in methane, and 100% methane. For the metal samples, the test programme involved the assessment of hydrogen uptake on the tensile properties. For the polyethylene samples, the test programme looked at the assessment of possible hydrogen absorption/desorption and its effect on electrofusion jointing.The trials concluded that the majority of metallic materials showed no significant deterioration in mechanical (tensile) properties when stored in hydrogen environments compared to those stored in analogous methane or blended gas atmospheres up to 2 barg. Polymeric materials showed no deterioration to efficiency of squeeze-off or collar electrofusion in socket or shoulder orientations following soaking in hydrogen, methane or hydrogen blends.     

Effect of hydrogen on the tensile properties of 42CrMo4 steel quenched and tempered at different temperatures

The influence of hydrogen on the mechanical behaviour of a 42CrMo4 tempered martensitic steel was investigated by means of tensile tests on both smooth and circumferentially-notched round-bar specimens pre-charged with gaseous hydrogen in a pressurized reactor.Hydrogen solubility was seen to decrease with increasing tempering temperature. Moreover, hydrogen embrittlement measured in notched specimens was much greater in the grades with higher hardness, tempered at the lowest temperatures, where a change in the fracture micromechanism from ductile in the absence of hydrogen to intermediate and brittle in the presence of hydrogen was clearly observed. Results were discussed through FEM simulations of local stresses acting on the process zone.     

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.     

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.     

The effects of double notches on the mechanical properties of a high-strength pipeline steel under hydrogen atmosphere

Tensile tests and fatigue life tests are performed on double-notched specimens in hydrogen and nitrogen atmospheres to investigate the effects of double notches on the mechanical properties of a high strength pipeline steel. The results show that the fracture occurs at the notch with a lower stress concentration factor (Kt), which is governed by the combination of the stress concentration and the strain hardening caused by plastic deformation in the tensile process. Hydrogen gas accelerates the crack initiation and growth, but it doesn't affect the competitive mechanism of stress concentration and strain hardening.     

模拟沼气发动机掺氢燃烧的试验研究

在一台改装的单缸柴油机上进行了模拟沼气掺氢燃烧的试验。模拟沼气由天然气含量为50%～80%,CO2含量为20%～50%组成,掺烧氢气的比例为10%～40%。结果表明,随着模拟沼气中CO2比例的增加,发动机动力性降低,排放污染物中CO和NOx排放减少,但HC排放增加。适当增加模拟沼气发动机的掺氢比例,发动机缸内最高压力和最大转矩升高,过多的掺氢比例会降低发动机的动力性。排放污染物中随着掺氢比例的增加,CO排放增多,HC排放减少,NOx排放量与模拟沼气中CO2的比例有关。     

Quantifying the hydrogen embrittlement of pipeline steels for safety considerations

In a near future, with an increasing use of hydrogen as an energy vector, gaseous hydrogen transport as well as high capacity storage may imply the use of high strength steel pipelines for economical reasons. However, such materials are well known to be sensitive to hydrogen embrittlement (HE). For safety reasons, it is thus necessary to improve and clarify the means of quantifying embrittlement. The present paper exposes the changes in mechanical properties of a grade API X80 steel through numerous mechanical tests, i.e. tensile tests, disk pressure test, fracture toughness and fatigue crack growth measurements, WOL tests, performed either in neutral atmosphere or in high-pressure of hydrogen gas. The observed results are then discussed in front of safety considerations for the redaction of standards for the qualification of materials dedicating to hydrogen transport.     

Recommendations on X80 steel for the design of hydrogen gas transmission pipelines

By limiting the pipes thickness necessary to sustain high pressure, high-strength steels could prove economically relevant for transmitting large gas quantities in pipelines on long distance. Up to now, the existing hydrogen pipelines have used lower-strength steels to avoid any hydrogen embrittlement. The CATHY-GDF project, funded by the French National Agency for Research, explored the ability of an industrial X80 grade for the transmission of pressurized hydrogen gas in large diameter pipelines. This project has developed experimental facilities to test the material under hydrogen gas pressure. Indeed, tensile, toughness, crack propagation and disc rupture tests have been performed. From these results, the effect of hydrogen pressure on the size of some critical defects has been analyzed allowing proposing some recommendations on the design of X80 pipe for hydrogen transport. Cost of Hydrogen transport could be several times higher than natural gas one for a given energy amount. Moreover, building hydrogen pipeline using high grade steels could induce a 10 to 40% cost benefit instead of using low grade steels, despite their lower hydrogen susceptibility.     

Effects of stress concentration on the mechanical properties of X70 in high-pressure hydrogen-containing gas mixtures

This study aims to investigate the mechanical properties of X70 pipeline steel under the synergistic influence of hydrogen and stress concentration. Slow strain rate tensile tests and low-cycle fatigue tests were performed on the specimens with different stress concentration factors (Kt) in 10 MPa nitrogen/hydrogen mixtures. Results show that the degradation degree of the ductility and fatigue life of X70 steel induced by hydrogen increases with the increase of Kt, and as the hydrogen partial pressure in mixtures increases, the influence of Kt on hydrogen-induced degradation increases as well. In addition, finite element analysis was performed via a modified hydrogen diffusion/plasticity coupled model to study the effect of Kt on hydrogen distribution in the specimens, which can influence the mechanical properties of X70. The maximum hydrogen concentration consistently appears at the notch tip of the specimen and increases with the increase of Kt, which is proposed to be one of the reasons for the severe hydrogen embrittlement of the specimens with large Kt. As the axial tensile force on the specimen increases, the maximum hydrogen concentration at the notch tip begins to be dominated by hydrogen in the normal interstitial lattice sites and, subsequently, in the trapping sites.     

Effect of hydrogen charging on the mechanical properties of advanced high strength steels

The present work investigates the influence of hydrogen on the mechanical properties of four multiphase high strength steels by means of tensile tests on notched samples. This was done by performing mechanical tests on both hydrogen charged and uncharged specimens at a cross-head displacement speed of 5 mm/min. A considerable hydrogen influence was observed, as the ductility dropped by 8–60%. In order to demonstrate the influence of diffusible hydrogen, some parameters in the experimental set-up were varied. After tensile tests, fractography was performed. It was found that hydrogen charging caused a change from ductile to transgranular cleavage failure near the notch with a transition zone to a fracture surface with ductile features near the centre.     

Effects of internal hydrogen and surface-absorbed hydrogen on the hydrogen embrittlement of X80 pipeline steel

Effects of internal hydrogen and surface-absorbed hydrogen on hydrogen embrittlement (HE) of X80 pipeline steel were investigated by using different strain rate tensile test, annealing and hydrogen permeation tests. HE of X80 pipeline steel is affected by internal hydrogen and surface-absorbed hydrogen, and the latter plays a major role due to its higher effective hydrogen concentration. The HE susceptibility decreases with increasing the strain rate because it is more difficult for hydrogen to be captured by dislocations at the high strain rate. Annealing at 200 °C can weakened HE caused by internal hydrogen, while it has little effect on HE caused by surface-absorbed hydrogen. HE of X80 pipeline steel is mainly determined by the behavior of dislocation trapping hydrogen, which can be attributed to the interaction between hydrogen and dislocation.     

Hydrogen induced blister cracking and mechanical failure in X65 pipeline steels

The present work aims to investigate the role of hydrogen induced blisters cracking on degradation of tensile and fatigue properties of X65 pipeline steel. Both tensile and fatigue specimens were electrochemically charged with hydrogen at 20 mA/cm² for a period of 4 h. Hydrogen charging resulted in hydrogen induced cracking (HIC) and blister formation throughout the specimen surface. Nearly all the blisters formed during hydrogen charging showed blister wall cracking (BWC). Inclusions mixed in Al-Si-O were found to be the potential sites for HIC and BWC. Slow strain rate tensile (SSRT) test followed by fractographic analysis confirmed significant hydrogen embrittlement (HE) susceptibility of X65 steel. Short fatigue crack growth framework, on the other hand, specifically highlighted the role of BWC on accelerated crack growth in the investigated material. Coalescence of propagating short fatigue crack with BWC resulted in rapid increase in the crack length and reduced the number of cycles for crack propagation to the equivalent crack length.     

Numerical simulation of leakage and diffusion distribution of natural gas and hydrogen mixtures in a closed container

The transportation and utilization of hydrogen blended natural gas have received extensive attention. The dangerous characteristics of hydrogen such as high diffusivity and wide flammability/explosion limit also increase the leakage risk of hydrogen blended natural gas. In this paper, a numerical model is established for the leakage and diffusion of hydrogen blended natural gas in a closed container. The evolution of the distribution, diffusion law and flammable area of different proportions of hydrogen blended natural gas after leaking into a closed container is investigated. The results show that the flammable area with low hydrogen ratios (20% and below) will disappear within 2.7 s–11.1 s after the leakage, which is relatively safer, while the high hydrogen ratio (80% and above) reaches 3875 s–4555 s with a significant increase in risk duration. After the 50% hydrogen ratio leakage, the thickness of the flammable area is higher than 15.67% for the 80% hydrogen ratio and 30.25% higher than pure hydrogen at 120 s after leakage, and the risk is higher in a short time. Due to the difference in the diffusion rates between methane and hydrogen, hydrogen diffuses to the middle and lower part of the enclosed container faster, and the risk in the middle and lower part also deserves attention.     

Effective use of hydrogen sulfide and natural gas resources available in the Black Sea for hydrogen economy

In this article, we propose a novel system to effectively deploy an integrated fuel processing system for hydrogen sulfide and natural gas resources available in the Black Sea to be used for a quick transition to the hydrogen economy. In this regard, the proposed system utilizes offshore wind and offshore photovoltaic power plants to meet the electricity demand of the electrolyzer. A PEM electrolyzer unit generates hydrogen from hydrogen sulfide that is available in the Black Sea deep water. The generated hydrogen and sulfur gas from hydrogen sulfide are stored in high-pressure tanks for later use. Hydrogen is blended with natural gas, and the blend is utilized for industrial and residential applications. The investigated system is modeled with the Aspen Plus software, and hydrogen production, blending, and combustion processes are analyzed accordingly. With the hydrogen addition up to 20% in the blend, the carbon dioxide emissions of combustion decrease from 14.7 kmol/h to 11.7 kmol/h, when the annual cost of natural gas is reduced from 9 billion $ to 8.3 billion $. The energy and exergy efficiencies for the combustion process are increased from 84% to 97% and from 62% to 72%, respectively by a 20% by volume hydrogen addition into natural gas.     

Effect of tensile stress on the hydrogen adsorption of X70 pipeline steel

The effect of stress on the cathodic hydrogen evolution behavior of X70 pipeline steel was investigated by electrochemical tests, tensile tests, and microstructural characterization. The results indicated that the tensile stress enhanced the activity of hydrogen adsorption sites on the metal surface, which was considered as the dominating factor a?ecting generation, adsorption, and permeation of hydrogen atoms. The subsurface hydrogen atom concentrations quantified by Cyclic voltammetry (CV) tests and the data calculated by hydrogen permeation experiments showed a good correspondence. The results indicated that the tensile stress enhanced the adsorption of hydrogen atoms on the surface and an inhibitory effect on the Tafel and Heyrovsky reaction, thereby leading to the increase of the subsurface hydrogen atom concentration, enhance the hydrogen embrittlement susceptibility of the X70 steel material as demonstrated by plasticity loss in the tensile tests.