Hydrogen embrittlement in different materials: A review

Hydrogen embrittlement (HE) is a widely known phenomenon in high strength materials. HE is responsible for subcritical crack growth in material, fracture initiation and catastrophic failure with subsequent loss in mechanical properties such as ductility, toughness and strength. This hydrogen is induced in the material during electrochemical reaction and high-pressure gaseous hydrogen environment. LIST, SSRT and TDS techniques are performed to know the effect in mechanical properties and amount of hydrogen available in the material. For microstructure examination SEM, FESEM and TEM are performed to know the effect of hydrogen in the internal crystal structure. Also, various mechanisms which are responsible for crack growth and final fracture are discussed. This paper deals with HE definition, mechanisms which causes HE, subcritical crack growth, the concentration of hydrogen measurement and prevention activities are discussed which act as a barrier for hydrogen diffusion.     

Detection of voids in hydrogen embrittled iron using transmission X-ray microscopy

Hydrogen embrittlement remains a barrier to widespread adoption of hydrogen as a carbon-neutral energy source. Here, hydrogen embrittlement mechanisms are investigated across length scales in iron using transmission X-ray microscopy (TXM), digital image correlation (DIC), and notched tensile testing during in-situ electrochemical hydrogen charging. TXM reveals void size and spatial distribution ahead of a propagating crack. We find hydrogen charging leads to voids within ～10 μm of the crack tip and suppression of voids beyond this distance. Near the crack tip, voids are elongated in the direction of the crack and are smaller than voids in an uncharged sample. In the presence of hydrogen, these voids lead to quasi-cleavage fracture and a sharper crack tip. DIC shows localization and reduction of plastic strain with hydrogen charging, and tensile testing reveals a reduction in fracture energy and elongation at failure. These results are discussed in the context of hydrogen embrittlement mechanisms.     

Compatibility of materials with hydrogen. Particular case: Hydrogen embrittlement of titanium alloys

A review of the effect of hydrogen on materials is addressed in this paper. General aspects of the interaction of hydrogen and materials, hydrogen embrittlement, low temperature effects, material suitability for hydrogen service and materials testing are the main subjects considered in the first part of the paper. As a particular case of the effect of hydrogen in materials, the hydride formation of titanium alloys is considered. Hydrogen absorption and the possible associated problems must be taken into account when considering titanium as a candidate material for high responsibility applications. The sensitivity of three different titanium alloys to the Hydrogen Assisted Stress Cracking phenomena has been studied by means of the Slow Strain Rate Technique (SSRT). The testing media have been sea water and hydrogen has been produced on the specimen surface during the test by cathodic polarization. Tested specimens have been characterized by metallography and scanning electron microscopy. Results obtained show that the microstructure of the materials, particularly the β-phase content, plays an important role on the sensitivity of the studied alloys to the Hydrogen Assisted Stress Cracking Phenomena.     

Unraveling the effect of dislocations and deformation-induced boundaries on environmental hydrogen embrittlement behavior of a cold-rolled Al–Zn–Mg–Cu alloy

The effect of dislocation substructure, and deformation-induced boundaries on the hydrogen embrittlement (HE) behavior and the fracture mechanism of a 7xxx series aluminum alloy was investigated using X-ray diffraction line-profile analysis, electron backscatter diffraction, transmission electron microscopy, thermal desorption spectroscopy, and visualization of hydrogen. Hydrogen resides at interstitial lattice sites, statistically-stored dislocations (SSDs), and high-angle boundaries (HABs). SSDs are not the main trap site affecting HE behavior of the alloy. However, the HABs with the high desorption energy act as an almost irreversible trap site, which strongly absorbs hydrogen. It was firstly reported that the higher density of HABs as a strong trap site in a deformed 7xxx series aluminum alloy leads to decreasing the possibility of building up a critical hydrogen concentration required for crack initiation in a typical HAB, resulting in an excellent hydrogen embrittlement resistance.     

Hydrogen embrittlement associated with strain localization in a precipitation-hardened Fe–Mn–Al–C light weight austenitic steel

Hydrogen embrittlement of a precipitation-hardened Fe–26Mn–11Al-1.2C (wt.%) austenitic steel was examined by tensile testing under hydrogen charging and thermal desorption analysis. While the high strength of the alloy (>1 GPa) was not affected, hydrogen charging reduced the engineering tensile elongation from 44 to only 5%. Hydrogen-assisted cracking mechanisms were studied via the joint use of electron backscatter diffraction analysis and orientation-optimized electron channeling contrast imaging. The observed embrittlement was mainly due to two mechanisms, namely, grain boundary triple junction cracking and slip-localization-induced intergranular cracking along micro-voids formed on grain boundaries. Grain boundary triple junction cracking occurs preferentially, while the microscopically ductile slip-localization-induced intergranular cracking assists crack growth during plastic deformation resulting in macroscopic brittle fracture appearance.     

Predictive environmental hydrogen embrittlement on fracture toughness of commercial ferritic steels with hydrogen-modified fracture strain model

In this work, a practical numerical model with few parameters was proposed for the prediction of environmental hydrogen embrittlement. The proposed method adopts hydrogen enhanced plasticity-based mechanism in a fracture strain model to describe hydrogen embrittlement. Fracture toughness degradation of three commercial steels SA372J70, AISI4130 and X80 in high pressure hydrogen environment were investigated. Firstly, governing equations for hydrogen distribution and material damage evolution was established. Hydrogen enhanced localized flow softening effect was coupled within fracture strain dependency on stress triaxiality. Then, the numerical implementation and identification process of model parameters was described. Model parameters of the investigated steels were determined based on experiment results from literatures. Finally, with the calibrated model, fracture toughness reduction of the steels was predicted in a wide range of hydrogen pressure. The prediction results were compared with experimental results. Reasonable accuracy was reached. The proposed method is an attempt to reach balance between physical accurate prediction and engineering practicality. It is promising to provide a simplified numerical tool for the design and fit for service evaluation of hydrogen storage vessels.     

Effect of hydrogen in advanced high strength steel materials

The effect of hydrogen in AHSS material (automobile and structural component) was discussed. Dual Phase steels were highly susceptible to hydrogen-related failure when working on hydrogen environment. The influence of hydrogen on TRIP steel was seen during fractographic examination where the brittle transgranular fracture was presented. TWIP steels results were inconsistent. The mechanisms which were responsible for crack growth are discussed. LIST and SSRT testing were performed for mechanical properties evaluation and SEM and TEM were used for microstructural examination of fractured samples. Simultaneous preventing methods to reduce hydrogen embrittlement such as coating, alloying and providing diffusion layer were discussed.     

Numerical simulation of the hydrogen trapping effect on crack propagation in API 5CT P110 steel under cathodic overprotection

The possibility of the development of hydrogen embrittlement processes increases in cathodic protection systems when cathodic overprotection occurs, and large amounts of hydrogen are produced. Additionally, the hydrogen embrittlement susceptibility of steel depends on solubility, diffusivity, and hydrogen trapping. This paper presents a numerical simulation of the reversible and irreversible hydrogen trapping effects on crack propagation in API 5CT P110 steel using a model based on a synthesis of fracture mechanics and continuum damage mechanics, in which the trapping term of the diffusion equation was replaced by the trapping terms of other more complete model. The simulation was performed with using a C(T) specimen loaded in the tensile opening mode, in the linear elastic regime, in plane strain state, under the action of a static mechanical loading and the effect of hydrogen. The simulations showed that the material degradation ahead of the crack tip increases with increases in hydrogen concentration at the crack tip due to the hydrogen trapping effect. Furthermore, the process of onset and crack growth in material with irreversible traps is slower than that in material with reversible traps. These results are consistent with macroscopic observations of the trapping effect, providing a better understanding of the hydrogen embrittlement in structural steels.     

Origin of hydrogen embrittlement in vanadium-based hydrogen separation membranes

Hydrogen embrittlement in metals is a challenging technical issue in the proper use of hydrogen energy. Despite extensive investigations, the underlying mechanism has not been clearly understood. Using atomistic simulations, we focused on the hydrogen embrittlement in vanadium-based hydrogen separation membrane. We found that, contrary to the conventional reasoning for the embrittlement of vanadium, the hydrogen-enhanced localized plasticity (HELP) mechanism is the most promising mechanism. Hydrogen enhances the nucleation of dislocations near the crack tip, which leads to the localized plasticity, and eventually enhances the void nucleation that leads to the failure. Those results provide an insight into the complex atomic scale process of hydrogen embrittlement in vanadium and also help us design a new alloy for hydrogen separation membranes.     

Electron microscope investigation on hydrogen storage materials: A review

Hydrogen energy is a highly efficient and renewable energy carrier. The rapid and sophisticated development of nanotechnologies has promoted the transition of hydrogen storage systems from gaseous/liquid to solid-state. In order to clarify the intrinsic relationship between structure and performance, and to understand the hydrogen absorption and desorption mechanism of materials, electron microscopy (EM) can effectively help us obtain a series of information such as particle size, phase and composition determination, morphology and structure of the materials at nanoscale. The most recent progress of advanced EM techniques applied in solid-state hydrogen storage materials are summarized, which should also inspire future research on energy storage related materials.     

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.     

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.     

Permeation barriers for hydrogen embrittlement prevention in metals – A review on mechanisms,materials suitability and efficiency

To develop large-scale use of hydrogen as an environmentally sensible alternative to fossil energy sources, the design of safe and innovative storage and transportation infrastructure is a crucial issue. In direct contact with the high-pressure hydrogen, structural materials, especially traditional alloys, are indeed susceptible to degradation of their mechanical properties due to the diffusion of hydrogen atoms into their atomic lattice structure. This phenomenon leads to materials' embrittlement and results in severe damage to the employed components. Therefore, the prevention of hydrogen atom diffusion is one key consideration to avoid its adverse effects on materials' mechanical properties. This paper aims to review the mechanisms and factors responsible for the hydrogen embrittlement phenomenon. The main specifications to fulfill while selecting appropriate materials are hence considered for hydrogen energy uses. Finally, the effective surface modification solutions are reviewed for implementation as a permeation barrier to protect the structural materials from hydrogen degradation.     

Crack propagation analysis of hydrogen embrittlement based on peridynamics

We introduced a coupled peridynamic hydrogen diffusion and fracture model to solve the hydrogen embrittlement fracture of low alloy steel AISI 4340. In this model, the influence of temperature on hydrogen diffusion coefficient is considered, and a new peridynamic constitutive analysis method is used to simulate the crack propagation of hydrogen embrittlement. We verified the model in 3D using the experimental test of the hydrogen embrittlement cracking process of AISI 4340 steel in 0.1 N H₂SO₄ solution from the literature. Considering different ambient temperatures, it is found that the crack propagation is highly similar to the experimental results. Based on the numerical analysis of peridynamics, the model can numerically simulate the hydrogen embrittlement fracture of AISI 4340 steel, and obtain a visual demonstration of the entire process of hydrogen atom diffusion and crack growth.     

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.     

Investigation on hydrogen induced cracking behaviors of Ni-base alloy

Hydrogen embrittlement of a Ni-base alloy at room temperature was investigated by slow strain rate tensile test (SSRT) under precharging or dynamic charging conditions. It was found that hydrogen embrittlement susceptibility of this alloy increased with increasing charging current density in both charging conditions. In-situ observation of hydrogen induced cracking revealed that surface crack initiation at both grain boundaries and slip bands, which should be attributed to decomposition of hydride phase during aging at room temperature. SSRT result exhibited that hydrogen diffusion in the alloy could be facilitated by deformation and as a result induced transgranular fracture of the sample. Both hydrogen induced cracking and the interaction between hydrogen and deformation played combined roles on hydrogen embrittlement of this alloy.     

Effect of inside diameter on design fatigue life of stationary hydrogen storage vessel based on fracture mechanics

Design fatigue life of stationary hydrogen storage vessel constructed of the practical materials of low alloy steels was analyzed based on fracture mechanics in hydrogen and air of 45, 85 and 105 MPa using cylindrical model with inside diameter (Di) of 150, 250 and 350 mm. Design fatigue life of five typical model materials was also analyzed to discuss the effect of Di on the design fatigue life by hydrogen-induced crack growth of the vessel. K_IC of all the practical materials qualified the leak before burst. Design fatigue life generally increased slightly with increasing Di in air, while design fatigue life by K_IH was much shorter than that in air. Hydrogen influence on design fatigue life increased with increasing Di due to that K_I at initial crack increased with increasing Di. The design fatigue life data of the model materials under the conditions of Di, pressure, ultimate tensile strength, K_IH, fatigue crack growth rate and regulations in both hydrogen and air were proposed quantitatively for materials selection and development for stationary hydrogen storage vessel.     

Potential structural material problems in a hydrogen energy system

Potential structural material problems that may be encountered in the three components of a hydrogen energy system—production, transmission/storage, and utilization—have been identified. Hydrogen embrittlement, corrosion, oxidation, and erosion may occur during the production of hydrogen. Hydrogen embrittlement is of major concern during both transmission and utilization of hydrogen. Specific materials research and development programs necessary to support a hydrogen energy system are described. An awareness of probable shortages of strategic materials has been maintained in these suggested programs.     

Dependence of hydrogen embrittlement on hydrogen in the surface layer in type 304 stainless steel

Hydrogen embrittlement (HE) together with the hydrogen transport behavior in hydrogen-charged type 304 stainless steel was investigated by combined tension and outgassing experiments. The hydrogen release rate and HE of hydrogen-charged 304 specimens increase with the hydrogen pressure for hydrogen-charging (or hydrogen content) and almost no HE is observed below the hydrogen content of 8.5 mass ppm. Baking at 433 K for 48 h can eliminate HE of the hydrogen-charged 304 specimen, while removing the surface layer will restore HE, which indicates that hydrogen in the surface layer plays the primary role in HE. Scanning electron microscopy (SEM) and scanning tunnel microscopy (STM) observations show that particles attributed to the strain-induced α′ martensite formation break away from the matrix and the small holes form during deformation on the specimen surface. With increasing strain, the connection among small holes along {111} slip planes of austenite will cause crack initiation on the surface, and then the hydrogen induced crack propagates from the surface to interior.     

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.