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.     

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.     

Selection of structural materials for hydrogen pipelines and storage vessels

The feasibility, both of using present transmission lines, and of developing new resistant line pipe and pressure vessel steels, is explored. Both appear possible but simple extrapolation of existing conditions for natural gas storage and transmission is inappropriate. Specifically, composition, heat treatment and weldability requirements are more severe for hydrogen transport; pressure vessel steels are susceptible to hydrogen embrittlement and thus seamless vessels and/or protective liners are required; and high-strength resistant steels must be developed for compressors, valves and related equipment. These problems, while solvable, provide an urgent challenge to the materials engineer.     

Challenges associated with hydrogen storage systems due to the hydrogen embrittlement of high strength steels

Hydrogen is a promising alternative to fossil fuels and is extensively used in process industries. The transportation industry is gearing up towards the use of fuel cells where hydrogen, as a fuel, plays a major role. Irrespective of the application/sector, safe handling and storage of hydrogen are crucial. Storing hydrogen in metal cylinders as compressed gas is a common practice. However, hydrogen embrittlement is a challenge in such cases and needs to be addressed. Embrittlement leads to the deterioration of the metal cylinders in which the hydrogen gas is stored and is therefore a safety concern. High-strength steels are more susceptible to hydrogen embrittlement as susceptibility to the phenomenon increases with strength. Safe hydrogen storage systems demand improved storage materials and modification of existing ones. Few materials and methods are available to reduce hydrogen diffusion in these steels. However, a detailed microstructural analysis of high-strength steel is necessary to make it a hydrogen-impermeable material. Multilayered coatings can be effective in the prevention of embrittlement. In this article, the analysis of current hydrogen storage methods along with the various coatings and deposition techniques that can reduce hydrogen permeation in high-strength steels is carried out.     

Assessment of resistance to fatigue crack growth of natural gas line pipe steels carrying gas mixed with hydrogen

Hydrogen embrittlement of line pipe steels in the natural gas transmission and distribution network is investigated. The objective is to assess whether the existing network can be used to safely transport a mixture of hydrogen and natural gas. The surveyed literature indicates that the hydrogen-induced acceleration of fatigue crack growth induced by natural gas pressure fluctuations can be the most probable type of failure. We analyzed the fatigue crack growth in line pipe steels containing a long axial crack in the inner diameter (ID) surface by accounting for random cyclic loading due to random and realistic pressure fluctuations, crack closure, and accurate calculation of the stress intensity factor. Using the available experimental data for the crack growth rate vs. stress intensity factor range in the presence of hydrogen, we simulated crack growth over a period of 100 years. The results show that under typical pressure fluctuations in the natural gas network, cracks with depths less than 40% of the wall thickness will never reach depths equal to 75% of the wall thickness. This is a conservative estimate that results from i) the nature of the geometry of the initial flaw in the ID surface that we used in the analysis, ii) the fact that the existing experimental data for the effect of hydrogen on the Paris law are for pressures that are orders of magnitude larger than the partial pressures intended for the hydrogen gas in the mixture, and iii) the experimental data are for fatigue crack growth in pure hydrogen gas without impurities normally present in natural gas, such as oxygen or methane, that can inhibit hydrogen uptake.     

Effect of vanadium content on hydrogen embrittlement of 1400 MPa grade high strength bolt steels

In this work, the hydrogen embrittlement (HE) characteristics of 1400 MPa bolt steels with three different vanadium contents of 0, 0.17 wt% and 0.34 wt% were evaluated. The characteristics of the microstructure and dislocation density of the experimental steels were analyzed, and their effects on HE were also discussed. The results showed that with increasing V content, the HE resistance of the experimental steels was improved, and the experimental steel with the highest V content possessed the best HE resistance. The V-precipitates of steels with V contents of 0.17 wt% and 0.34 wt% were reversible hydrogen traps, and the inhibitory effect of V-precipitates on hydrogen-dislocation interactions improved HE resistance. In addition, a lower dislocation density and finer martensitic structure were also beneficial for hindering hydrogen-induced cracking (HIC).     

Resistance of pearlite against hydrogen-assisted fatigue crack growth

Recent progress in realizing hydrogen society requires higher-strength steels having decent hydrogen embrittlement resistance via optimized microstructural controls. The present communication first reports the fatigue crack growth (FCG) property of pearlitic steel in a high-pressure, i.e., 90 MPa, hydrogen gas environment to probe this standard microstructure's potency for becoming a constructive reinforcing agent in future hydrogen-compatible structural materials. As-transformed eutectoid steel with 1080 MPa-tensile strength exhibited hydrogen-induced FCG acceleration to a lesser extent relative to martensite with an equivalent strength level and occasionally to pure ferritic iron. Furthermore, the superiority over martensite was augmented under slow loading-rate conditions, suppressing time-dependent cracking, a critical issue in implementing defect tolerant design on high-strength steels for hydrogen gas applications.     

Overview of hydrogen embrittlement in high-Mn steels

Hydrogen and fuels derived from it will serve as the energy carriers of the future. The associated rapidly growing demand for hydrogen energy-related infrastructure materials has stimulated multiple engineering and scientific studies on the hydrogen embrittlement resistance of various groups of high performance alloys. Among these, high-Mn steels have received special attention owing to their excellent strength – ductility – cost relationship. However, hydrogen-induced delayed fracture has been reported to occur in deep-drawn cup specimens of some of these alloys. Driven by this challenge we present here an overview of the hydrogen embrittlement research carried out on high-Mn steels. The hydrogen embrittlement susceptibility of high-Mn steels is particularly sensitive to their chemical composition since the various alloying elements simultaneously affect the material's stacking fault energy, phase stability, hydrogen uptake behavior, surface oxide scales and interstitial diffusivity, all of which affect the hydrogen embrittlement susceptibility. Here, we discuss the contribution of each of these factors to the hydrogen embrittlement susceptibility of these steels and discuss pathways how certain embrittlement mechanisms can be hampered or even inhibited. Examples of positive effects of hydrogen on the tensile ductility are also introduced.     

Hydrogen related degradation in pipeline steel: A review

To support our increasing energy demand, steel pipelines are deployed in transporting oil and natural gas resources for long distances. However, numerous steel structures experience catastrophic failures due to the evolution of hydrogen from their service environments initiated by corrosion reactions and/or cathodic protection. This process results in deleterious effect on the mechanical strength of these ferrous steel structures and their principal components. The major sources of hydrogen in offshore/subsea pipeline installations are moisture as well as molecular water reduction resulting from cathodic protection. Hydrogen induced cracking comes into effect as a synergy of hydrogen concentration and stress level on susceptible steel materials, leading to severe hydrogen embrittlement (HE) scenarios. This usually manifests in the form of induced-crack episodes, e.g., hydrogen induced cracking (HIC), stress-oriented hydrogen induced cracking (SOHIC) and sulfide stress corrosion cracking (SSCC). In this work, we have outlined sources of hydrogen attack as well as their induced failure mechanisms. Several past and recent studies supporting them have also been highlighted in line with understanding of the effect of hydrogen on pipeline steel failure. Different experimental techniques such as Devanathan–Stachurski method, thermal desorption spectrometry, hydrogen microprint technique, electrochemical impedance spectroscopy and electrochemical noise have proven to be useful in investigating hydrogen damage in pipeline steels. This has also necessitated our coverage of relatively comprehensive assessments of the effect of hydrogen on contemporary high-strength pipeline steel processed by thermomechanical controlled rolling. The effect of HE on cleavage planes and/or grain boundaries has prompted in depth crystallographic texture analysis within this work as a very important parameter influencing the corrosion behavior of pipeline steels. More information regarding microstructure and grain boundary interaction effects have been presented as well as the mechanisms of crack interaction with microstructure. Since hydrogen degradation is accompanied by other corrosion-related causes, this review also addresses key corrosion causes affecting offshore pipeline structures fabricated from steel. We have enlisted and extensively discussed several recent corrosion mitigation trials and performance tests in various media at different thermal and pressure conditions.     

The synergistic effects of hydrogen embrittlement and transient gas flow conditions on integrity assessment of a precracked steel pipeline

We are reporting in this study the hydrogen permeation in the lattice structure of a steel pipeline designed for natural gas transportation by investigating the influence of blending gaseous hydrogen into natural gas flow and resulted internal pressure values on the structural integrity of cracked pipes. The presence of cracks may provoke pipeline failure and hydrogen leakage. The auto-ignition of hydrogen leaks, although been small, leads to a flame difficult to be seen. The latter makes such a phenomenon extremely dangerous as explosions became very likely to happen. In this paper, a reliable method is presented that can be used to predict the acceptable defect in order to reduce risks caused by pipe failure due to hydrogen embrittlement. The presented model takes into account the synergistic effects of transient gas flow conditions in pipelines and hydrogen embrittlement of steel material due to pressurized hydrogen gas permeation. It is found that blending hydrogen gas into natural gas pipelines increases the internal load on the pipeline walls due to overpressure values that may be reached in a transient gas flow regime. Also, the interaction between transient hydrogen gas flow and embrittlement of API 5L X52 steel pipeline was investigated using Failure Assessment Diagram (FAD) and the results have shown that transient flow enhances pipeline failure due to hydrogen permeation. It was shown that hydrogen embrittlement of steel pipelines in contact with the hydrogen environment, together with the transient gas flow and significantly increased transient pressure values, also increases the probability of failure of a cracked pipeline. Such a situation threatens the integrity of high stress pipelines, especially under the real working conditions of hydrogen gas transportation.     

Research and demonstration on hydrogen compatibility of pipelines: a review of current status and challenges

Hydrogen transportation by pipelines gradually becomes a critical engineering route in the worldwide adaptation of hydrogen as a form of clean energy. However, due to the hydrogen embrittlement effect, the compatibility of linepipe steels and associated welds with hydrogen is a major concern when designing hydrogen-carrying pipelines. When hydrogen enters the steels, their ductility, fracture resistance, and fatigue properties can be adversely altered. This paper reviews the status of several demonstration projects for natural gas-hydrogen blending and pure hydrogen transportation, the pipeline materials used and their operating parameters. This paper also compares the current standards of materials specifications for hydrogen pipeline systems from different parts of the world. The hydrogen compatibility and tolerance of varying grades of linepipe steels and the relevant testing methods for assessing the compatibility are then discussed, and the conservatism or the inadequacies of the test conditions of the current standards are pointed out for future improvement.     

Establishment of an in-situ small punch test method for characterizing hydrogen embrittlement behaviors under hydrogen gas environments and new influencing factor

The hydrogen embrittlement (HE) behaviors of structural materials used to handle hydrogen must be tested at their use environments. In this study, an in-situ small punch (SP) test method was established to characterize HE behaviors of SA372 and STS304 steels under hydrogen gas environments at high pressures and low temperatures. In addition, a new influencing factor, relative reduction of thickness (RRT) was proposed to quantify the HE sensitivity of structural steels. Under 10 MPa H₂ gas environment, load-displacement curves obtained and fractographic morphologies of the recovered specimens were analyzed to investigate the HE behaviors based on punch velocity and test temperature. When the HE sensitivity was evaluated by RRT, STS304 steel appeared to be vulnerable to HE as compared to SA372 steel across the tested temperature range. As a result, it was found that in-situ SP test and RRT can be used to quantify the HE sensitivity for structural materials screening regardless of test environments.     

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.     

A focused review of the hydrogen storage tank embrittlement mechanism process

Hydrogen embrittlement is a widely known phenomenon in high-strength and storage materials. Hydrogen embrittlement is responsible for subcritical crack growth in material, fracture initiation, subsequent loss in mechanical properties, and catastrophic failure. Hydrogen is induced in the material during an electrochemical reaction between the hydrogen, storage materials, and high-pressure gaseous hydrogen environment. Various mechanisms which are responsible for crack development, growth, and fracture have been deliberated and reported. However, the fundamental mechanism of hydrogen embrittlement remains unclear. Several techniques such as linearly increasing stress test techniques (LIST), constant extension rate test (CERT) and slow strain rate testing (SSRT), thermal desorption spectroscopy (TDS), permeation testing (PT), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) have been utilized to determine the amount of hydrogen diffused and available in the hydrogen storage material. The review intends to categorize and provide a clear understanding of the degradation mechanism that occurs during hydrogen embrittlement. The improvement in mitigating the hydrogen embrittlement degradation as a function of modifying the structure and surfaces of the material is established. Prospects for addressing hydrogen embrittlement degradation through further experimental and numerical research are suggested. Lastly, this paper through recommendation endeavors to prevent hydrogen storage tank degradation and reduces high costs associated with the replacement of the component in renewable energy applications.     

Effect of microstructure inhomogeneity on hydrogen embrittlement susceptibility of X80 welding HAZ under pressurized gaseous hydrogen

Hydrogen embrittlement (HE) of high-grade pipeline welded joint is a threat to hydrogen gas transport. In this research, slow strain rate tension (SSRT) tests in high-pressure hydrogen gas, combined with hydrogen permeation tests and microstructure analysis were conducted on X80 steel, intercritical heated-affected zone (ICHAZ), fine-grained heat-affected zone (FGHAZ) and coarse-grained heat-affected zone (CGHAZ). The change of HE susceptibility from high to low was CGHAZ, FGHAZ, ICHAZ, and base metal. Microstructure was the important factor influencing hydrogen permeation and susceptibility to HE. Susceptibility to HE was increased in the order of “fine-grained massive ferrite (MF) and acicular ferrite (AF)”, “fine-grained granular bainite (GB) and MF”, “coarse-grained GB and bainite ferrite (BF) embedded with martensite-austenite (M-A) constitute”. The fine-grained MF and AF in base metal with lower hydrogen diffusivity can impede the embrittlement behaviour, while the coarse-grained GB and BF with higher hydrogen diffusivity in CGHAZ increased its susceptibility to HE.     

A systematic study on the influence of electrochemical charging conditions on the hydrogen embrittlement behaviour of a pipeline steel

Although hydrogen embrittlement (HE) has been the subject of extensive research over the past century, a systematic study on the HE susceptibility of steels under different electrochemical charging conditions has been lacking. This study specifically targets this knowledge gap by evaluating the HE behaviour of a typical pipeline steel X65 after hydrogen-charging in acidic, neutral, and alkaline electrolytes that simulate various industrial environments. Results from a series of experiments show that the HE susceptibility of X65 steel varied significantly with hydrogen-charging electrolytes and, to a smaller extent, with electrochemical charging variables. The highest and lowest HE susceptibilities were found from specimens charged in acidic and alkaline electrolytes, respectively. An increase in yield strength was observed for almost all hydrogen-charged specimens, regardless of the charging conditions. Under severe electrochemical charging conditions, blistering was detected and mechanical properties were substantially decreased. Discussion has been made in comprehending these relationships.     

Material performance of age-hardened beryllium–copper alloy,CDA-C17200, in a high-pressure,gaseous hydrogen environment

In order to develop safer and more energy-efficient, hydrogen pre-cooling systems for use in hydrogen refueling stations, it is necessary to identify a high-strength metallic material with greater thermal conductivity and lower susceptibility to hydrogen embrittlement, as compared with ordinary, stable austenitic stainless steels. To accomplish this task, the hydrogen compatibility of a precipitation-hardened, high-strength, copper-based alloy was investigated by slow-strain-rate tensile (SSRT), fatigue-life, fatigue-crack-growth (FCG) and fracture toughness tests in 115-MPa hydrogen gas at room temperature. The hydrogen solubility and diffusivity of the alloy were also determined. The hydrogen solubility of the alloy was two or three orders of magnitude lower than that of austenitic stainless steels. The alloy also demonstrated absolutely no hydrogen-induced degradation of its strength properties, a factor which could contribute to the reduction of costs related to the construction and maintenance of hydrogen refueling stations, owing to the downsizing and improved cooling performance of the pre-cooling systems.     

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 cryogenic and tempered treatment on the hydrogen embrittlement susceptibility of TRIP-780 steels

Cryogenic and Tempered (CT) treatments were performed on commercial TRIP 780 steels in order to reduce the hydrogen embrittlement (HE) susceptibility. The HE behavior was assessed immediately after cathodically hydrogen charging on both CT treated and untreated samples. Slow strain-rate tensile (SSRT) tests were conducted to evaluate their HE performance. It is shown that samples with CT treatments behave higher resistance to HE comparing with their untreated counterparts. Meanwhile, microstructure characterization and magnetization measurements were adopted to reveal the evolution of retained austenite (A_r) and its stabilization due to CT treatment. Moreover, hydrogen-induced cracking (HIC) accompanied with martensite phase transformation in TRIP steel was studied by electron backscattering diffraction (EBSD) technique and it was proved that cracks initiated from the fresh untempered martensite inherited from phase transformation of unstable A_r upon straining. Finally, results in this study demonstrate the relationship between A_r stability and HE susceptibility, and provide a possible solution to reduce HE susceptibility in TRIP steels.     

Structural materials use in a hydrogen energy economy

Many common structural alloys are subject to gross embrittlement by hydrogen. Since hydrogen-induced fracture in such cases can result in catastrophic failures of equipment, it is very important to consider appropriate design measures and alternative materials choices for hydrogen service. There are two areas of concern for hydrogen energy applications: systems to generate hydrogen or hydrogen-bearing gases at high temperatures and pressures, and high pressure hydrogen transmission and storage systems. It appears possible in each area to identify the desirable classes of structural materials for hydrogen service.