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We investigated the influence of two fillers-CB (carbon black) and silica-on the H

This study investigated the effect of the hydrogen charging time on the hydrogen embrittlement of hot-rolled and accelerated-cooling treated API X70 steel by using the electrochemical hydrogen charging method. Tensile and V-notch Charpy impact test were completed for the specimens of hydrogen charged for 0, 2, 4, and 10 h, and then microstructural observation were performed. The tensile and yield strength tended to decrease slightly and the total elongation started to decrease rapidly up to 2 h charging time and then these gradually decreased with the hydrogen charging time. The post-uniform elongation increased slightly after the holding time of 2 h due to the occurrence of two-step stress reduction phenomenon and its mechanism has suggested. The effect of the hydrogen embrittlement on impact absorption energy according to the hydrogen charging time were also investigated. The fracture surface of the hydrogen charged ones are generally composed of cleavage fracture surfaces. It was demonstrated that the external cracks were formed on the outside of tensile tested specimen and the external shape of the fracture portion was fractured without large elongation at hydrogen charged specimens.

Hydrogen embrittlement has been recognized as one of major degradation mechanisms causing the decrease of ductility and fracture toughness of several kinds of materials. In accordance with the demand for hydrogen fuels, it becomes more important to ensure safety of relevant facilities like pressure vessels, storage tanks and so on. The objective of this study is to examine fracture resistance of American Petroleum Institute (API)-X70 steel under highly pressurized hydrogen gaseous condition. The extended finite element method (XFEM) was adopted to predict J-R curves via a crack growth simulation approach. At first, preliminary analyses for SM490A carbon steel were carried out to demonstrate applicability of the XFEM, of which result was comparable to test data within 14 %. Subsequently, iterative numerical analyses were conducted to calibrate appropriate damage parameters for the API-X70 steel by using notched round bar specimens. Finally, crack growth simulations of 1T-compact tension (CT) specimens were performed adopting the calibrated parameters. JIC values determined from predicted J-R curves were compared with 1/2T-CT CTOD test data and relevant constraint effect was discussed.

We introduce a volumetric analysis technique to characterize the solubility of hydrogen dissolved in polymers and its diffusion coefficient by electrical capacitance measurement electrodes to determine the water level in graduated cylinders. This new and simple technique measures the volume of hydrogen released from rubber inside a graduated cylinder after a sample is exposed to high-pressure hydrogen and subsequent decompression. A diffusion analysis program is utilized to determine the total uptake (C0) and diffusivity (D) of hydrogen, which are used to calculate the solubility (S) and permeability (P). This method is applied to spherical rubber samples of nitrile butadiene rubber (NBR), ethylene propylene diene monomer (EPDM), and fluoroelastomer (FKM), which are potential sealing materials for H2 energy infrastructures. C0 follows Henry's law for all samples. No sample size and pressure dependence is observed for S, whereas an appreciable size dependence for the three rubbers is detected for D. The uncertainty is evaluated by considering uncertainty factors that affect the measurement. The correlation between D and density of rubber is found. The developed method can be utilized as a standard test for the transport properties versus pressure of various polymer membranes regardless of the sample shapes and size.

Simple screening technology for hydrogen embrittlement (HE) of steels for hydrogen energy facilities using the in-situ small punch (SP) test method has been established. The HE behaviors of API X70 steel base metal and welds for pipelines were investigated using the relative reduction of thickness (RRT) obtained by the in-situ SP test. As a result, it was found that API X70 steel exhibited similar HE sensitivity regardless of test conditions and weld regions. In this study, to give data application reliability to the RRT obtained by the in-situ SP test of ferritic steels, a simple in-situ slow strain-rate tensile (SSRT) test method using a hollow-type specimen was devised. It was used to evaluate the HE sensitivity of the API X70 steel and welds at various temperatures, and the obtained relative reduction of area (RRA) was used to compare to the RRT by in-situ SP test. As a result, it can be found that RRT by in-situ SP test showed a generally good relationship with RRA by the SSRT, even though some variation existed depending on the test temperature, confirming that the in-situ SP test can be effectively applied to the HE sensitivity screening of pipeline steels and welds in high-pressure hydrogen environments.

An investigation of the effects of hydrogen on tensile flow, strain-hardening and fracture characteristics of low nickel-type 316L austenitic stainless steel was quantified by means of slow strain rate tensile (SSRT) tests. Both thermal precharged and gaseous hydrogen conditions will be considered. The strain-hardening parameters were derived for an idealized true-stress/true-strain curve expressed by Hollomon’s equation. It was found that hydrogen affects the strain-hardening rate and reduces the overall strain-hardening exponents with a similar tendency for diminution of reduction area and fracture strain. The severity of hydrogen embrittlement was observed to be greater in a gaseous hydrogen environment than when tested in the hydrogen pre-charged specimen. Moreover, the fracture mechanism caused by hydrogen pre-charged and gaseous hydrogen environments were different. Hydrogen-induced cracks in hydrogen were found to appear at the interior of the grain boundary, in which there was a strain-induced martensite transformation phase, and crack formation at the grain boundary was predominant gaseous hydrogen specimens.

We have investigated the volume effects on hydrogen diffusion properties in both sorption and desorption processes by employing a volumetric analysis technique. The total uptake (𝐶∞), total desorbed content (𝐶0), sorption diffusion coefficient (Ds), desorption diffusion coefficient (Dd), sorption and desorption equilibrium time of hydrogen in two rubbery polymers are determined relative to the diameter and thickness of the cylindrical sample in the two processes. 𝐶∞ and 𝐶0 do not demonstrate the appreciable volume dependence for all rubbers. The identical values in 𝐶∞ and 𝐶0 indicate the reversibility between sorption and desorption, which is interpreted by the occurrence of physisorption rather than chemisorption by introducing hydrogen molecules. The larger Dd values in the desorption process than Ds may be attributed to increased amorphous phase and volume swelling caused by increased hydrogen voids and polymer chain scission after decompression. The time to reach equilibrium in both sorption and desorption processes was found to be linearly proportional to the square of thickness above an aspect ratio of 3.7, which is consistent with the numerical simulations based on the solution of Fick’s law. This finding could be used to predict the equilibrium adsorption time depending on the sample size in the polymer.

An in-situ small punch (SP) test method has recently been developed as a simple screening technique for evaluating the properties of metallic materials used in high-pressure hydrogen environments. With this method, the test conditions including temperature and gas pressure can easily be adjusted to those used in practice. In this study, specimens of STS316L steel and 18 wt% Mn steel were prepared at two different surface roughness, fabricated using wire-cutting and mechanical polishing. Their effects on hydrogen embrittlement (HE) were evaluated using in-situ SP testing at both room temperature and a lower temperature where HE was shown to occur under 10 MPa hydrogen. Both steels were evaluated using two variables obtained from in-situ SP testing, the SP energy, and the relative reduction of thickness (RRT), to quantitatively determine the effect of specimen surface roughness on HE susceptibility. Their fracture characteristics due to HE under 10 MPa hydrogen showed little difference with surface finish. Surface roughness had a negligible influence on these quantitative factors describing HE, indicating that it is not a dominant factor to be considered in in-situ SP testing when it is used to screen for HE compatibility in steels used in high-pressure hydrogen environments.

A simple screening technique of hydrogen embrittlement (HE) of steels for hydrogen energy facilities using an in-situ small-punch (SP) test method under external hydrogen condition has been established. Using this method, we investigated the HE behaviors of API X70 steel welds under test conditions mimicking pipeline operating environments. The HE sensitivity at each region of the base metal, heat-affected zone, and weld metal of the steel weld was examined qualitatively and quantitatively and compared to one another. Under 8 MPa H2 gas, the welds showed pronounced HE: the HE behaviors induced were similar across all tested regions. This shows that the in-situ SP test is effective for screening HE susceptibility of pipeline steel welds in high-pressure hydrogen environments.

We report volumetric analysis techniques to analyze the transport properties of hydrogen dissolved in cylindrical-shaped polymers. The techniques utilize the volume measurement of the released hydrogen from rubber by gas collection in a graduated cylinder after charging sample with high-pressure hydrogen and subsequent decompression. We further improve the graduated cylinder with some modifications, such as reading the electrical capacitance of the water level using electrodes and changing the sample loading position. From the measurement results, the uptake (C∞), diffusion coefficient (D), and solubility (S) of hydrogen are quantified with an upgraded diffusion analysis program. These methods are applied to three cylindrical rubbers. Dual adsorption behaviors with increasing pressure are observed for all the samples. C∞ follows Henry's law up to ~15 MPa, whereas Langmuir model applies up to 90 MPa. D shows Knudsen and bulk diffusion behavior below and above pressure, respectively. A COMSOL simulation is compared with experimental observations.

The susceptibility of low nickel content type 316L austenitic stainless steel to hydrogen was quantified using low strain rate tensile tests and strain-controlled low-cycle fatigue life measurements. Both tests were performed under air condition after charging with high-pressure 10-MPa hydrogen gas at 300 °C for eight days. No significant influence of hydrogen was recognized in 0.2% proof stress, but the strain at fracture and reduction area was decreased significantly in both hydrogen pre-charged and in gaseous hydrogen conditions compared to companion tests conducted in air. The decrease of fatigue life in the high strain amplitude region was related to a significant decrease in the plastic component while the effect of hydrogen on the elastic component was negligible. Highly localized deformation and a pronounced martensite transformation occurred near the site of the fracture surface in the high strain amplitude regime, resulting in the early formation of abundant micro-surface cracks in this regime of the hydrogen pre-charged samples.

Nondestructive impedance spectroscopy (IS) was developed and demonstrated to detect the effects of hydrogen on nitrile butadiene rubber exposed to hydrogen gas (H2) at high pressures up to 10 MPa. IS was applied to obtain an in situ and real-time quantification of H2 penetration into and its desorption out of rubber under high pressure. The diffusion coefficients of H2 were also obtained from the time evolution of the capacitance, which were compared with those obtained by thermal desorption gas analysis. The in situ measurements of the capacitance and the dissipation factor under various pressures during cyclic stepwise pressurization and decompression demonstrated the diffusion behaviour of H2, the phase of the rubber under high pressure, the transport properties of H2 gas, and the physicochemical interaction between H2 and the rubber. These phenomena were supported by a COMSOL simulation based on the electric current conservation equation and scanning electron microscopy (SEM) observations.

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.

Low-temperature mechanical properties of a high-manganese austenitic steel were evaluated with and without hydrogen pre-charging to examine the applicability of the alloy as a material for hydrogen infrastructure. The high-manganese steel, along with the conventional 304 and 316 L austenitic steels, was examined for hydrogen-related properties including hydrogen content after gas-phase pre-charging, tensile properties, and Charpy impact toughness at different temperatures ranging from room temperature to −80 and −196 °C, respectively, and the resultant fracture surfaces. Under hydrogen-charged conditions, the high-manganese steel showed low-temperature mechanical properties comparable to those of conventional austenitic steels, suggesting the potential of the alloy for structural applications in hydrogen environment.

Rubber materials play a key role in preventing hydrogen gas leakage in high-pressure hydrogen facilities. Therefore, it is necessary to investigate rubber materials exposed to high-pressure hydrogen to ensure operational safety. In this study, permeation, volume swelling, hydrogen content, and mechanical characteristics of acrylonitrile butadiene rubber (NBR), ethylene propylene diene monomer (EPDM), and fluorocarbon (FKM) samples exposed to pressures of 35 and 70 MPa were investigated. The results showed that the volume recovery and hydrogen desorption behavior of EPDM with the highest permeation were fast whereas those of FKM with the lowest permeation were slow. The volume of NBR with the highest hydrogen content expanded after decompression. In contrast, FKM swelled the most despite having the lowest hydrogen content. After exposure to high-pressure hydrogen, the compression set (CS) slightly increased due to internal cracks, but the tensile strength decreased significantly with increasing pressure despite the absence of cracks in the fracture area of all tensile specimens. It was concluded that the decrease in tensile strength is closely related to the volume increase because of the relationship between the relative true strength and the volume ratio.

The strain-controlled low-cycle fatigue behavior of P91 steel is investigated under various strain amplitudes ranging from 0.20% to 1.0% at 25, 538, and 566 °C. The fatigue life decreases with an increase in the test temperature; however, a clear reduction is observed at low strain amplitudes, resulting in the degradation of the fatigue limits. The amount of cyclic softening increases with an increase in the strain amplitude and is significantly higher at elevated temperatures. Based on experimental results, Basquin-Coffin-Mason models are established to express the relationship between the strain amplitude-fatigue life curves and the cyclic stress-strain. The transition fatigue life increased from 6677 reversals at 25 °C to approximately 12000 reversals at the elevated temperatures of 538 and 566 °C. The more pronounced effect of temperature at the very low strain amplitude condition is attributed to the occurrence of multiple oxidation-enhanced crack initiations after long-term exposure to elevated temperatures.

Recently, a simple screening technique based on the quantitative evaluation of the hydrogen embrittlement (HE) sensitivity of the metallic materials using an in-situ small-punch (SP) test method was developed by the author group. The in-situ SP test can be easily carried out even under a high-pressure hydrogen gas environment. It makes possible to investigate the HE behaviors of metallic materials quantitatively adopting as a characterizing performance factor of the relative reduction of thickness (RRT) measured at the fractured parts of specimen after SP tests. In this paper, the application of the newly established in-situ SP test method for the hydrogen compatibility screening of austenitic stainless steels was performed at room and low temperatures. The influence of punch velocity on RRT of the HE sensitivity was examined for various austenitic stainless steels. Their HE sensitivities were evaluated quantitatively using RRT and checked by comparing to a factor, the relative reduction of area (RRA) obtained by SSRT tests.

We established an ex-situ technique for evaluating hydrogen gas permeability by thermal desorption analysis (TDA) gas chromatography (GC) and by self-developed diffusion analysis software. Absorbed hydrogen mass in rubber, related to the GC-peak area, is recorded as a function of elapsed time after decompressing the hydrogen under high-pressure. From the charging amount (CH0) and diffusivity (D) obtained by the developed diffusion analysis program, the solubility(S) and permeability(P) is evaluated via Henry’s law and P = SD, respectively. The techniques were applied to ethylene propylene diene monomer (EPDM) rubber, sealing material candidates in hydrogen infrastructures. EPDM sample mixed with carbon black fillers showed dual hydrogen diffusion behaviors, whereas EPDM sample without carbon black showed a single hydrogen diffusion behavior. There was no appreciable pressure or size dependence on D, S and P. P are consistent with that measured by different researcher within the expanded uncertainty.

Various efforts have been made to improve the safety of high-pressure gas cylinders for hydrogen or natural gas with high strength steel liners. Metal liners with high tensile strength have a safety concern, particularly with hydrogen gas or hydrogen generating environments. The hydrogen can permeate into the liner material, and make the material brittle, causing hydrogen damage. This study investigated resistance to hydrogen damage for two kinds of 34CrMo4 steel with different strength levels. Hydrogen was charged with the electrochemical method, and the material strength was measured by the small punch testing technique. Hydrogen concentration of the specimen was also measured for every testing condition, with various charging periods. The specimens with high tensile strength absorbed more hydrogen than the regular tensile strength specimens. The absorbed hydrogen caused internal damage of intergranular cracking and blistering. Material ductility at failure decreased, as the hydrogen concentration of the specimen increased. But the hydrogen concentration had virtually no effect on the strength of the materials with hydrogen. These results confirm that the susceptibility to hydrogen damage of the high tensile strength materials is much higher than that of the materials with regular strength. If the metal liner of a hoop-wrapped cylinder vessel of type II has high tensile strength, general corrosion at the liner surface can cause a hydrogen rich environment, and the cylinder can suffer hydrogen damage and embrittlement. Therefore, controlling the strength level under an optimal level is critical for the safety of a cylinder made with 34CrMo4 steel.

The influence of hydrogen embrittlement on the fatigue behaviors of AISI 304 stainless steel is investigated. The fatigue endurance limits of the untreated and hydrogen-embrittled materials were almost the same at 400 MPa, and hydrogen embrittlement had little influence even though the sample contained about 8.1 times more hydrogen. Thus, the sensitivity of hydrogen gas in this material is very low. A surface crack initiation, growth, coalescence, and micro ridge model is proposed in this study. Slip line formation ⇒ microcrack formation ⇒ increases in the crack width, and blunting of the crack tip as it grows ⇒ formation of many slip lines because of deformation in the shear direction ⇒ growth of the crack in the shear direction, forming micro ridges, coalescence with adjacent cracks ⇒ continuous initiation, growth, coalescence, and ridge formation of surface cracks and specimen breakage.

In-situ small-punch (SP) tests have recently been used to characterize the susceptibility to hydrogen embrittlement (HE) of various steels. Most techniques for HE evaluation have been based on the use of initially hydrogen pre-charged specimens. However, in internal hydrogen conditions, consistent results are not obtained for the embrittlement and fracture behavior in comparison to those under external hydrogen conditions. In this study, an in-situ SP test was used to evaluate the HE susceptibility in 316L austenitic stainless steel. The test was carried out in 10-MPa gas environments at room temperature (RT) and below with different punch velocities. The results showed that at 10-MPa H2 gas, STS316L steel exhibited good resistance to HE at RT and −10 °C. However, the susceptibility to HE depended on the test temperature and punch velocity. A numerical simulation of the SP test was used to systematically compensate for the insufficient explanation of the crack formation that occurred during in-situ SP testing and to investigate the interaction of the punch velocity and the stress field in regard to the HE effect. The numerical analysis results support the experimental findings and provide a detailed explanation of factors such as the friction coefficient, strain rate, and stress state which lead to crack formation through their interaction in hydrogen-embrittled steel.

본 연구는 실온에서 미처리재와 UNSM처리재, 수소취화재(100 bar, 300℃에서 120 h) 및 이 수소취화재의 UNSM처리재의 스테인리스강 316L 시험편의 재료특성파악을 위한 실험을 실시하였다. 여기서 수소취화재는 기존의 미처리재의 S-N곡선보다 피로강도가 약간 감소하는 경향을 나타내었으며, 수소취화효과는 적게 나타났다. 미처리재에 비해서 UNSM처리재의 피로한도는 약 43.8 % 상승하였고, 수소취화재의 UNSM처리재는 수소취화재보다 약 57.1 % 상승하는 경향을 나타내었다. EBSD에 의한 IQ, IPF 및 KAM 맵에서 UNSM처리 후, 이 처리의 영향을 받는 나노 입자 표면층의 두께는 약 152 μm이다. 그러나 세 가지 맵에서 수소취화의 깊이 영향을 정량적으로 평가할 수 없었다. 시험편상에서 발생하는 표면균열은 수소취화의 영향으로 평균입경(35 μm)보다 작은 균열의 비율이 약 90 %를 차지하였다.