Japan
Threshold Stress Intensity Factor for Hydrogen Assisted Cracking of Cr-Mo Steel Used as Stationary Storage Buffer of a Hydrogen Refueling Station
Oct 2015
Publication
In order to determine appropriate value for threshold stress intensity factor for hydrogen-assisted cracking (KIH) constant-displacement and rising-load tests were conducted in high-pressure hydrogen gas for JIS-SCM435 low alloy steel (Cr-Mo steel) used as stationary storage buffer of a hydrogen refuelling station with 0.2% proof strength and ultimate tensile strength equal to 772 MPa and 948 MPa respectively. Thresholds for crack arrest under constant displacement and for crack initiation under rising load were identified. The crack arrest threshold under constant displacement was 44.3 MPa m1/2 to 44.5 MPa m1/2 when small-scale yielding and plane-strain criteria were satisfied and the crack initiation threshold under rising load was 33.1 MPa m1/2 to 41.1 MPa m1/2 in 115 MPa hydrogen gas. The crack arrest threshold was roughly equivalent to the crack initiation threshold although the crack initiation threshold showed slightly more conservative values. It was considered that both test methods could be suitable to determine appropriate value for KIH for this material.
Numerical Study on Detailed Mechanism of H2-Air Flame Jet Ignition
Sep 2013
Publication
Jet ignition was recognized in the 1970s and has since been applied to automobile engines such as the Honda CVCC. In the 1990s jet ignition was observed in explosions and was seen as a problem that may relate to jet ignition. Our group presented jet ignition experimentally and numerically in 1999 and later using LIF measurements with the same experimental vessel as used in 1999. However the detailed mechanism of jet ignition was not clarified at that time. The target of this study is to clarify how jet ignition happens and to understand the detailed mechanism of flame jet ignition.
Real-size Calculation of High-pressure Hydrogen Flow and its Auto-ignition in Cylindrical Tube
Sep 2013
Publication
A real-size calculation is performed for high-pressure hydrogen release in a tube using the axisymmetric Navier–Stokes equations with the full hydrogen chemistry. A Harten–Yee-type total variation diminishing scheme and point-implicit method are used to integrate the governing equations. The calculated real-size results show that the leading shock wave velocity is similar to that calculated using a smaller tube. The mixing process and ignition behaviour of high-pressure hydrogen are explained in detail; the velocity shear layer and Kelvin–Helmholtz instability are the main causes of mixing of hydrogen with air and ignition in the high-temperature region behind the leading shock wave.
Effect of Hydrogen on Fatigue Limit of SCM435 Low-Alloy Steel
Dec 2019
Publication
The objective of this study is to gain a basic understanding of the effect of hydrogen on the fatigue limit. The material was a low-alloy steel modified to be sensitive to hydrogen embrittlement by heat treatment. A statistical fatigue test was carried out using smooth and deep-notched specimens at a loading frequency of 20 Hz. The environment was laboratory air and hydrogen gas. The hydrogen gas pressure was 0.1 MPa in gauge pressure. The fatigue limit of the smooth specimen was higher in the hydrogen gas than that in air although the material showed severe hydrogen embrittlement during the SSRT (Slow Strain Rate Test). The fatigue limit of the deep-notched specimen in the hydrogen gas was the same as that in air. For the smooth specimen the fatigue limit was determined by whether or not a crack was initiated. For the deep-notched specimen the fatigue limit was determined by whether or not a crack propagated. The results can be interpreted as that hydrogen has no significant effect on crack initiation in the high-cycle fatigue regime and affected the threshold of the crack propagation.
Hydrogen Storage Mechanism in Sodium-Based Graphene Nanoflakes: A Density Functional Theory Study
Jan 2022
Publication
Carbon materials such as graphene nanoflakes carbon nanotubes and fullerene can be widely used to store hydrogen and doping these materials with lithium (Li) generally increases their H2 -storage densities. Unfortunately Li is expensive; therefore alternative metals are required to realize a hydrogen-based society. Sodium (Na) is an inexpensive element with chemical properties that are similar to those of lithium. In this study we used density functional theory to systematically investigate how hydrogen molecules interact with Na-doped graphene nanoflakes. A graphene nanoflake (GR) was modeled by a large polycyclic aromatic hydrocarbon composed of 37 benzene rings with GR-Na-(H2 )n and GR-Na+ -(H2 )n (n = 0–12) clusters used as hydrogen storage systems. Data obtained for the Na system were compared with those of the Li system. The single-H2 GR-Li and GR-Na systems (n = 1) exhibited binding energies (per H2 molecule) of 3.83 and 2.72 kcal/mol respectively revealing that the Li system has a high hydrogen-storage ability. This relationship is reversed from n = 4 onwards; the Na systems exhibited larger or similar binding energies for n = 4–12 than the Li-systems. The present study strongly suggests that Na can be used as an alternative metal to Li in H2 -storage applications. The H2 -storage mechanism in the Na system is also discussed based on the calculated results.
Development and Functionalization of Visible-Light-Driven Water-Splitting Photocatalysts
Jan 2022
Publication
With global warming and the depletion of fossil resources our fossil fuel-dependent society is expected to shift to one that instead uses hydrogen (H2) as a clean and renewable energy. To realize this the photocatalytic water-splitting reaction which produces H2 from water and solar energy through photocatalysis has attracted much attention. However for practical use the functionality of water-splitting photocatalysts must be further improved to efficiently absorb visible (Vis) light which accounts for the majority of sunlight. Considering the mechanism of water-splitting photocatalysis researchers in the various fields must be employed in this type of study to achieve this. However for researchers in fields other than catalytic chemistry ceramic (semiconductor) materials chemistry and electrochemistry to participate in this field new reviews that summarize previous reports on water-splitting photocatalysis seem to be needed. Therefore in this review we summarize recent studies on the development and functionalization of Vis-light-driven water-splitting photocatalysts. Through this summary we aim to share current technology and future challenges with readers in the various fields and help expedite the practical application of Vis-light-driven water-splitting photocatalysts.
The Residual Strength of Automotive Hydrogen Cylinders After Exposure to Flames
Sep 2017
Publication
Fuel cell vehicles and some compressed natural gas vehicles are equipped with carbon fiber reinforced plastic (CFRP) composite cylinders. Each of the cylinders has a pressure relief device designed to detect heat and release the internal gas to prevent the cylinder from bursting in a vehicle fire accident. Yet in some accident situations the fire may be extinguished before the pressure relief device is activated leaving the high-pressure fuel gas inside the fire-damaged cylinder. To handle such a cylinder safely after an accident it is necessary that the cylinder keeps a sufficient post-fire strength against its internal gas pressure but in most cases it is difficult to accurately determine cylinder strength at the accident site. One way of solving this problem is to predetermine the post-fire burst strengths of cylinders by experiments. In this study automotive CFRP cylinders having no pressure relief device were exposed to a fire to the verge of bursting; then after the fire was extinguished the residual burst strengths and the overall physical state of the test cylinders were examined. The results indicated that the test cylinders all recorded a residual burst strength at least twice greater than their internal gas pressure for tested cylinders with new cylinder burst to nominal working pressure in the range 2.67–4.92 above the regulated ratio of 2.25.
Exchange Current Density of Reversible Solid Oxide Cell Electrodes
Mar 2022
Publication
Reversible solid oxide cells (r-SOCs) can be operated in either solid oxide fuel cell or solid oxide electrolysis cell mode. They are expected to become important in the support of renewable energy due to their high efficiency for both power generation and hydrogen generation. The exchange current density is one of the most important parameters in the quantification of electrode performance in solid oxide cells. In this study four different fuel electrodes and two different air electrodes are fabricated using different materials and the microstructures are compared. The temperature fuel humidification and oxygen concentration at the air electrode are varied to obtain the apparent exchange current density for the different electrode materials. In contrast to ruthenium-and-gadolinia-doped ceria (Rh-GDC) as well as nickel-and-gadolinia-doped ceria (Ni-GDC) electrodes significant differences in the apparent exchange current density were observed between electrolysis and fuel cell modes for the nickel-scandia-stabilized zirconia (Ni-ScSZ) cermet. Variation of gas concentration revealed that surface adsorption sites were almost completely vacant for all these electrodes. The apparent exchange current densities obtained in this study are useful as a parameter for simulation of the internal properties of r-SOCs.
Heuristic Design of Advanced Martensitic Steels That Are Highly Resistant to Hydrogen Embrittlement by ε-Carbide
Feb 2021
Publication
Many advanced steels are based on tempered martensitic microstructures. Their mechanical strength is characterized by fine sub-grain structures with a high density of free dislocations and metallic carbides and/or nitrides. However the strength for practical use has been limited mostly to below 1400 MPa owing to delayed fractures that are caused by hydrogen. A literature survey suggests that ε-carbide in the tempered martensite is effective for strengthening. A preliminary experimental survey of the hydrogen absorption and hydrogen embrittlement of a tempered martensitic steel with ε-carbide precipitates suggested that the proper use of carbides in steels can promote a high resistance to hydrogen embrittlement. Based on the surveys martensitic steels that are highly resistant to hydrogen embrittlement and that have high strength and toughness are proposed. The heuristic design of the steels includes alloying elements necessary to stabilize the ε-carbide and procedures to introduce inoculants for the controlled nucleation of ε-carbide.
Hydrogen Technologies and Developments in Japan
Jan 2019
Publication
The successful development of hydrogen-energy technologies has several advantages and benefits. Hydrogen energy development could prevent global warming as well as ensure energy security for countries without adequate energy resources. The successful development of hydrogen would provide energy for transportation and electric power. It is a unique energy carrier as it can be produced from various energy sources such as wind fossil fuels and biomass and when it is combusted it emits no CO2 emissions. The other advantage is the wide distribution of resources globally that can be used to produce hydrogen. In Japan the Ministry of Economy Trade and Industry (METI) published a ‘Strategic Roadmap for Hydrogen and Fuel Cells’ in 2014 with a revised update published in March 2016. The goal of the roadmap is to achieve a hydrogen society. The roadmap aims to resolve technical problems and secure economic efficiency. The roadmap has been organized into the following three phases: Phase 1—Installation of fuel cells; Phase 2—Hydrogen power plant/mass supply chain; Phase 3—CO2- free hydrogen. This paper reports on the current status of fuel cells and fuel-cell vehicles in Japan and gives a description and status of the R&D programmes along with the results of global energy model study towards 2050.
Mach 4 Simulating Experiment of Pre-Cooled Turbojet Engine Using Liquid Hydrogen
Jan 2022
Publication
This study investigated a pre-cooled turbojet engine for a Mach 5 class hypersonic transport aircraft. The engine was demonstrated under takeoff and Mach 2 flight conditions and a Mach 5 propulsion wind tunnel test is planned. The engine is composed of a pre-cooler a core engine and an afterburner. The engine was tested under simulated Mach 4 conditions using an air supply facility. High-temperature air under high pressure was supplied to the engine components through an airflow control valve and an orifice flow meter and liquid hydrogen was supplied to the pre-cooler and the core engine. The results confirmed that the starting sequence of the engine components was effective under simulated Mach 4 conditions using liquid hydrogen fuel. The pre-cooling effect caused no damage to the rotating parts of the core engine in the experiment.
Safety Design of Compressed Hydrogen Trailers with Composite Cylinders
Sep 2013
Publication
Compressed hydrogen is delivered by trailers in steel cylinders at 19.6 MPa in Japan. Kawasaki Heavy Industries Ltd. developed two compressed hydrogen trailers with composite cylinders in collaboration with JX Nippon Oil in a project of the New Energy and Industrial Technology Development Organization (NEDO).<br/>The first trailer which was the first hydrogen trailer with composite cylinder in Japan has 35 MPa cylinders and the second trailer has 45 MPa cylinders. These trailers have been operated transporting hydrogen and feedstock to hydrogen refuelling stations without the accident. This paper describes the safety design including compliance with regulations the influence of vibrations and safety verification in case of a collision.
Safety Concept of Nuclear Cogeneration of Hydrogen and Electricity
Oct 2015
Publication
There is a significant potential for nuclear combined heat and power (CHP) in quite a number of industries. The reactor concepts of the next generation would be capable to open up in particular the high temperature heat market where nuclear energy is applicable to the production processes of hydrogen (or liquid fuels) by steam reforming or water splitting. Due to the need to locate a nuclear facility near the hydrogen plant an overall safety concept has to deal with the question of safety of the combined nuclear/industrial system by taking into account a qualitatively new class of events characterized by interacting influences. Specific requirements will be determined by such factors as the reactor type the nature of the industrial process the separation distances of the industrial facility and population centers from the nuclear plant and prevailing public attitudes. Based on the Japanese concept of the GTHTR300C nuclear reactor for electricity and hydrogen cogeneration theoretical studies were conducted on the release dispersive transport and explosion of a hydrogen cloud in the atmosphere for the sake of assessing the required minimum separation distance to avoid any risk to the nuclear plant's safety systems. In the case of sulfur-iodine water splitting the accidental release of process intermediates including large amounts of sulfur dioxide sulfur trioxide and sulfuric acid need to be investigated as well to estimate the potential risk to nuclear installations like the operators' room and estimate appropriate separation distances against toxic gas propagation. Results of respective simulation studies will be presented.
Self-acceleration of a Spherically Expanding Hydrogen-air Flame at Elevated Pressure
Sep 2019
Publication
Self-acceleration of a spherically expanding hydrogen-air flame was experimentally investigated in a closed dual-chamber apparatus with the quartz windows enabled to a flame diameter with up to 240 mm. The flame radius and flame speed in lean hydrogen-air mixtures at elevated pressure were evaluated using a high speed Schlieren photography. The experimental results from hydrogen-air explosion at elevated pressure validated the prediction model for self-similar propagation. The flame radius and its speed calculated by the prediction models agree well with the experimental results of hydrogen-air explosions at elevated pressure. Furthermore the acceleration exponent α is evaluated by plotting the flame radius with time. The results show the α value increase with the dimensionless flame radius r/rcl. It is indicated that the self-acceleration and the transition regime to self-similar propagation exist in the spherically expanding hydrogen-air flame.
Dependency of Equivalence Ratio on Hydrogen Cylindrical Detonation Induced by Direct Initiation
Sep 2011
Publication
A hydrogen fuel is expected to expand its demand in the future. However hydrogen has to be treated with enough caution because of wide combustible conditions and easiness to ignite. Detonation accidents are caused in hydrogen gas such as the explosion accident in Fukushima first nuclear plant (2011). Therefore it is necessary to comprehend initiation conditions of detonation to prevent its detonation explosion. In the present study cylindrical detonation induced by direct initiation is simulated to understand the dependency of equivalence ratios in hydrogen-oxygen mixture. The several detailed kinetic models are compared to select the most appropriate model for detonation in a wide range of equivalence ratios. The Petersen-Hanson model is used in the present study due to the best agreement among the other models. In the numerical results of cylindrical detonation induced by direct initiation a cellular structure which is similar to the experimental smoked foil record is observed. The local pressure is up to 12 MPa under the condition at the standard state. The ignition process of cylindrical detonation has two stages. At the first stage the normalized cell width /L1/2 at each equivalence ratio increases linearly. At the second stage cell bifurcations appear due to a generation of new transverse waves. It is observed that a transverse wave transforms to a transverse detonation at the end of the first stage and after that some disturbance is developed to be a new transverse wave at the beginning of the second stage.
Materials Towards Carbon-free, Emission-free and Oil-free Mobility: Hydrogen Fuel-cell Vehicles—Now and in the Future
Jul 2010
Publication
In the past material innovation has changed society through new material-induced technologies adding a new value to society. In the present world engineers and scientists are expected to invent new materials to solve the global problem of climate change. For the transport sector the challenge for material engineers is to change the oil-based world into a sustainable world. After witnessing the recent high oil price and its adverse impact on the global economy it is time to accelerate our efforts towards this change.
Industries are tackling global energy issues such as oil and CO2 as well as local environmental problems such as NOx and particulate matter. Hydrogen is the most promising candidate to provide carbon-free emission-free and oil-free mobility. As such engineers are working very hard to bring this technology into the real society. This paper describes recent progress of vehicle technologies as well as hydrogen-storage technologies to extend the cruise range and ensure the easiness of refuelling and requesting material scientists to collaborate with industry to fight against global warming.
Link to document download on Royal Society Website
Industries are tackling global energy issues such as oil and CO2 as well as local environmental problems such as NOx and particulate matter. Hydrogen is the most promising candidate to provide carbon-free emission-free and oil-free mobility. As such engineers are working very hard to bring this technology into the real society. This paper describes recent progress of vehicle technologies as well as hydrogen-storage technologies to extend the cruise range and ensure the easiness of refuelling and requesting material scientists to collaborate with industry to fight against global warming.
Link to document download on Royal Society Website
Numerical Investigation of Vented Hydrogen-air Deflagration in a Chamber
Oct 2015
Publication
This paper shows numerical investigation related to hydrogen-air deflagration venting. The aim of this study is to clarify the influence of concentration gradient on the pressure histories and peak pressures in a chamber. The numerical analysis target is a 27 m3 cubic chamber which has 2.6 m2 vent area on the sidewall. The vent opening pressure is set to be gauge 10 kPa. Two different conditions of the hydrogen concentration are assumed which are uniform and gradient. In the uniform case 15 20 25 30 and 35 vol.% concentrations are assumed. In the gradient case the concentration linearly increases from 0 vol.% (at the ground) to 30 40 50 60 70 vol.% (at the ceiling). The initial total mass of hydrogen inside the chamber is the same as the uniform case. Moreover three different ignition points are assumed: on the rear center and the front of the chamber relative to the vent. The deflagrations are initiated by a single ignition source. In most gradient cases the highest peak is lower than in the uniform case though the initial total mass of hydrogen inside the chamber is the same as in the uniform case. This is because the generated burned gas per time is smaller in the gradient case than in the uniform case. In 15 vol.% gradient case however the peak pressure gets higher than in the uniform case. This is because in 15 vol.% gradient case the burning velocity around the ignition point gets faster and the flame surface gets larger which induces larger amount of burned gas per time.
Numerical Investigation of Hydrogen Leakage from a High Pressure Tank and its Explosion
Oct 2015
Publication
We numerically investigated the initial behaviour of leakage and diffusion from high-pressure hydrogen storage tank assumed in hydrogen station. First calculations are carried out to validate the present numerical approach and compare with the theoretical distribution of hydrogen mass fraction to the direction which is vertical to the jet direction in the case of hydrogen leaking out from the circular injection port whose diameter is 0.25 mm. Then performing calculations about hydrogen leakage and diffusion behaviour on different tank pressures the effects are examined to reduce damage by gas explosion assumed in the hydrogen station. There is no significant difference in the diffusion distance to the jet direction from a start to 0.2 ms. After 0.2 ms it is seen the difference in the diffusion distance to the jet direction in different pressure. As tank pressures become large the hydrogen diffusion not only to the jet direction but also to the direction which is vertical to the jet direction is remarkably seen. Then according to histories of the percentage of the flammable mass to total one in the space it drastically increases up to 30%2between 0 and 0.05 ms. After 0.05 ms it uniformly increases so it is shown that the explosion risk becomes high over time. The place where mass within flammability range distributes at a certain time is shown. Hydrogen widely diffuses to jet direction and distributes in each case and time. Therefore it is found that when it is assumed that ignition occurs by some sources in place where high-pressure hydrogen is leaked and diffused the magnitude of the explosion damage can be predicted when and where ignition occurs.
Visualization of Auto-ignition Phenomenon Under the Controlled Burst Pressure
Oct 2015
Publication
A high-pressure hydrogen jet released into the air has the possibility of igniting in a tube without any ignition source. The mechanism of this phenomenon called spontaneous ignition is considered to be that hydrogen diffuses into the hot air caused by the shock wave from diaphragm rupture and the hydrogen-oxidizer mixed region is formed enough to start chemical reaction. Recently flow visualization studies on the spontaneous ignition process have been conducted to understand its detailed mechanism but such ignition has not yet been well clarified. In this study the spontaneous ignition phenomenon was observed in a rectangular tube. The results confirm the presence of a flame at the wall of the tube when the shock wave pressure reaches 1.2–1.5 MPa in more than 9 MPa burst pressure and that ignition occurs near the wall followed by multiple ignitions as the shock wave propagates with the ignitions eventually combining to form a flame.
Numerical Investigation of Detonation in Stratified Combustible Mixture and Oxidizer with Concentration Gradients
Sep 2019
Publication
Hydrogen leakage in a closed space is one of the causes of serious accidents because of its high detonability. Assuming the situation that hydrogen is accumulated in a closed space two-dimensional numerical simulation for hydrogen oxygen detonation which propagates in stratified fuel and oxidizer with concentration gradient is conducted by using detailed chemical reaction model. The concentration gradient between fuel and oxidizer is expressed by changing the number of hydrogen moles by using sigmoid function. Strength of discontinuity at the boundary is controlled by changing the gain of the function. The maximum pressure history shows that the behaviour of triple points is different depending on the strength of discontinuity between the two kind of gas. In without concentration gradient case the transverse waves are reflected at the boundary because of the sudden change of acoustic impedance ratio between two kind of gas. In contrast in with concentration gradient case the transverse wavs are not reflected in the buffer zone and they are flowed into the oxidizer as its structures are kept. As a result the confined effect declines as the strength of discontinuity between the two kind of gas is weakened and the propagating distance of detonation changes
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