Japan
Quantitative Evaluations of Hydrogen Diffusivity in V-X (X = Cr, Al, Pd) Alloy Membranes Based on Hydrogen Chemical Potential
Jan 2021
Publication
Vanadium (V) has higher hydrogen permeability than Pd-based alloy membranes but exhibits poor resistance to hydrogen-induced embrittlement. The alloy elements are added to reduce hydrogen solubility and prevent hydrogen-induced embrittlement. To enhance hydrogen permeability the alloy elements which improve hydrogen diffusivity in V are more suitable. In the present study hydrogen diffusivity in V-Cr V-Al and V-Pd alloy membranes was investigated in view of the hydrogen chemical potential and compared with the previously reported results of V-Fe alloy membranes. The additions of Cr and Fe to V improved the mobility of hydrogen atoms. In contrast those of Al and Pd decreased hydrogen diffusivity. The first principle calculations revealed that the hydrogen atoms cannot occupy the first-nearest neighbour T sites (T1 sites) of Al and Pd in the V crystal lattice. These blocking effects will be a dominant contributor to decreasing hydrogen diffusivity by the additions of Al and Pd. For V-based alloy membranes Fe and Cr are more suitable alloy elements compared with Al and Pd in view of hydrogen diffusivity.
Charge Carrier Mapping for Z-scheme Photocatalytic Water-splitting Sheet via Categorization of Microscopic Time-resolved Image Sequences
Jun 2021
Publication
Photocatalytic water splitting system using particulate semiconductor materials is a promising strategy for converting solar energy into hydrogen and oxygen. In particular visible-light-driven ‘Z-scheme’ printable photocatalyst sheets are cost-effective and scalable. However little is known about the fundamental photophysical processes which are key to explaining and promoting the photoactivity. Here we applied the pattern-illumination time-resolved phase microscopy for a photocatalyst sheet composed of Mo-doped BiVO4 and Rh-doped SrTiO3 with indium tin oxide as the electron mediator to investigate photo-generated charge carrier dynamics. Using this method we successfully observed the position- and structure-dependent charge carrier behavior and visualized the active/inactive sites in the sheets under the light irradiation via the time sequence images and the clustering analysis. This combination methodology could provide the material/synthesis optimization methods for the maximum performance of the photocatalyst sheets.
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
The Effect of Graphite Size on Hydrogen Absorption and Tensile Properties of Ferritic Ductile Cast Iron
Jun 2019
Publication
Ductile cast iron (DCI) is one of prospective materials used for the hydrogen equipment because of low-cost good workability and formability. The wide range of mechanical properties of DCI is obtained by controlling microstructural factors such as graphite size volume fraction of graphite matrix structure and so on. Therefore it is important to find out an optimal microstructural condition that is less susceptible to hydrogen embrittlement. In this study the effects of graphite size on the hydrogen absorption capability and the hydrogen-induced ductility loss of ferritic DCI were investigated.<br/>Several kinds of ferritic DCIs with a different graphite diameter of about 10 µm - 30 µm were used for the tensile test and the hydrogen content measurement. Hydrogen charging was performed prior to the tensile test by exposing a specimen to high-pressure hydrogen gas. Then the tensile test was performed in air at room temperature. The hydrogen content of a specimen was measured by a thermal desorption analyzer.<br/>It was found that the amount of hydrogen stored in DCI was dependent on the graphite size. As the graphite diameter increased the hydrogen content sharply increased at a certain graphite diameter and then it became nearly constant irrespective of increase in graphite diameter. In other words there was the critical graphite diameter that significantly changed the hydrogen absorption capability. The ductility was decreased by hydrogen and the hydrogen-induced ductility loss was dependent on the hydrogen content. Therefore the hydrogen embrittlement of DCI became remarkable when the graphite size was larger than the critical value.
Unusual Hydrogen Implanted Gold with Lattice Contraction at Increased Hydrogen Content
Mar 2021
Publication
The experimental evidence for the contraction of volume of gold implanted with hydrogen at low doses is presented. The contraction of lattice upon the addition of other elements is very rare and extraordinary in the solid-state not only for gold but also for many other solids. To explain the underlying physics the pure kinetic theory of absorption is not adequate and the detailed interaction of hydrogen in the lattice needs to be clarified. Our analysis points to the importance of the formation of hydride bonds in a dynamic manner and explains why these bonds become weak at higher doses leading to the inverse process of volume expansion frequently seen in metallic hydrogen containers.
The Study on Permissible Value of Hydrogen Gas Concentration in Purge Gas of Fuel Cell Vehicles
Sep 2019
Publication
Ignition conditions and risks of ignition on a permissible value of hydrogen concentration in purge gas prescribed by HFCV-GTR were reevaluated. Experiments were conducted to investigate burning behavior and thermal influence of continuous evacuation of hydrogen under continuous purge of air / hydrogen premixed gas which is close to an actual purge condition of FCV and thermal evacuation of hydrogen. As a result of the re-evaluation it was shown from the viewpoint of safety that the permissible value of hydrogen concentration in purge gas prescribed by the current HFCV GTR is appropriate.
Comparative Technical and Economic Analyses of Hydrogen-Based Steel and Power Sectors
Mar 2024
Publication
Decarbonizing the current steel and power sectors through the development of the hydrogen direct-reduction iron ore–electric arc furnace route and the 100% hydrogen-fired gas turbine cycle is crucial. The current study focuses on three clusters of research works. The first cluster covers the investigation of the mass and energy balance of the route and the subsequent application of these values in experiments to optimize the reduction yield of iron ore. In the second cluster the existing gas turbine unit was selected for the complete replacement of natural gas with hydrogen and for finding the most optimal mass and energy balance in the cycle through an Aspen HYSYS model. In addition the chemical kinetics in the hydrogen combustion process were simulated using Ansys Chemkin Pro to research the emissions. In the last cluster a comparative economic analysis was conducted to identify the levelized cost of production of the route and the levelized cost of electricity of the cycle. The findings in the economic analysis provided good insight into the details of the capital and operational expenditures of each industrial sector in understanding the impact of each kg of hydrogen consumed in the plants. These findings provide a good basis for future research on reducing the cost of hydrogen-based steel and power sectors. Moreover the outcomes of this study can also assist ongoing large-scale hydrogen and ammonia projects in Uzbekistan in terms of designing novel hydrogen-based industries with cost-effective solutions.
Fabrication of CdS/β-SiC/TiO2 Tri-composites That Exploit Hole- and Electron-transfer Processes for Photocatalytic Hydrogen Production Under Visible Light
Dec 2017
Publication
In this work CdS/SiC/TiO2 tri-composite photocatalysts that exploit electron- and hole-transfer processes were fabricated using an easy two-step method in the liquid phase. The photocatalyst with a 1:1:1 M ratio of CdS/SiC/TiO2 exhibited a rate of hydrogen evolution from an aqueous solution of sodium sulfite and sodium sulfide under visible light of 137 μmol h−1 g−1 which is 9.5 times that of pure CdS. β-SiC can act as a sink for the photogenerated holes because the valence band level of β-SiC is higher than the corresponding bands in CdS and TiO2. In addition the level of the conduction band of TiO2 is lower than those of CdS and β-SiC so TiO2 can act as the acceptor of the photogenerated electrons. Our results demonstrate that hole transfer and absorption in the visible light region lead to an effective hydrogen-production scheme.
Evaluation of Safety Measures of a Hydrogen Fueling Station Using Physical Modeling
Oct 2018
Publication
Hydrogen fueling stations are essential for operating fuel cell vehicles. If multiple safety measures in a hydrogen fueling station fail simultaneously it could lead to severe consequences. To analyze the risk of such a situation we developed a physical model of a hydrogen fueling station which when using the temperature pressure and flow rate of hydrogen could be simulated under normal and abnormal operating states. The physical model was validated by comparing the analytical results with the experimental results of an actual hydrogen fueling station. By combining the physical model with a statistical method we evaluated the significance of the safety measures in the event wherein multiple safety measures fail simultaneously. We determined the combinations of failures of safety measures that could lead to accidents and suggested a measure for preventing and mitigating the accident scenario.
Crack Size Dependency of Shear-mode Fatigue Threshold in Bearing Steel Subjected to Continuous Hydrogen Charging
Jun 2019
Publication
Premature delamination failure characterized by the white structure flaking (WSF) or the white etching crack (WEC) often occurs in rolling element bearings and it deteriorates the durability of bearing substantially. It is known that this failure is caused by shear-mode (Mode II and Mode III) crack growth in conjunction with evolution and invasion of hydrogen into material during operation. To ensure the structural integrity associated with rolling element bearing it is important to clarify the effect of hydrogen on the shear-mode fatigue crack growth behavior near the threshold level.<br/>In our previous study the effect of hydrogen on the shear-mode fatigue crack growth behavior in a bearing steel of JIS SUJ2 was examined near the threshold level. Consequently it was shown that the threshold stress intensity factor (SIF) range for shear-mode fatigue crack growth decreased significantly by action of hydrogen. However the investigation was made only for a crack with a surface length of about 900 mm. To thoroughly understand the critical condition for delamination failure it is important to investigate the crack size dependency of the threshold level for a shear-mode small fatigue crack in the presence of hydrogen. In the present study correspondingly the threshold SIF ranges for a shear-mode crack with different length were additionally measured in the same material by using a novel technique that enables continuous charging of hydrogen in a specimen during long-term fatigue test. Then a clear reduction in crack growth rate and a crack size dependency of the threshold SIF range were observed under the environmental condition of continuous hydrogen charging.
A Fully Renewable and Efficient Backup Power System with a Hydrogen-biodiesel-fueled IC Engine
Jan 2019
Publication
Renewable energy is free abundant clean and could contribute towards a significant reduction of the global warming emissions. It is massively introduced as a source of electricity production across the globe and is expected to become the primary source of energy within the following decades. However despite the naturally replenished energy the supply is not always available. For this reason it is necessary at times of excess energy any surplus quantity to be sufficiently captured stored and later used when a deficit occurs. In this paper an overview of a backup power system operating with a hydrogen-biodiesel dual-fuel internal combustion engine is provided. The system is utilizing the organic chemical hydride method for safe hydrogen storage and transportation. The high energy content of hydrogen stored in the form of an organic hydride under ambient conditions makes it an ideal energy backup medium for large-scale and long-term applications. The research work focusses on the operation and emissions output of the dual-fuel internal combustion engine running on fully renewable fuels and the results are compared with the conventional petroleum-derived diesel engine. Biodiesel-hydrogen operation shows significant benefits in the reduction of carbon and soot emissions but deteriorates the NOx formation compared to the conventional diesel-powered engines. The operation of the engine at high loads can provide high exhaust thermal energy while alternative combustion strategies are necessary to be implemented at low load conditions for the optimum operation of the backup power system.
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.
Simulation of a Multi-Functional Energy System for Cogeneration of Steam, Power and Hydrogen in a Coke Making Plant
Mar 2013
Publication
In this paper a multifunctional energy system (MES) is proposed for recovering energy from the extra of coke oven gas (COG) which is usually flared or vented out as a waste stream in coke making plants. The proposed system consists of a pressure swing adsorption (PSA) unit for extracting some of the hydrogen from COG a gas turbine for producing heat and power from PSA offgas and a heat recovery steam generator (HRSG) for generating the steam required by the plant's processes. o assess the performance of the system practically simulations are carried out on the basis of the design and operational conditions of Zarand Coke Making Plant in Iran. The results indicate that by utilizing about 4.39 tons of COG per hour 6.5 MW of net electric power can be approximately produced by the gas turbine which can supply the coke making plant's total electrical power demand. Furthermore through recovering heat from gas turbine's exhaust close to 57% of the plant's steam demand can be supplied by the HRSG unit. It is also found that around 350 kilograms per hour of nearly pure hydrogen (99.9% purity) at 200 bar can be produced by the PSA unit. According to the sensitivity analysis results if the hydrogen content of the coke oven gas decreases by about 10% the gross power output of the gas turbine also declines by around 5.2% due to the reduction of LHV of the PSA offgas. Moreover economic evaluation of the system shows that the payback period of the investment which is estimated at 36.1 M$ is about 5.5 years. The net present value (NPV) and internal rate of return on investment (ROI) are calculated to be 17.6% and 43.3 M$ respectively.
Removing the Bottleneck on Wind Power Potential to Create Liquid Fuels from Locally Available Biomass
Jun 2021
Publication
In order to reduce global greenhouse gas emissions renewable energy technologies such as wind power and solar photovoltaic power systems have recently become more widespread. However Japan as a nation faces high reliance on imported fossil fuels for electricity generation despite having great potential for further renewable energy development. The focus of this study examines untapped geographical locations in Japan’s northern most prefecture Hokkaido that possess large wind power potential. The possibility of exploiting this potential for the purpose of producing green hydrogen is explored. In particular its integration with a year-round conversion of Kraft lignin into bio-oil from nearby paper pulp mills through a near critical water depolymerization process is examined. The proposed bio-oil and aromatic chemical production as well as the process’ economics are calculated based upon the total available Kraft lignin in Hokkaido including the magnitude of wind power capacity that would be required for producing the necessary hydrogen for such a large-scale process. Green hydrogen integration with other processes in Japan and in other regions is also discussed. Finally the potential benefits and challenges are outlined from an energy policy point-of-view.
Impact of Hydrogen Fuel for CO2 Emission Reduction in Power Generation Sector in Japan
Jun 2017
Publication
Japan’s energy consumption derives mostly from fossil fuels which are un-secure and release a much greenhouse gas emissions. To meet goals of reducing GHG hydrogen gas can be utilized in power generation in hydrogen fired and firing / co-combustion power plants. This paper analyses the impact of hydrogen in the power generation sector using the MARKAL-TIMES Japan optimization model framework. Two models are used: a base scenario without hydrogen and hydrogen scenario in which hydrogen is supplied from 2020 onwards. In the hydrogen scenario other processes which are normally supplied by natural gas are reduced because the gas is instead used to generate power. Adding hydrogen to the energy supply leads to a decrease in projected use of fossil fuels. The hydrogen scenario produces fewer emissions than the base scenario; by 2050 the hydrogen scenario’s estimated 388 metric tons of CO2 emissions is over 250 tons less than the base scenario’s emissions of 588 metric tons.
Near-term Location of Hydrogen Refueling Stations in Yokohama City from the Perspective of Safety
Sep 2019
Publication
The roll-out of hydrogen refuelling stations is a key step in the transition to a hydrogen economy. Since Japan has been shifting from the demonstration stage to the implementation stage of a hydrogen economy a near-term city-level roll-out plan is required. The aim of this study is to plan near-term locations for building hydrogen refuelling stations in Yokohama City from a safety perspective. Our planning provides location information for hydrogen refuelling stations in Yokohama City for the period 2020–2030. Mobile type and parallel siting type refuelling stations have been considered in our planning and locations were determined by matching supply and demand to safety concerns. Supply and demand were estimated from hybrid vehicle ownership data and from space availability in existing gas stations. The results reaffirmed the importance of hydrogen station location planning and showed that use of mobile type stations is a suitable solution in response to the uncertain fuel cell vehicle fuel demand level during the implementation stage of a hydrogen economy.
Marked Degradation of Tensile Properties Induced by Plastic Deformation after Interactions between Strain-Induced Martensite Transformation and Hydrogen for Type 316L Stainless Steel
Jul 2020
Publication
Marked degradation of tensile properties induced by plastic deformation after dynamic interactions between strain-induced martensite transformation and hydrogen has been investigated for type 316L stainless steel by hydrogen thermal desorption analysis. Upon modified hydrogen charging reported previously the amount of hydrogen desorbed in the low temperature range increases; the degradation of tensile properties induced by interactions between plastic deformation and hydrogen at 25 °C or induced by interactions between martensite transformation and hydrogen at −196 °C occurs even for the stainless steel with high resistance to hydrogen embrittlement. The hydrogen thermal desorption behavior is changed by each interaction suggesting changes in hydrogen states. For specimen fractured at 25 °C the facet-like morphology and transgranular fracture are observed on the outer part of the fracture surface. At −196 °C a quasi-cleave fracture is observed at the initiation area. Modified hydrogen charging significantly interacts both plastic deformation and martensite transformation eventually enhancing the degradation of tensile properties. Upon plastic deformation at 25° C after the interactions between martensite transformation and hydrogen by straining to 0.2 at −196 °C cracks nucleate in association with martensite formed by the interactions at −196 °C and marked degradation of tensile properties occurs. It is likely that the interactions between martensite transformation and hydrogen induce damage directly related to the degradation thereby affecting subsequent deformation. Upon dehydrogenation after the interactions between the martensite transformation and hydrogen no degradation of tensile properties is observed. The damage induced by the interactions between martensite transformation and hydrogen probably changes to harmless defects during dehydrogenation.
Characterization of Hydrogen Transport Accidents in Japan Based on Network Theory
Sep 2019
Publication
Realizing the hydrogen economy in Japan entails a risk assessment of its domestic hydrogen supply especially hydrogen transport by road. The first step of the risk assessment is to characterize the hydrogen transport accidents from different energy carriers. However it is difficult to characterize the accidents because hydrogen transport systems have not been fully implemented in Japan. The aim of this study is to characterize the hydrogen transport accidents from different energy carriers in Japan. We studied three major energy carriers namely compressed hydrogen liquefied hydrogen and liquid organic hydride. The accident networks based on network theory were constructed to capture the comprehensive accident processes and quantitatively characterized the hydrogen transport accidents from different energy carriers. The results clarified the differences and similarities in the accident process amongst the energy carriers. Furthermore key accident events were identified. This study contributes to the development of comprehensive hydrogen transport accident scenarios for risk assessment.
Large-Scale Hydrogen Deflagrations and Detonations
Sep 2005
Publication
Large-scale deflagration and detonation experiments of hydrogen and air mixtures provide fundamental data needed to address accident scenarios and to help in the evaluation and validation of numerical models. Several different experiments of this type were performed. Measurements included flame front time of arrival (TOA) using ionization probes blast pressure heat flux high-speed video standard video and infrared video. The large-scale open-space tests used a hemispherical 300-m3 facility that confined the mixture within a thin plastic tent that was cut prior to initiating a deflagration. Initial homogeneous hydrogen concentrations varied from 15% to 30%. An array of large cylindrical obstacles was placed within the mixture for some experiments to explore turbulent enhancement of the combustion. All tests were ignited at the bottom center of the facility using either a spark or in one case a small quantity of high explosive to generate a detonation. Spark-initiated deflagration tests were performed within the tunnel using homogeneous hydrogen mixtures. Several experiments were performed in which 0.1 kg and 2.2 kg of hydrogen were released into the tunnel with and without ventilation. For some tunnel tests obstacles representing vehicles were used to investigate turbulent enhancement. A test was performed to investigate any enhancement of the deflagration due to partial confinement produced by a narrow gap between aluminium plates. The attenuation of a blast wave was investigated using a 4-m-tall protective blast wall. Finally a large-scale hydrogen jet experiment was performed in which 27 kg of hydrogen was released vertically into the open atmosphere in a period of about 30 seconds. The hydrogen plume spontaneously ignited early in the release.
Numerical Simulation of Hydrogen Explosion Tests with a Barrier Wall for Blast Mitigation
Sep 2005
Publication
We have investigated hydrogen explosion risk and its mitigation focusing on compact hydrogen refuelling stations in urban areas. In this study numerical analyses were performed of hydrogen blast propagation and the structural behaviour of barrier walls. Parametric numerical simulations of explosions were carried out to discover effective shapes for blast-mitigating barrier walls. The explosive source was a prismatic 5.27 m3 volume that contained 30% hydrogen and 70% air. A reinforced concrete wall 2 m tall by 10 m wide and 0.15 m thick was set 2 or 4 m away from the front surface of the source. The source was ignited at the bottom centre by a spark for the deflagration case and 10 g of C-4 high explosive for two detonation cases. Each of the tests measured overpressures on the surfaces of the wall and on the ground displacements of the wall and strains of the rebar inside the wall. The blast simulations were carried out with an in-house CFD code based on the compressive Euler equation. The initial energy estimated from the volume of hydrogen was a time-dependent function for the deflagration and was released instantaneously for the detonations. The simulated overpressures were in good agreement with test results for all three test cases. DIANA a finite element analysis code released by TNO was used for the structural simulations of the barrier wall. The overpressures obtained by the blast simulations were used as external forces. The analyses simulated the displacements well but not the rebar strains. The many shrinkage cracks that were observed on the walls some of which penetrated the wall could make it difficult to simulate the local behaviour of a wall with high accuracy and could cause strain gages to provide low-accuracy data. A parametric study of the blast simulation was conducted with several cross-sectional shapes of barrier wall. A T-shape and a Y-shape were found to be more effective in mitigating the blast.
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