Transmission, Distribution & Storage
Synthesis of Spherical V-Nb-Mo-Ta-W High-Entropy Alloy Powder Using Hydrogen Embrittlement and Spheroidization by Thermal Plasma
Dec 2019
Publication
V-Nb-Mo-Ta-W high-entropy alloy (HEA) one of the refractory HEAs is considered as a next-generation structural material for ultra-high temperature uses. Refractory HEAs have low castability and machinability due to their high melting temperature and low thermal conductivity. Thus powder metallurgy becomes a promising method for fabricating components with refractory HEAs. Therefore in this study we fabricated spherical V-Nb-Mo-Ta-W HEA powder using hydrogen embrittlement and spheroidization by thermal plasma. The HEA ingot was prepared by vacuum arc melting and revealed to have a single body-centered cubic phase. Hydrogen embrittlement which could be achieved by annealing in a hydrogen atmosphere was introduced to get the ingot pulverized easily to a fine powder having an angular shape. Then the powder was annealed in a vacuum atmosphere to eliminate the hydrogen from the hydrogenated HEA resulting in a decrease in the hydrogen concentration from 0.1033 wt% to 0.0003 wt%. The angular shape of the HEA powder was turned into a spherical one by inductively-coupled thermal plasma allowing to fabricate spherical V-Nb-Mo-Ta-W HEA powder with a d50 value of 28.0 μm.
Insight into Anomalous Hydrogen Adsorption on Rare Earth Metal Decorated on 2 Dimensional Hexagonal Boron Nitride a Density Functional Theory Study
Mar 2020
Publication
Hydrogen interaction with metal atoms is of prime focus for many energy related applications like hydrogen storage hydrogen evolution using catalysis etc. Although hydrogen binding with many main group alkaline and transition metals is quite well understood its binding properties with lanthanides are not well reported. In this article by density functional theory studies we show how a rare earth metal cerium binds with hydrogen when decorated over a heteropolar 2D material hexagonal boron nitride. Each cerium adatom is found to bind eight hydrogen molecules which is a much higher number than has been reported for transition metal atoms. However the highest binding energy occurs at four hydrogen molecules. This anomaly therefore is investigated in the present article using first-principles calculations. The number density of hydrogen molecules adsorbed over the cerium adatom is explained by investigating the electronic charge volume interactions owing to a unique geometrical arrangement of the guest hydrogen molecules. The importance of geometrical encapsulation in enhancing electronic interactions is explained.
Critical Assessment of the Effect of Atmospheric Corrosion Induced Hydrogen on Mechanical Properties of Advanced High Strength Steel
Dec 2020
Publication
Hydrogen absorption into steel during atmospheric corrosion has been of a strong concern during last decades. It is technically important to investigate if hydrogen absorbed under atmospheric exposure conditions can significantly affect mechanical properties of steels. The present work studies changes of mechanical properties of dual phase (DP) advanced high strength steel specimens with sodium chloride deposits during corrosion in humid air using Slow Strain Rate Test (SSRT). Additional annealed specimens were used as reference in order to separate the possible effect of absorbed hydrogen from that of corrosion deterioration. Hydrogen entry was monitored in parallel experiments using hydrogen electric resistance sensor (HERS) and thermal desorption mass spectrometry (TDMS). SSRT results showed a drop in elongation and tensile strength by 42% and 6% respectively in 27 days of atmospheric exposure. However this decrease cannot be attributed to the effect of absorbed hydrogen despite the increase in hydrogen content with time of exposure. Cross-cut analysis revealed considerable pitting which was suggested to be the main reason for the degradation of mechanical properties
Seasonal Energy Storage in Aluminium for 100 Percent Solar Heat and Electricity Supply
Sep 2019
Publication
In order to reduce anthropogenic global warming governments around the world have decided to reduce CO2 emissions from fossil fuels dramatically within the next decades. In moderate and cold climates large amounts of fossil fuels are used for space heating and domestic hot water production in winter. Although on an annual base solar energy is available in large quantities in these regions least of the solar resource is available in winter when most of the energy is needed. Therefore solutions are needed to store and transfer renewable energy from summer to winter. In this paper a seasonal energy storage based on the aluminium redox cycle (Al3+→Al→ Al3+) is proposed. For charging electricity from solar or other renewable sources is used to convert aluminium oxide or aluminium hydroxide to elementary aluminium (Al3+→Al). In the discharging process aluminium is oxidized (Al→Al3+) releasing hydrogen heat and aluminium hydroxide or aluminium oxide as a by-product. Hydrogen is used in a fuel cell to produce electricity. Heat produced from the aluminium oxidation process and by the fuel cell is used for domestic hot water production and space heating. The chemical reactions and energy balances are presented and simulation results are shown for a system that covers the entire energy demand for electricity space heating and domestic hot water of a new multi-family building with rooftop photovoltaic energy in combination with the seasonal Al energy storage cycle. It shows that 7–11 kWp of photovoltaic installations and 350–530 kg Al would be needed per apartment for different Swiss climates. Environmental life cycle data shows that the global warming potential and non-renewable primary energy consumption can be reduced significantly compared to today's common practice of heating with natural gas and using electricity from the ENTSO-E network. The presumptive cost were estimated and indicate a possible cost-competitiveness for this system in the near future.
Highly Porous Organic Polymers for Hydrogen Fuel Storage
Apr 2019
Publication
Hydrogen (H2) is one of the best candidates to replace current petroleum energy resources due to its rich abundance and clean combustion. However the storage of H2presents a major challenge. There are two methods for storing H2 fuel chemical and physical both of which have some advantages and disadvantages. In physical storage highly porous organic polymers are of particular interest since they are low cost easy to scale up metal-free and environmentally friendly.
In this review highly porous polymers for H2 fuel storage are examined from five perspectives:
(a) brief comparison of H2 storage in highly porous polymers and other storage media;
(b) theoretical considerations of the physical storage of H2 molecules in porous polymers;
(c) H2 storage in different classes of highly porous organic polymers;
(d) characterization of microporosity in these polymers; and
(e) future developments for highly porous organic polymers for H2 fuel storage. These topics will provide an introductory overview of highly porous organic polymers in H2 fuel storage.
In this review highly porous polymers for H2 fuel storage are examined from five perspectives:
(a) brief comparison of H2 storage in highly porous polymers and other storage media;
(b) theoretical considerations of the physical storage of H2 molecules in porous polymers;
(c) H2 storage in different classes of highly porous organic polymers;
(d) characterization of microporosity in these polymers; and
(e) future developments for highly porous organic polymers for H2 fuel storage. These topics will provide an introductory overview of highly porous organic polymers in H2 fuel storage.
Freeze-dried Ammonia Borane-polyethylene Oxide Composites: Phase Behaviour and Hydrogen Release
Feb 2018
Publication
A solid-state hydrogen storage material comprising ammonia borane (AB) and polyethylene oxide (PEO) has been produced by freeze-drying from aqueous solutions from 0% to 100% AB by mass. The phase mixing behaviour of AB and PEO has been investigated using X-ray diffraction which shows that a new ‘intermediate’ crystalline phase exists different from both AB and PEO as observed in our previous work (Nathanson et al. 2015). It is suggested that hydrogen bonding interactions between the ethereal oxygen atom (–O–) in the PEO backbone and the protic hydrogen atoms attached to the nitrogen atom (N–H) of AB molecules promote the formation of a reaction intermediate leading to lowered hydrogen release temperatures in the composites compared to neat AB. PEO also acts to significantly reduce the foaming of AB during hydrogen release. A temperature-composition phase diagram has been produced for the AB-PEO system to show the relationship between phase mixing and hydrogen release.
Flexible Power and Hydrogen Production: Finding Synergy Between CCS and Variable Renewables
Dec 2019
Publication
The expansion of wind and solar power is creating a growing need for power system flexibility. Dispatchable power plants with CO2 capture and storage (CCS) offer flexibility with low CO2 emissions but these plants become uneconomical at the low running hours implied by renewables-based power systems. To address this challenge the novel gas switching reforming (GSR) plant was recently proposed. GSR can alternate between electricity and hydrogen production from natural gas offering flexibility to the power system without reducing the utilization rate of the capital stock embodied in CCS infrastructure. This study assesses the interplay between GSR and variable renewables using a power system model which optimizes investment and hourly dispatch of 13 different technologies. Results show that GSR brings substantial benefits relative to conventional CCS. At a CO2 price of V100/ton inclusion of GSR increases the optimal wind and solar share by 50% lowers total system costs by 8% and reduces system emissions from 45 to 4 kgCO2/MWh. In addition GSR produces clean hydrogen equivalent to about 90% of total electricity demand which can be used to decarbonize transport and industry. GSR could therefore become a key enabling technology for a decarbonization effort led by wind and solar power.
Expert Opinion Analysis on Renewable Hydrogen Storage Systems Potential in Europe
Nov 2016
Publication
Among the several typologies of storage technologies mainly on different physical principles (mechanical electrical and chemical) hydrogen produced by power to gas (P2G) from renewable energy sources complies with chemical storage principle and is based on the conversion of electrical energy into chemical energy by means of the electrolysis of water which does not produce any toxic or climate-relevant emission. This paper aims to pinpoint the potential uses of renewable hydrogen storage systems in Europe analysing current and potential locations regulatory framework governments’ outlooks economic issues and available renewable energy amounts. The expert opinion survey already used in many research articles on different topics including energy has been selected as an effective method to produce realistic results. The obtained results highlight strategies and actions to optimize the storage of hydrogen produced by renewables to face varying electricity demand and generation-driven fluctuations reducing the negative effects of the increasing share of renewables in the energy mix of European Countries.
Study on Early Business Cases for H2 In Energy Storage and More Broadly Power to H2 Applications
Jun 2017
Publication
Hydrogen is widely recognised as a promising option for storing large quantities of renewable electricity over longer periods. For that reason in an energy future where renewables are a dominant power source opportunities for Power to- Hydrogen in the long-term appear to be generally acknowledged. The key challenge today is to identify concrete short-term investment opportunities based on sound economics and robust business cases. The focus of this study is to identify these early business cases and to assess their potential replicability within the EU from now until 2025. An essential part and innovative approach of this study is the detailed analysis of the power sector including its transmission grid constraints.
Metal Hydride Hydrogen Compressors
Feb 2014
Publication
Metal hydride (MH) thermal sorption compression is an efficient and reliable method allowing a conversion of energy from heat into a compressed hydrogen gas. The most important component of such a thermal engine – the metal hydride material itself – should possess several material features in order to achieve an efficient performance in the hydrogen compression. Apart from the hydrogen storage characteristics important for every solid H storage material (e.g. gravimetric and volumetric efficiency of H storage hydrogen sorption kinetics and effective thermal conductivity) the thermodynamics of the metal–hydrogen systems is of primary importance resulting in a temperature dependence of the absorption/desorption pressures). Several specific features should be optimised to govern the performance of the MH-compressors including synchronisation of the pressure plateaus for multi-stage compressors reduction of slope of the isotherms and hysteresis increase of cycling stability and life time together with challenges in system design associated with volume expansion of the metal matrix during the hydrogenation.<br/>The present review summarises numerous papers and patent literature dealing with MH hydrogen compression technology. The review considers (a) fundamental aspects of materials development with a focus on structure and phase equilibria in the metal–hydrogen systems suitable for the hydrogen compression; and (b) applied aspects including their consideration from the applied thermodynamic viewpoint system design features and performances of the metal hydride compressors and major applications.
Aging Effects on Modelling and Operation of a Photovoltaic System with Hydrogen Storage
Jun 2021
Publication
In this work the aging effects on modelling and operation of a photovoltaic system with hydrogen storage in terms of energy production decrease and demand for additional hydrogen during 10 years of the system operation was analysed for the entire energy system for the first time. The analyses were performed with the support of experimental data for the renewable energy system composed of photovoltaic modules fuel cell electrolysers hydrogen storage and hydrogen backup.<br/>It has been found that the total degradation of the analysed system can be described by the proposed parameter – unit additional hydrogen consumption ratio. The results reveal a 33.2–36.2% increase of the unit fuel requirement from an external source after 10 years in reference to the initial condition. Degradation of the components can on the other hand be well described with the unit hydrogen consumption ratio by fuel cell for electricity or the unit electricity consumption ratio by electrolyser for hydrogen production which has been found to vary for the electrolyser in the range of 4.6–4.9% and for the fuel cell stack in the range of 13.4–15.1% during the 10 years of the system operation. The analyses indicate that this value depends on the load profile and PV module types and the system performance decline is non-linear."
Balancing Wind-power Fluctuation Via Onsite Storage Under Uncertainty Power-to-hydrogen-to-power Versus Lithium Battery
Oct 2019
Publication
Imbalance costs caused by forecasting errors are considerable for grid-connected wind farms. In order to reduce such costs two onsite storage technologies i.e. power-to-hydrogen-to-power and lithium battery are investigated considering 14 uncertain technological and economic parameters. Probability density distributions of wind forecasting errors and power level are first considered to quantify the imbalance and excess wind power. Then robust optimal sizing of the onsite storage is performed under uncertainty to maximize wind-farm profit (the net present value). Global sensitivity analysis is further carried out for parameters prioritization to highlight the key influential parameters. The results show that the profit of power-to-hydrogen-to-power case is sensitive to the hydrogen price wind forecasting accuracy and hydrogen storage price. When hydrogen price ranges in (2 6) €/kg installing only electrolyzer can earn profits over 100 k€/MWWP in 9% scenarios with capacity below 250 kW/MWWP under high hydrogen price (over 4 €/kg); while installing only fuel cell can achieve such high profits only in 1.3% scenarios with capacity below 180 kW/MWWP. Installing both electrolyzer and fuel cell (only suggested in 22% scenarios) results in profits below 160 k€/MWWP and particularly 20% scenarios allow for a profit below 50 k€/MWWP due to the contradictory effects of wind forecasting error hydrogen and electricity price. For lithium battery investment cost is the single highly influential factor which should be reduced to 760 €/kWh. The battery capacity is limited to 88 kW h/MWWP. For profits over 100 k€/MWWP (in 3% scenarios) the battery should be with an investment cost below 510 €/kWh and a depth of discharge over 63%. The power-to-hydrogen-to-power case is more advantageous in terms of profitability reliability and utilization factor (full-load operating hours) while lithium battery is more helpful to reduce the lost wind and has less environmental impact considering current hydrogen market.
Location-dependent Effect of Nickel on Hydrogen Dissociation and Diffusion on Mg (0001) Surface: Insights into Hydrogen Storage Material Design
Apr 2021
Publication
Density functional theory (DFT) calculations have been performed to investigate the hydrogen dissociation and diffusion on Mg (0001) surface with Ni incorporating at various locations. The results show that Ni atom is preferentially located inside Mg matrix rather than in/over the topmost surface. Further calculations reveal that Ni atom locating in/over the topmost Mg (0001) surface exhibits excellent catalytic effect on hydrogen dissociation with an energy barrier of less than 0.05 eV. In these cases the rate-limiting step has been converted from hydrogen dissociation to surface diffusion. In contrast Ni doping inside Mg bulk not only does little help to hydrogen dissociation but also exhibits detrimental effect on hydrogen diffusion. Therefore it is crucial to stabilize the Ni atom on the surface or in the topmost layer of Mg (0001) surface to maintain its catalytic effect. For all the case of Ni-incorporated Mg (0001) surfaces the hydrogen atom prefers firstly immigrate along the surface and then penetrate into the bulk. It is expected that the theoretical findings in the present study could offer fundamental guidance to future designing on efficient Mg-based hydrogen storage materials.
Modifications in the Composition of CuO/ZnO/Al2O3 Catalyst for the Synthesis of Methanol by CO2 Hydrogenation
Jun 2021
Publication
Renewable methanol obtained from CO2 and hydrogen provided from renewable energy was proposed to close the CO2 loop. In industry methanol synthesis using the catalyst CuO/ZnO/Al2O3 occurs at a high pressure. We intend to make certain modification on the traditional catalyst to work at lower pressure maintaining high selectivity. Therefore three heterogeneous catalysts were synthesized by coprecipitation to improve the activity and the selectivity to methanol under mild conditions of temperature and pressure. Certain modifications on the traditional catalyst Cu/Zn/Al2O3 were employed such as the modification of the synthesis time and the addition of Pd as a dopant agent. The most efficient catalyst among those tested was a palladium-doped catalyst 5% Pd/Cu/Zn/Al2O3. This had a selectivity of 64% at 210 °C and 5 bar.
Seasonal and Multi-Seasonal Energy Storage by Power-to-Methane Technology
Jun 2021
Publication
The time-range of applicability of various energy-storage technologies are limited by self-discharge and other inevitable losses. While batteries and hydrogen are useful for storage in a time-span ranging from hours to several days or even weeks for seasonal or multi-seasonal storage only some traditional and quite costly methods can be used (like pumped-storage plants Compressed Air Energy Storage or energy tower). In this paper we aim to show that while the efficiency of energy recovery of Power-to-Methane technology is lower than for several other methods due to the low self-discharge and negligible standby losses it can be a suitable and cost-effective solution for seasonal and multi-seasonal energy storage.
Molecular Dynamics Studies of Hydrogen Effect on Intergranular Fracture in α-Iron
Nov 2020
Publication
In the current study the effect of hydrogen atoms on the intergranular failure of α-iron is examined by a molecular dynamics (MD) simulation. The effect of hydrogen embrittlement on the grain boundary (GB) is investigated by diffusing hydrogen atoms into the grain boundaries using a bicrystal body-centered cubic (BCC) model and then deforming the model with a uniaxial tension. The Debye Waller factors are applied to illustrate the volume change of GBs and the simulation results suggest that the trapped hydrogen atoms in GBs can therefore increase the excess volume of GBs thus enhancing intergranular failure. When a constant displacement loading is applied to the bicrystal model the increased strain energy can barely be released via dislocation emission when H is present. The hydrogen pinning effect occurs in the current dislocation slip system <111>{112}. The hydrogen atoms facilitate cracking via a decrease of the free surface energy and enhance the phase transition via an increase in the local pressure. Hence the failure mechanism is prone to intergranular failure so as to release excessive pressure and energy near GBs. This study provides a mechanistic framework of intergranular failure and a theoretical model is then developed to predict the intergranular cracking rate
Research on the Concept of Hydrogen Supply Chains and Power Grids Powered by Renewable Energy Sources: A Scoping Review with the Use of Text Mining
Jan 2022
Publication
The key direction of political actions in the field of sustainable development of the energy sector and economy is the process of energy transformation (decarbonization) and increasing the share of renewable energy sources (RES) in the supply of primary energy. Regardless of the indisputable advantages RES are referred to as unstable energy sources. A possible solution might be the development of the concept of hydrogen supply chains especially the so-called green hydrogen obtained in the process of electrolysis from electricity produced from RES. The aim of the research undertaken in the article is to identify the scope of research carried out in the area of hydrogen supply chains and to link this research with the issues of the operation of electricity distribution networks powered by RES. As a result of the scoping review and the application of the text-mining method using the IRaMuTeQ tool which includes the analysis of the content of 12 review articles presenting the current research achievements in this field over the last three years (2016–2020) it was established that the issues related to hydrogen supply chains including green hydrogen are still not significantly associated with the problem of the operation of power grids. The results of the conducted research allow formulating recommendations for further research areas.
Evaluation of Corrosion, Mechanical Properties and Hydrogen Embrittlement of Casing Pipe Steels with Different Microstructure
Dec 2021
Publication
In the research the corrosion and mechanical properties as well as susceptibility to hydrogen embrittlement of two casing pipe steels were investigated in order to assess their serviceability in corrosive and hydrogenating environments under operation in oil and gas wells. Two carbon steels with different microstructures were tested: the medium carbon steel (MCS) with bainitic microstructure and the medium-high carbon steel (MHCS) with ferrite–pearlite microstructure. The results showed that the corrosion resistance of the MHCS in CO2-containing acid chloride solution simulating formation water was significantly lower than that of the MCS which was associated with microstructure features. The higher strength MCS with the dispersed microstructure was less susceptible to hydrogen embrittlement under preliminary electrolytic hydrogenation than the lower strength MHCS with the coarse-grained microstructure. To estimate the embrittlement of steels the method of the FEM load simulation of the specimens with cracks was used. The constitutive relations of the true stress–strain of the tested steels were defined. The stress and strain dependences in the crack tip were calculated. It was found that the MHCS was characterized by the lower plasticity on the stage of the neck formation of the specimen and the lower fracture toughness than the other one. The obtained results demonstrating the limitations of the usage of casing pipes made of the MHCS with the coarse-grained ferrite/pearlite microstructure in corrosive and hydrogenating environments were discussed.
Prospects of Enhancing the Understanding of Material-hydrogen Interaction by Novel In-situ and In-operando Methods
Jan 2022
Publication
A main scientific and technical challenge facing the implementation of new and sustainable energy sources is the development and improvement of materials and components. In order to provide commercial viability of these applications an intensive research in material-hydrogen (H) interaction is required. This work provides an overview of recently developed in-situ and in-operando H-charging methods and their applicability to investigate mechanical properties H-absorption characteristics and H embrittlement (HE) susceptibility of a wide range of materials employed in H-related technologies such as subsea oil and gas applications nuclear fusion and fuel cells.
Influence of Pressure, Temperature and Organic Surface Concentration on Hydrogen Wettability of Caprock; Implications for Hydrogen Geo-storage
Sep 2021
Publication
Hydrogen (H2) as a cleaner fuel has been suggested as a viable method of achieving the decarbonization objectives and meeting increasing global energy demand. However successful implementation of a full-scale hydrogen economy requires large-scale hydrogen storage (as hydrogen is highly compressible). A potential solution to this challenge is injecting hydrogen into geologic formations from where it can be withdrawn again at later stages for utilization purposes. The geostorage capacity of a porous formation is a function of its wetting characteristics which strongly influence residual saturations fluid flow rate of injection rate of withdrawal and containment security. However literature severely lacks information on hydrogen wettability in realistic geological and caprock formations which contain organic matter (due to the prevailing reducing atmosphere). We therefore measured advancing (θa) and receding (θr) contact angles of mica substrates at various representative thermo-physical conditions (pressures 0.1-25 MPa temperatures 308–343 K and stearic acid concentrations of 10−9 - 10−2 mol/L). The mica exhibited an increasing tendency to become weakly water-wet at higher temperatures lower pressures and very low stearic acid concentration. However it turned intermediate-wet at higher pressures lower temperatures and increasing stearic acid concentrations. The study suggests that the structural H2 trapping capacities in geological formations and sealing potentials of caprock highly depend on the specific thermo-physical condition. Thus this novel data provides a significant advancement in literature and will aid in the implementation of hydrogen geo-storage at an industrial scale.
Linking Ab Initio Data on Hydrogen and Carbon in Steel to Statistical and Continuum Descriptions
Mar 2018
Publication
We present a selection of scale transfer approaches from the electronic to the continuum regime for topics relevant to hydrogen embrittlement. With a focus on grain boundary related hydrogen embrittlement we discuss the scale transfer for the dependence of the carbon solution behavior in steel on elastic effects and the hydrogen solution in austenitic bulk regions depending on Al content. We introduce an approximative scheme to estimate grain boundary energies for varying carbon and hydrogen population. We employ this approach for a discussion of the suppressing influence of Al on the substitution of carbon with hydrogen at grain boundaries which is an assumed mechanism for grain boundary hydrogen embrittlement. Finally we discuss the dependence of hydride formation on the grain boundary stiffness
Dynamic Operation of Fischer-Tropsch Reactors for Power-to-liquid Concepts: A Review
Apr 2022
Publication
The Fischer-Tropsch synthesis (FTS) is considered as a power-to-X (PtX) storage concept for converting temporally available excess energy to fuels or chemical compounds without the need of fossil resources. Fluctuating energy supplies demand a load-flexible energy system and a dynamically operating FTS reactor might be beneficial compared to traditional steady-state operations which rely on expensive upstream buffer capacities. This review provides an overview of recent experimental and simulation studies dealing with dynamic FTS operation and summarizes the main findings. The results are presented the two categories process intensification and PtX application. The review further discusses the experimentally difficult task of wide-ranging product characterization with a high temporal resolution. While dynamic reactor operation is often related to a complicated process control which challenges a save and efficient reactor performance the literature findings indicate that for dynamic FTS operation such concerns might not be as critical as assumed at least within well-known boundaries. Researchers further agree that dynamic operation might be a tool for process intensification. Especially hydrogen pulsing seems to be a potentially beneficial operating technique to remove accumulated liquid products restore initial catalyst activity and increase diesel-range productivity. The main challenge in this context is the prevention of high methane selectivity. A lucid future engineering goal seems to be the combination of the two applications: a robust and reliable FTS reactor in a PtX scenario that not only handles a fluctuating feed but uses such variations for process enhancement.
Cohesive Zone Modelling of Hydrogen Assisted Fatigue Crack Growth: The Role of Trapping
Apr 2022
Publication
We investigate the influence of microstructural traps in hydrogen-assisted fatigue crack growth. To this end a new formulation combining multi-trap stress-assisted diffusion mechanism-based strain gradient plasticity and a hydrogen- and fatigue-dependent cohesive zone model is presented and numerically implemented. The results show that the ratio of loading frequency to effective diffusivity governs fatigue crack growth behaviour. Increasing the density of beneficial traps not involved in the fracture process results in lower fatigue crack growth rates. The combinations of loading frequency and carbide trap densities that minimise embrittlement susceptibility are identified providing the foundation for a rational design of hydrogen-resistant alloys.
H21- Leeds City Gate Project Report
Jul 2016
Publication
The H21 Leeds City Gate project is a study with the aim of determining the feasibility from both a technical and economic viewpoint of converting the existing natural gas network in Leeds one of the largest UK cities to 100% hydrogen. The project has been designed to minimise disruption for existing customers and to deliver heat at the same cost as current natural gas to customers. The project has shown that:
The project has provided costs for the scheme and has modelled these costs in a regulatory finance model. In addition the availability of low-cost bulk hydrogen in a gas network could revolutionise the potential for hydrogen vehicles and via fuel cells support a decentralised model of combined heat and power and localised power generation.
This report and any attachment is freely available on the ENA Smarter Networks Portal here. IGEM Members can download the report and any attachment directly by clicking on the pdf icon above.
- The gas network has the correct capacity for such a conversion
- It can be converted incrementally with minimal disruption to customers
- Minimal new energy infrastructure will be required compared to alternatives
- The existing heat demand for Leeds can be met via steam methane reforming and salt cavern storage using technology in use around the world today
The project has provided costs for the scheme and has modelled these costs in a regulatory finance model. In addition the availability of low-cost bulk hydrogen in a gas network could revolutionise the potential for hydrogen vehicles and via fuel cells support a decentralised model of combined heat and power and localised power generation.
This report and any attachment is freely available on the ENA Smarter Networks Portal here. IGEM Members can download the report and any attachment directly by clicking on the pdf icon above.
Pressurized Hydrogen from Charged Liquid Organic Hydrogen Carrier Systems by Electrochemical Hydrogen Compression
Feb 2021
Publication
We demonstrate that the combination of hydrogen release from a Liquid Organic Hydrogen Carrier (LOHC) system with electrochemical hydrogen compression (EHC) provides three decisive advantages over the state-of-the-art hydrogen provision from such storage system: a) The EHC device produces reduced hydrogen pressure on its suction side connected to the LOHC dehydrogenation unit thus shifting the thermodynamic equilibrium towards dehydrogenation and accelerating the hydrogen release; b) the EHC device compresses the hydrogen released from the carrier system thus producing high value compressed hydrogen; c) the EHC process is selective for proton transport and thus the process purifies hydrogen from impurities such as traces of methane. We demonstrate this combination for the production of compressed hydrogen (absolute pressure of 6 bar) from perhydro dibenzyltoluene at dehydrogenation temperatures down to 240 °C in a quality suitable for fuel cell operation e.g. in a fuel cell vehicle. The presented technology may be highly attractive for providing compressed hydrogen at future hydrogen filling stations that receive and store hydrogen in a LOHC-bound manner.
Numerical Simulations of Cryogenic Hydrogen Cooling in Vortex Tubes with Smooth Transitions
Mar 2021
Publication
Improving efficiency of hydrogen cooling in cryogenic conditions is important for the wider applications of hydrogen energy systems. The approach investigated in this study is based on a Ranque-Hilsch vortex tube (RHVT) that generates temperature separation in a working fluid. The simplicity of RHVT is also a valuable characteristic for cryogenic systems. In the present work novel shapes of RHVT are computationally investigated with the goal to raise efficiency of the cooling process. Specifically a smooth transition is arranged between a vortex chamber where compressed gas is injected and the main tube with two exit ports at the tube ends. Flow simulations have been carried out using STAR-CCM+ software with the real-gas Redlich-Kwong model for hydrogen at temperatures near 70 K. It is determined that a vortex tube with a smooth transition of moderate size manifests about 7% improvement of the cooling efficiency when compared vortex tubes that use traditional vortex chambers with stepped transitions and a no-chamber setup with direct gas injection.
Investigation of Mechanical Tests for Hydrogen Embrittlement in Automotive PHS Steels
Aug 2019
Publication
The problem of hydrogen embrittlement in ultra-high-strength steels is well known. In this study slow strain rate four-point bending and permeation tests were performed with the aim of characterizing innovative materials with an ultimate tensile strength higher than 1000 MPa. Hydrogen uptake in the case of automotive components can take place in many phases of the manufacturing process: during hot stamping due to the presence of moisture in the furnace atmosphere high-temperature dissociation giving rise to atomic hydrogen or also during electrochemical treatments such as cataphoresis. Moreover possible corrosive phenomena could be a source of hydrogen during an automobile’s life. This series of tests was performed here in order to characterize two press-hardened steels (PHS)—USIBOR 1500® and USIBOR 2000®—to establish a correlation between ultimate mechanical properties and critical hydrogen concentration.
Hydrogen Embrittlement Evaluation of Micro Alloyed Steels by Means of J-Integral Curve
Jun 2019
Publication
The aim of this work is the evaluation of the hydrogen effect on the J-integral parameter. It is well-known that the micro alloyed steels are affected by Hydrogen Embrittlement phenomena only when they are subjected at the same time to plastic deformation and hydrogen evolution at their surface. Previous works have pointed out the absence of Hydrogen Embrittlement effects on pipeline steels cathodically protected under static load conditions. On the contrary in slow strain rate tests it is possible to observe the effect of the imposed potential and the strain rate on the hydrogen embrittlement steel behavior only after the necking of the specimens. J vs. Δa curves were measured on different pipeline steels in air and in aerated NaCl 3.5 g/L solution at free corrosion potential or under cathodic polarization at −1.05 and −2 V vs. SCE. The area under the J vs. Δa curves and the maximum crack propagation rate were taken into account. These parameters were compared with the ratio between the reduction of area in environment and in air obtained by slow strain rate test in the same environmental conditions and used to rank the different steels.
The Effect of Hydrogen on the Nanoindentation Behavior of Heat Treated 718 Alloy
Oct 2020
Publication
In this study the effect of precipitates on the surface mechanical properties in the presence of hydrogen (H) is investigated by in situ electrochemical nanoindentation. The nickel superalloy 718 is subjected to three different heat treatments leading to different sizes of the precipitates: (i) solution annealing (SA) to eliminate all precipitates (ii) the as-received (AR) sample with fine dispersed precipitates and (iii) the over-aged (OA) specimen with coarser precipitates. The nanoindentation is performed using a conical tip and a new method of reverse imaging is employed to calculate the nano-hardness. The results show that the hardness of the SA sample is significantly affected by H diffusion. However it could be recovered by removing the H from its matrix by applying an anodic potential. Since the precipitates in the OA and AR samples are different they are influenced by H differently. The hardness increase for the OA sample is more significant in −1200mV while for the AR specimen the H is more effective in −1500mV. In addition the pop-in load is reduced when the samples are exposed to cathodic charging and it cannot be fully recovered by switching to an anodic potential.
Integration of Wind Energy, Hydrogen and Natural Gas Pipeline Systems to Meet Community and Transportation Energy Needs: A Parametric Study
Apr 2014
Publication
The potential benefits are examined of the “Power-to-Gas” (P2G) scheme to utilize excess wind power capacity by generating hydrogen (or potentially methane) for use in the natural gas distribution grid. A parametric analysis is used to determine the feasibility and size of systems producing hydrogen that would be injected into the natural gas grid. Specifically wind farms located in southwestern Ontario Canada are considered. Infrastructure requirements wind farm size pipeline capacity geographical dispersion hydrogen production rate capital and operating costs are used as performance measures. The model takes into account the potential production rate of hydrogen and the rate that it can be injected into the local gas grid. “Straw man” systems are examined centered on a wind farm size of 100 MW integrating a 16-MW capacity electrolysis system typically producing 4700 kg of hydrogen per day.
Pt Catalytic Effects on the Corrosion and Hydrogen Chemisorption Properties of Zircaloy-2
Dec 2020
Publication
Noble metals are added to boiling water reactors (BWRs) to mitigate stress corrosion cracking of structural components made from steels and Ni-based alloys and this technology is referred to as Noble Metal Chemical Addition (NMCA) or NobleChemTM. There is a growing concern that NMCA can cause unwanted harmful effects on the corrosion and hydrogen uptake properties of Zircaloy-2 fuel cladding. To investigate this we have subjected Zircaloy-2 fuel claddings to out-of-pile BWR conditions in a custom-built autoclave. These claddings are oxidized in pressurized hot water (280 °C 9 MPa) for 25 60 and 150 days wherein Pt nanoparticles (~10 nm) were simultaneously injected. Cross-sectional focused ion beam cuts made at the oxide-metal interface reveal that the oxide growth is not significantly influenced by the local Pt loadings (≤ 1 µg·cm-2). Surprisingly an inverse correlation was observed between oxide thicknesses and metal's hydrogen contents. Interestingly Pt catalysts have led to diminished hydrogen absorption in specimens with liner exposed to the hot water. Overall Pt catalysts exhibited no detrimental effects on the corrosion rate and hydrogen absorption in Zircaloy-2.
Thickness-Prediction Method Involving Tow Redistribution for the Dome of Composite Hydrogen Storage Vessels
Feb 2022
Publication
Traditional thickness-prediction methods underestimate the actual dome thickness at polar openings leading to the inaccurate prediction of the load-bearing capacity of composite hydrogen storage vessels. A method of thickness prediction for the dome section of composite hydrogen storage vessels was proposed which involved fiber slippage and tow redistribution. This method considered the blocking effect of the port on sliding fiber tows and introduced the thickness correlation to predict the dome thickness at polar openings. The arc length corresponding to the parallel circle radius was calculated and then the actual radius values corresponding to the bandwidth were obtained by the interpolation method. The predicted thickness values were compared with the actual measured thickness. The maximum relative error of the predicted thickness was 4.19% and the mean absolute percentage error was 2.04%. The results show that the present method had a higher prediction accuracy. Eventually this prediction method was used to perform progressive damage analysis on vessels. By comparing with the results of the cubic spline function method the analysis results of the present method approached the actual case. This showed that the present method improved the accuracy of the design.
Polymer–Ceramic Composite Membranes for Water Removal in Membrane Reactors
Jun 2021
Publication
Methanol can be obtained through CO2 hydrogenation in a membrane reactor with higher yield or lower pressure than in a conventional packed bed reactor. In this study we explore a new kind of membrane with the potential suitability for such membrane reactors. Silicone–ceramic composite membranes are synthetized and characterized for their capability to selectively remove water from a mixture containing hydrogen CO2 and water at temperatures typical for methanol synthesis. We show that this membrane can achieve selective permeation of water under such harsh conditions and thus is an alternative candidate for use in membrane reactors for processes where water is one of the products and the yield is limited by thermodynamic equilibrium.
Review on the Influence of Temperature upon Hydrogen Effects in Structural Alloys
Mar 2021
Publication
It is well-documented experimentally that the influence of hydrogen on the mechanical properties of structural alloys like austenitic stainless steels nickel superalloys and carbon steels strongly depends on temperature. A typical curve plotting any hydrogen-affected mechanical property as a function of temperature gives a temperature THEmax where the degradation of this mechanical property reaches a maximum. Above and below this temperature the degradation is less. Unfortunately the underlying physico-mechanical mechanisms are not currently understood to the level of detail required to explain such temperature effects. Though this temperature effect is important to understand in the context of engineering applications studies to explain or even predict the effect of temperature upon the mechanical properties of structural alloys could not be identified. The available experimental data are scattered significantly and clear trends as a function of chemistry or microstructure are difficult to see. Reported values for THEmax are in the range of about 200–340 K which covers the typical temperature range for the design of structural components of about 230–310 K (from −40 to +40 °C). That is the value of THEmax itself as well as the slope of the gradient might affect the materials selection for a dedicated application. Given the current lack of scientific understanding a statistical approach appears to be a suitable way to account for the temperature effect in engineering applications. This study reviews the effect of temperature upon hydrogen effects in structural alloys and proposes recommendations for test temperatures for gaseous hydrogen applications
Application of the Incremental Step Loading Technique to Small Punch Tests on S420 Steel in Acid Environments
Dec 2020
Publication
The Small Punch test has been recently used to estimate mechanical properties of steels in aggressive environments. This technique very interesting when there is shortage of material consists in using a small plane specimen and punch it until it fails. The type of tests normally used are under a constant load in an aggressive environment with the target to determine the threshold stress. However this is an inaccurate technique which takes time as the tests are quite slow. In this paper the Small Punch tests are combined with the step loading technique collected in the standard ASTM F1624 [1] to obtain the value of threshold stress of an S420 steel in a total time of approximately one week. The ASTM F1624 indicates how to apply constant load steps in hydrogen embrittlement environments increasing them subsequently and adapting their duration until the specimen fails. The environment is created by means of cathodic polarization of cylindrical tensile specimens in an acid electrolyte. A batch of standard tests are performed to validate the methodology.
Recent Advances in Pd-Based Membranes for Membrane Reactors
Jan 2017
Publication
Palladium-based membranes for hydrogen separation have been studied by several research groups during the last 40 years. Much effort has been dedicated to improving the hydrogen flux of these membranes employing different alloys supports deposition/production techniques etc. High flux and cheap membranes yet stable at different operating conditions are required for their exploitation at industrial scale. The integration of membranes in multifunctional reactors (membrane reactors) poses additional demands on the membranes as interactions at different levels between the catalyst and the membrane surface can occur. Particularly when employing the membranes in fluidized bed reactors the selective layer should be resistant to or protected against erosion. In this review we will also describe a novel kind of membranes the pore-filled type membranes prepared by Pacheco Tanaka and coworkers that represent a possible solution to integrate thin selective membranes into membrane reactors while protecting the selective layer. This work is focused on recent advances on metallic supports materials used as an intermetallic diffusion layer when metallic supports are used and the most recent advances on Pd-based composite membranes. Particular attention is paid to improvements on sulfur resistance of Pd based membranes resistance to hydrogen embrittlement and stability at high temperature.
Atomistic Modelling of Light-element Co-segregation at Structural Defects in Iron
Dec 2018
Publication
Studying the behaviour of hydrogen in the vicinity of extended defects such as grain boundaries dislocations nanovoids and phase boundaries is critical in understanding the phenomenon of hydrogen embrittlement. A key complication in this context is the interplay between hydrogen and other segregating elements. Modelling the competition of H with other light elements requires an efficient description of the interactions of compositionally complex systems with the system sizes needed to appropriately describe extended defects often precluding the use of direct ab initio approaches. In this regard we have developed novel electronic structure approaches to understand the energetics and mutual interactions of light elements at representative structural features in high-strength ferritic steels. Using this approach we examine the co-segregation of hydrogen with carbon at chosen grain boundaries in α-iron. We find that the strain introduced by segregated carbon atoms at tilt grain boundaries increases the solubility of hydrogen close to the boundary plane giving a higher H concentration in the vicinity of the boundary than in a carbon-free case. Via simulated tensile tests we find that the simultaneous presence of carbon and hydrogen at grain boundaries leads to a significant decrease in the elongation to fracture compared with the carbon-free case.
Decrease in Hydrogen Embrittlement Susceptibility of 10B21 Screws by Bake Aging
Aug 2016
Publication
The effects of baking on the mechanical properties and fracture characteristics of low-carbon boron (10B21) steel screws were investigated. Fracture torque tests and hydrogen content analysis were performed on baked screws to evaluate hydrogen embrittlement (HE) susceptibility. The diffusible hydrogen content within 10B21 steel dominated the fracture behavior of the screws. The fracture torque of 10B21 screws baked for a long duration was affected by released hydrogen. Secondary ion mass spectroscopy (SIMS) result showed that hydrogen content decreased with increasing baking duration and thus the HE susceptibility of 10B21 screws improved. Diffusible hydrogen promoted crack propagation in high-stress region. The HE of 10B21 screws can be prevented by long-duration baking.
Hydrogen Induced Damage in Heavily Cold-Drawn Wires of Lean Duplex Stainless Steel
Sep 2017
Publication
The paper addresses the sensitivity to hydrogen embrittlement of heavily cold-drawn wires made of the new generation of lower alloyed duplex stainless steels often referred to as lean duplex grades. It includes comparisons with similar data corresponding to cold-drawn eutectoid and duplex stainless steels. For this purpose fracture tests under constant load were carried out with wires in the as-received condition and fatigue-precracked in air and exposed to ammonium thiocyanate solution. Microstructure and fractographic observations were essential means for the cracking analysis. The effect of hydrogen-assisted embrittlement on the damage tolerance of lean duplex steels was assessed regarding two macro-mechanical damage models that provide the upper bounds of damage tolerance and accurately approximate the failure behavior of the eutectoid and duplex stainless steels wires.
Energetics of LOHC: Structure-Property Relationships from Network of Thermochemical Experiments and in Silico Methods
Feb 2021
Publication
The storage of hydrogen is the key technology for a sustainable future. We developed an in silico procedure which is based on the combination of experimental and quantum-chemical methods. This method was used to evaluate energetic parameters for hydrogenation/dehydrogenation reactions of various pyrazine derivatives as a seminal liquid organic hydrogen carriers (LOHC) that are involved in the hydrogen storage technologies. With this in silico tool the tempo of the reliable search for suitable LOHC candidates will accelerate dramatically leading to the design and development of efficient materials for various niche applications.
Energy Transition: Measurement Needs for Carbon Capture, Usage and Storage
Jan 2021
Publication
This latest report describes the potential for CCUS as an important technology during the UK’s energy transition and focuses on the role that metrology (the science of measurement) could play in supporting its deployment. High priority measurement needs and challenges identified within this report include:
- Measuring and comparing the efficiency of different capture techniques and configurations to provide confidence in investments into technologies;
- Improving equations of state to support the development of accurate models used for controlling operational conditions;
- Improving CO2 flow measurement to support fiscal and financial metering as well as process control and;
- Improving the understanding and validation of dispersion models for emitted CO2 including plume migration to support safety assessment.
Combined Cooling and Power Management Strategy for a Standalone House Using Hydrogen and Solar Energy
May 2021
Publication
Tropical climate is characterized by hot temperatures throughout the year. In areas subject to this climate air conditioning represents an important share of total energy consumption. In some tropical islands there is no electric grid; in these cases electricity is often provided by diesel generators. In this study in order to decarbonize electricity and cooling production and to improve autonomy in a standalone application a microgrid producing combined cooling and electrical power was proposed. The presented system was composed of photovoltaic panels a battery an electrolyzer a hydrogen tank a fuel cell power converters a heat pump electrical loads and an adsorption cooling system. Electricity production and storage were provided by photovoltaic panels and a hydrogen storage system respectively while cooling production and storage were achieved using a heat pump and an adsorption cooling system respectively. The standalone application presented was a single house located in Tahiti French Polynesia. In this paper the system as a whole is presented. Then the interaction between each element is described and a model of the system is presented. Thirdly the energy and power management required in order to meet electrical and thermal needs are presented. Then the results of the control strategy are presented. The results showed that the adsorption cooling system provided 53% of the cooling demand. The use of the adsorption cooling system reduced the needed photovoltaic panel area the use of the electrolyzer and the use of the fuel cell by more than 60% and reduced energy losses by 7% (compared to a classic heat pump) for air conditioning.
Critical Review of Models for H2-permeation Through Polymers with Focus on the Differential Pressure Method
May 2021
Publication
To reduce loss of hydrogen in storage vessels with high energy-to-weight-ratio new materials especially polymers have to be developed as barrier materials. Very established methods for characterization of barrier materials with permeation measurements are the time-lag and flow rate method along with the differential pressure method which resembles the nature of hydrogen vessel systems very well. Long measurement durations are necessary to gain suitable measurement data for these evaluation methods and often restrictive conditions have to be fulfilled. For these reasons common models for hydrogen permeation through single-layer and multi-layer membranes as well as models for hydrogen gas properties were collected and reviewed. Using current computer power together with these models can reduce measurement time for characterization of the barrier properties of materials while additional information about the quality of the measurement results is obtained.
European Hydrogen Backbone
Jul 2020
Publication
This paper authored by eleven gas infrastructure companies and supported by Guidehouse describes how a dedicated hydrogen infrastructure can be created in
a significant part of the EU between 2030 and 2040 requiring work to start during the 2020s. The hydrogen infrastructure as proposed in this paper fits well with the ambitions of the EU Hydrogen Strategy and the Energy System Integration Strategy plus it aligns well with the goals of the recently announced Clean Hydrogen Alliance to scale up hydrogen enabled by hydrogen transport. Hydrogen clearly gains momentum and this paper aims to provide a contribution towards accelerating a large scale-up of hydrogen by enabling its transport from supply to demand across Europe.
This paper analyses the likely routes across Europe by 2030 2035 and 2040. The included maps show the suggested topology of hydrogen pipelines in ten European countries: Germany France Italy Spain the Netherlands Belgium Czech Republic Denmark Sweden and Switzerland.
You can download the whole report by clicking this link
a significant part of the EU between 2030 and 2040 requiring work to start during the 2020s. The hydrogen infrastructure as proposed in this paper fits well with the ambitions of the EU Hydrogen Strategy and the Energy System Integration Strategy plus it aligns well with the goals of the recently announced Clean Hydrogen Alliance to scale up hydrogen enabled by hydrogen transport. Hydrogen clearly gains momentum and this paper aims to provide a contribution towards accelerating a large scale-up of hydrogen by enabling its transport from supply to demand across Europe.
This paper analyses the likely routes across Europe by 2030 2035 and 2040. The included maps show the suggested topology of hydrogen pipelines in ten European countries: Germany France Italy Spain the Netherlands Belgium Czech Republic Denmark Sweden and Switzerland.
You can download the whole report by clicking this link
Geomechanical Simulation of Energy Storage in Salt Formations
Oct 2021
Publication
A promising option for storing large-scale quantities of green gases (e.g. hydrogen) is in subsurface rock salt caverns. The mechanical performance of salt caverns utilized for long-term subsurface energy storage plays a signifcant role in long-term stability and serviceability. However rock salt undergoes non-linear creep deformation due to long-term loading caused by subsurface storage. Salt caverns have complex geometries and the geological domain surrounding salt caverns has a vast amount of material heterogeneity. To safely store gases in caverns a thorough analysis of the geological domain becomes crucial. To date few studies have attempted to analyze the infuence of geometrical and material heterogeneity on the state of stress in salt caverns subjected to long-term loading. In this work we present a rigorous and systematic modeling study to quantify the impact of heterogeneity on the deformation of salt caverns and quantify the state of stress around the caverns. A 2D fnite element simulator was developed to consistently account for the non-linear creep deformation and also to model tertiary creep. The computational scheme was benchmarked with the already existing experimental study. The impact of cyclic loading on the cavern was studied considering maximum and minimum pressure that depends on lithostatic pressure. The infuence of geometric heterogeneity such as irregularly-shaped caverns and material heterogeneity which involves diferent elastic and creep properties of the diferent materials in the geological domain is rigorously studied and quantifed. Moreover multi-cavern simulations are conducted to investigate the infuence of a cavern on the adjacent caverns. An elaborate sensitivity analysis of parameters involved with creep and damage constitutive laws is performed to understand the infuence of creep and damage on deformation and stress evolution around the salt cavern confgurations.
Power to Hydrogen and Power to Water Using Wind Energy
May 2022
Publication
The need for energy and water security on islands has led to an increase in the use of wind power. However the intermittent nature of wind generation means it needs to be coupled with a storage system. Motivated by this two different models of surplus energy storage systems are investigated in this paper. In both models renewable wind energy is provided by a wind farm. In the first model a pumped hydro storage system (PHS) is used for surplus energy storage while in the second scenario a hybrid pumped hydrogen storage system (HPHS) is applied consisting of a PHS and a hydrogen storage system. The goal of this study is to compare the single and the hybrid storage system to fulfill the energy requirements of the island’s electricity load and desalination demands for domestic and irrigation water. The cost of energy (COE) is 0.287 EUR/kWh for PHS and 0.360 EUR/kWh for HPHS while the loss of load probability (LOLP) is 22.65% for PHS and 19.47% for HPHS. Sensitivity analysis shows that wind speed is the key parameter that most affects COE cost of water (COW) and LOLP indices while temperature affects the results the least.
Mechanical Spectroscopy Investigation of Point Defect-Driven Phenomena in a Cr Martensitic Steel
Oct 2018
Publication
The paper presents and discusses results of mechanical spectroscopy (MS) tests carried out on a Cr martensitic steel. The study regards the following topics: (i) embrittlement induced by Cr segregation; (ii) interaction of hydrogen with C–Cr associates; (iii) nucleation of Cr carbides. The MS technique permitted characterising of the specific role played by point defects in the investigated phenomena: (i) Cr segregation depends on C–Cr associates distribution in as-quenched material in particular a slow cooling rate (~150 K/min) from austenitic field involves an unstable distribution which leads to Cr concentration fluctuations after tempering at 973 K; (ii) hydrogen interacts with C–Cr associates and the phenomenon hinders hydrogen attack (HA) because hydrogen atoms bound by C–Cr associates are not able to diffuse towards grain boundaries and dislocation where CH4 bubbles may nucleate grow and merge to form the typical HA cracks; (iii) C–Cr associates take part in the nucleation mechanism of Cr7C3 carbides and specifically these carbides form by the aggregation of C–Cr associates with 1 Cr atom.
Multiscale Modelling of Hydrogen Transport and Segregation in Polycrystalline Steels
Jun 2018
Publication
A key issue in understanding and effectively managing hydrogen embrittlement in complex alloys is identifying and exploiting the critical role of the various defects involved. A chemo-mechanical model for hydrogen diffusion is developed taking into account stress gradients in the material as well as microstructural trapping sites such as grain boundaries and dislocations. In particular the energetic parameters used in this coupled approach are determined from ab initio calculations. Complementary experimental investigations that are presented show that a numerical approach capable of massive scale-bridging up to the macroscale is required. Due to the wide range of length scales accounted for we apply homogenisation schemes for the hydrogen concentration to reach simulation dimensions comparable to metallurgical process scales. Via a representative volume element approach an ab initio based scale bridging description of dislocation-induced hydrogen aggregation is easily accessible. When we extend the representative volume approach to also include an analytical approximation for the ab initio based description of grain boundaries we find conceptual limitations that hinder a quantitative comparison to experimental data in the current stage. Based on this understanding the development of improved strategies for further efficient scale bridging approaches is foreseen.
The Effect of Cold Rolling on the Hydrogen Susceptibility of 5083 Aluminium Alloy
Oct 2017
Publication
This work focuses in investigating the effect of cold deformation on the cathodic hydrogen charging of 5083 aluminum alloy. The aluminium alloy was submitted to a cold rolling process until the average thickness of the specimens was reduced by 7% and 15% respectively. A study of the structure microhardness and tensile properties of the hydrogen charged aluminium specimens with and without cold rolling indicated that the cold deformation process led to an increase of hydrogen susceptibility of this aluminum alloy.
Hydrogen Impacts on Downstream Installation and Appliances
Nov 2019
Publication
The report analyses the technical impacts to end-users of natural gas in Australian distribution networks when up to 10% hydrogen (by volume) is mixed with natural gas.
The full report can be found at this link.
The full report can be found at this link.
Formation Criterion of Hydrogen-Induced Cracking in Steel Based on Fracture Mechanics
Nov 2018
Publication
A new criterion for hydrogen-induced cracking (HIC) that includes both the embrittlement effect and the loading effect of hydrogen was obtained theoretically. The surface cohesive energy and plastic deformation energy are reduced by hydrogen atoms at the interface; thus the fracture toughness is reduced according to fracture mechanics theory. Both the pressure effect and the embrittlement effect mitigate the critical condition required for crack instability extension. During the crack instability expansion the hydrogen in the material can be divided into two categories: hydrogen atoms surrounding the crack and hydrogen molecules in the crack cavity. The loading effect of hydrogen was verified by experiments and the characterization methods for the stress intensity factor under hydrogen pressure in a linear elastic model and an elastoplastic model were analyzed using the finite-element simulation method. The hydrogen pressure due to the aggregation of hydrogen molecules inside the crack cavity regularly contributed to the stress intensity factor. The embrittlement of hydrogen was verified by electrolytic charging hydrogen experiments. According to the change in the atomic distribution during crack propagation in a molecular dynamics simulation the transition from ductile to brittle fracture and the reduction in the fracture toughness were due to the formation of crack tip dislocation regions suppressed by hydrogen. The HIC formation mechanism is both the driving force of crack propagation due to the hydrogen gas pressure and the resisting force reduced by hydrogen atoms.
Prospecting Stress Formed by Hydrogen or Isotope Diffused in Palladium Alloy Cathode
Oct 2018
Publication
The objective of this project is to take into account the mechanical constraints formed by diffusion of hydrogen or tritium in watertight palladium alloy cathode. To know the origin of these it was necessary to discriminating the damaging effects encountered. Effectively hydrogen and isotope induce deformation embrittlement stress corrosion cracking and cathodic corrosion in different regions of cathode. Palladium can be alloyed with silver or yttrium to favourably increase diffusion and reduce these constraints. Effects of electrochemical factors temperature cathode structure adsorbed transient complex of palladium and porous material support are given to estimate and to limit possible damage.
The Microstructure Study of the Hydrogenated Titanium Specimens Tested at High Temperature Creep for Long-term Tensile Strength
Feb 2020
Publication
Experimental tests of flat titanium samples at a temperature of 450 °C stretched with a constant force up to destruction were carried out. Titanium samples were hydrogenated in the Moscow Aviation Institute laboratory to a hydrogen content of 0.1 % 0.3 % and 0.6 % by weight of the specimen and then tested in the laboratory of Lomonosov Moscow State University. From the experiments the time to failure the localization time of the deformations and the stress distribution along the longitudinal coordinate of the sample over time were obtained. A metallographic study was conducted and the phase composition was investigated in Moscow Aviation Institute. The effect of hydrogen on long-term strength mechanical characteristics and phase composition has been elucidated.
Metastable Metal Hydrides for Hydrogen Storage
Oct 2012
Publication
The possibility of using hydrogen as a reliable energy carrier for both stationary and mobile applications has gained renewed interest in recent years due to improvements in high temperature fuel cells and a reduction in hydrogen production costs. However a number of challenges remain and new media are needed that are capable of safely storing hydrogen with high gravimetric and volumetric densities. Metal hydrides and complex metal hydrides offer some hope of overcoming these challenges; however many of the high capacity “reversible” hydrides exhibit a large endothermic decomposition enthalpy making it difficult to release the hydrogen at low temperatures. On the other hand the metastable hydrides are characterized by a low reaction enthalpy and a decomposition reaction that is thermodynamically favorable under ambient conditions. The rapid low temperature hydrogen evolution rates that can be achieved with these materials offer much promise for mobile PEM fuel cell applications. However a critical challenge exists to develop new methods to regenerate these hydrides directly from the reactants and hydrogen gas. This spotlight paper presents an overview of some of the metastable metal hydrides for hydrogen storage and a few new approaches being investigated to address the key challenges associated with these materials.
The Role of CCS in Meeting Climate Policy Targets
Oct 2017
Publication
Carbon capture and storage (CCS) refers to a set of technologies that may offer the potential for large-scale removal of CO2 emissions from a range of processes – potentially including the generation of electricity and heat industrial processes and the production of hydrogen and synthetic fuels. CCS has both proponents and opponents. Like other emerging low carbon technologies CCS is not without risks or uncertainties and there are various challenges that would need to be overcome if it were to be widely deployed. Policy makers’ decisions as to whether to pursue CCS should be based on a judgement as to whether the risks and uncertainties associated with attempting to deploy CCS outweigh the risks of not having it available as part of a portfolio of mitigation options in future years.
The full report can be found on the Global CSS Institute website at this link
The full report can be found on the Global CSS Institute website at this link
Effect of Cementite on the Hydrogen Diffusion/Trap Characteristics of 2.25Cr-1Mo-0.25V Steel with and without Annealing
May 2018
Publication
Hydrogen embrittlement (HE) is a critical issue that affects the reliability of hydrogenation reactors. The hydrogen diffusivity/trap characteristics of 2.25Cr-1Mo-0.25V steel are important parameters mainly used to study the HE mechanism of steel alloys. In this work the hydrogen diffusivity/trap characteristics of heat-treated (annealed) and untreated 2.25Cr-1Mo-0.25V steel were studied using an electrochemical permeation method. The microstructures of both 2.25Cr-1Mo-0.25V steels were investigated by metallurgical microscopy. The effect of cementite on the hydrogen diffusivity/trap mechanisms was studied using thermodynamics-based and Lennard–Jones potential theories. The results revealed that the cementite located at the grain boundaries and at the interfaces of lath ferrite served as a kind of hydrogen trap (i.e. an irreversible hydrogen trap). In addition hydrogen was transported from ferrite to cementite via up-hill diffusion thereby supporting the hypothesis of cementite acting as a hydrogen trap.
Hydrogen Assisted Macrodelamination in Gas Lateral Pipe
Jul 2016
Publication
Hydrogen assisted macrodelamination in the pipe elbows of 40-year exploited lateral pipelines located behind the compressor station was studied. The crack on the external surface of the pipe elbow was revealed. Macrodelamination was occurred in the steel being influenced by the joined action of working loads and hydrogen absorbed by metal during long-term operation. The causes of the material degradation were investigated by non-destructive testing using ultrasound thickness meter observing microstructure hydrostatic pressure testing and mechanical properties testing of pipe steel.<br/>Intensive degradation of steel primarily essential reduction of plasticity was revealed. The degradation degree of the pipe elbow steel was higher than of the straight pipe steel regardless of a section was tensioned or compressed. Basing on the tensile tests carried out on cylindrical smooth and notched specimens from the pipe elbow steel it was established that the plasticity of the damaged steel could be measured correctly only on the specimens with a circular notch due to concentration of deformation in the cross section location only. The limitations in using elongation and reduction in area for characterisation of plasticity of the pipe steel with extensive delamination were defined. The diagnostic features of macrodelamination namely an abnormal thickness meter readings and a sharp decrease in hardness and plasticity of the pipe elbow steel were established.
Electrochemical and Stress Corrosion Mechanism of Submarine Pipeline in Simulated Seawater in Presence of Different Alternating Current Densities
Jun 2018
Publication
In this study electrochemical measurements immersion tests and slow strain rate tensile (SSRT) tests were applied to investigate the electrochemical and stress corrosion cracking (SCC) behavior of X70 steel in simulated seawater with the interference of different alternating current (AC) densities. The results indicate that AC significantly strengthens the cathodic reaction especially the oxygen reduction reaction. Simultaneously hydrogen evolution reaction occurs when the limiting diffusion current density of oxygen reaches and thus icorr sharply increases with the increase in AC density. Additionally when AC is imposed the X70 steel exhibits higher SCC susceptibility in the simulated seawater and the susceptibility increases with the increasing AC density. The SCC mechanism is controlled by both anodic dissolution (AD) and hydrogen embrittlement (HE) with the interference of AC.
Hydrogen Embrittlement Mechanism in Fatigue Behavior of Austenitic and Martensitic Stainless Steels
May 2018
Publication
In the present study the influence of hydrogen on the fatigue behavior of the high strength martensitic stainless steel X3CrNiMo13-4 and the metastable austenitic stainless steels X2Crni19-11 with various nickel contents was examined in the low and high cycle fatigue regime. The focus of the investigations were the changes in the mechanisms of short crack propagation. Experiments in laboratory air with uncharged and precharged specimen and uncharged specimen in pressurized hydrogen were carried out. The aim of the ongoing investigation was to determine and quantitatively describe the predominant processes of hydrogen embrittlement and their influence on the short fatigue crack morphology and crack growth rate. In addition simulations were carried out on the short fatigue crack growth in order to develop a detailed insight into the hydrogen embrittlement mechanisms relevant for cyclic loading conditions. It was found that a lower nickel content and a higher martensite content of the samples led to a higher susceptibility to hydrogen embrittlement. In addition crack propagation and crack path could be simulated well with the simulation model.
Study on Flake Formation Behavior and Its Influence Factors in Cr5 Steel
Apr 2018
Publication
A flake is a crack that is induced by trapped hydrogen within steel. To study its formation mechanism previous studies mostly focused on the formation process and magnitude of hydrogen pressure in hydrogen traps such as cavities and cracks. However according to recent studies the hydrogen leads to the decline of the mechanical properties of steel which is known as hydrogen embrittlement is another reason for flake formation. In addition the phenomenon of stress induced hydrogen uphill diffusion should not be neglected. All of the three behaviors are at work simultaneously. In order to further explore the formation mechanism of flakes in steel the process of flake initiation and growth were studied with the following three coupling factors: trap hydrogen pressure hydrogen embrittlement and stress induced hydrogen re-distribution. The analysis model was established using the finite element method and a crack whose radius is 0.5 mm was set in its center. The cohesive method and Bilinear Traction Separate Law (BTSL) were used to address the coupling effect. The results show that trap hydrogen pressure is the main driving force for flake formation. After the high hydrogen pressure was generated around the trap a stress field formed. In addition the trap is the center of stress concentration. Then hydrogen is concentrated in a distribution around this trap and most of the steel mechanical properties are reduced. The trap size is a key factor for defining the critical hydrogen content for flake formation and propagation. However when the trap size exceeds the specified value the critical hydrogen content does not change any more. As for the crack whose radius is 0.5 mm the critical hydrogen content of Cr5VMo steel is 2.2 ppm which is much closer to the maximum safe hydrogen concentration of 2.0 ppm used in China. The work presented in this article increases our understanding of flake formation and propagation mechanisms in steel.
Reliability of Liquid Organic Hydrogen Carrier-based Energy Storage in a Mobility Applications
Jan 2020
Publication
Liquid organic hydrogen carriers (LOHC) are a technology that allows storing hy-drogen in a safe and dense manner by reversible chemical conversion. They consti-tute a very promising option for energy storage transport and release combined withelectric power generation by fuel cells in large-scale applications like trains. In orderto establish trains running on LOHC it is mandatory to ensure the reliability of thesystem. This study evaluates various system configurations concerning reliabilityand resilience. The fault tree analysis method has been used to quantify the prob-ability of failure. The S-P matrix was applied to assess the different failure modes incontext of severity as well as their probability. The MTTF of the system can be morethan doubled by introducing single redundancy for the fuel cell and the reactor whilemore than two redundant components diminish the positive effect on reliability dueto higher complexity. It is estimated that the systems full functionality is available formore than 97% of its operating time.
Failure Analysis of Cooling Duct of Top Engine Cowl Panel of Fighter Aircraft
Jun 2019
Publication
Present work describes the failure analysis of cooling duct of a fighter aircraft. The analyzed chemical composition of cooling duct indicates that it is manufactured from Al-based alloy (AA 3003 or its equivalent). Microstructure of cooling duct displays the presence of two phases namely matrix and insoluble particles. The hardness values at different locations within damaged area of cooling duct reflect nearly same and consistent. The fracture surface of the cooling duct exhibits transgranular features and cracks with little branching. The analyzed hydrogen content in cooling duct is significantly higher (∼ 12 ppm) than the specified one (< 1 ppm). However the alloy used to fabricate cooling duct is not susceptible to typical hydrogen embrittlement. This shows hydrogen pick up during operation. The presence of cracks with branching does reflect features of hydrogen embrittlement. In addition striations indicative of fatigue features are also observed. It thus appears that the cooling duct has failed due to pick up of large amount of hydrogen as well as vibrational fatigue.
Fractographic Features of Long Term Operated Gas Pipeline Steels Fracture Under Impact Loading
Jan 2020
Publication
Pipelines during their service life subjected to operational degradation i.e. their mechanical characteristics worsened with time. Pronounced texture of pipe steels associated with their manufacturing process revealed itself in an essential difference in impact toughness determined for specimens cut in mutually perpendicular directions with respect to the pipe axis. Higher KCV values for longitudinal specimens as compared with transverse ones were explained by the difference in a length of perlite grain strips separated by ferrite grains in specimens of different orientation. A role of hydrogen absorbed my metal during its operation in steel degradation was discussed.<br/>The main fractographic peculiarity for the operated steels comparing to the steels in the initial state is the appearance of delamination on the fracture surfaces which are oriented in the rolling direction. Correlation was found for the tested steels between fractographic sings of their embrittlement due to operational degradation and their loss of brittle fracture resistance. It is concluded that a decrease of impact toughness caused by long term operation of pipeline steels is definitely concerned with the amount of delamination on the fracture surfaces.
Investigation of Certain Mechanical and Magnetic Properties of a Stressed Low-carbon steel after corrosion in NaCl-water solution
Jun 2020
Publication
Atomic hydrogen produced by corrosion of a low-carbon steel in NaCl – Water solution may markedly affect its certain tensile mechanical and magnetic properties in a complex and peculiar manner. This influence was investigated by employing the intrinsic micromagnetic emission (ME)-response as well as tensile mechanical response of this ferromagnetic material and also by introduction a relevant measurement parameter of specific micromagnetic emission response. In this fashion it was shown that an increase in the hydrogen accumulation with corrosion time leads to an associated increase in the pervasive and embrittling influence expressed by a marked loss in ductility of the material. It was also shown that the competitive interplay of cumulative hydrogen applied stress and plastic strain-induced microstructural damage was related to a specific ME-response parameter by which an increased magnetic hardening tendency of material with corrosion time was established. In general embrittlement and magnetic hardening are parallel products of stress- assisted hydrogen accumulation where magnetic hardening process seems to be in a time processing advance of embrittlement one. The above findings allow to estimate that the magnetic properties are more susceptible to hydrogen effects than the mechanical ones.
Effect of Corrosion-induced Hydrogen Embrittlement and its Degradation Impact on Tensile Properties and Fracture Toughness of (Al-Cu-Mg) 2024 Alloy
Jul 2016
Publication
In the present work the effect of artificial ageing of AA2024-T3 on the tensile mechanical properties and fracture toughness degradation due to corrosion exposure will be investigated. Tensile and fracture toughness specimens were artificially aged to tempers that correspond to Under-Ageing (UA) Peak-Ageing (PA) and Over-Ageing (OA) conditions and then were subsequently exposed to exfoliation corrosion environment. The corrosion exposure time was selected to be the least possible according to the experimental work of Alexopoulos et al. (2016) so as to avoid the formation of large surface pits trying to simulate the hydrogen embrittlement degradation only. The mechanical test results show that minimum corrosion-induced decrease in elongation at fracture was achieved for the peak-ageing condition while maximum was noticed at the under-ageing and over-ageing conditions. Yield stress decrease due to corrosion is less sensitive to tempering; fracture toughness decrease was sensitive to ageing heat treatment thus proving that the S΄ particles play a significant role on the corrosion-induced degradation.
Recent Progress in Hydrogen Storage
Nov 2008
Publication
The ever-increasing demand for energy coupled with dwindling fossil fuel resources make the establishment of a clean and sustainable energy system a compelling need. Hydrogen-based energy systems offer potential solutions. Although in the long-term the ultimate technological challenge is large-scale hydrogen production from renewable sources the pressing issue is how to store hydrogen efficiently on board hydrogen fuel-cell vehicles.
Microalloyed Steels through History until 2018: Review of Chemical Composition, Processing and Hydrogen Service
May 2018
Publication
Microalloyed steels have evolved in terms of their chemical composition processing and metallurgical characteristics since the beginning of the 20th century in the function of fabrication costs and mechanical properties required to obtain high-performance materials needed to accommodate for the growing demands of gas and hydrocarbons transport. As a result of this microalloyed steels present a good combination of high strength and ductility obtained through the addition of microalloying elements thermomechanical processing and controlled cooling processes capable of producing complex microstructures that improve the mechanical properties of steels. These controlled microstructures can be severely affected and result in catastrophic failures due to the atomic hydrogen diffusion that occurs during the corrosion process of pipeline steel. Recently a martensite–bainite microstructure with acicular ferrite has been chosen as a viable candidate to be used in environments with the presence of hydrogen. The aim of this review is to summarize the main changes of chemical composition processing techniques and the evolution of the mechanical properties throughout recent history on the use of microalloying in high strength low alloy steels as well as the effects of hydrogen in newly created pipelines examining the causes behind the mechanisms of hydrogen embrittlement in these steels.
Study on Temper Embrittlement and Hydrogen Embrittlement of a Hydrogenation Reactor by Small Punch Test
Jun 2017
Publication
The study on temper embrittlement and hydrogen embrittlement of a test block from a 3Cr1Mo1/4V hydrogenation reactor after ten years of service was carried out by small punch test (SPT) at different temperatures. The SPT fracture energy Esp (derived from integrating the load-displacement curve) divided by the maximum load (Fm) of SPT was used to fit the Esp/Fm versus-temperature curve to determine the energy transition temperature (Tsp) which corresponded to the ductile-brittle transition temperature of the Charpy impact test. The results indicated that the ratio of Esp/Fm could better represent the energy of transition in SPT compared with Esp. The ductile-to-brittle transition temperature of the four different types of materials was measured using the hydrogen charging test by SPT. These four types of materials included the base metal and the weld metal in the as-received state and the base metal and the weld metal in the de-embrittled state. The results showed that there was a degree of temper embrittlement in the base metal and the weld metal after ten years of service at 390 °C. The specimens became slightly more brittle but this was not obvious after hydrogen charging. Because the toughness of the material of the hydrogenation reactor was very good the flat samples of SPT could not characterize the energy transition temperature within the liquid nitrogen temperature. Additionally there was no synergetic effect of temper embrittlement and hydrogen embrittlement found in 3Cr1Mo1/4V steel.
Towards Non-Mechanical Hybrid Hydrogen Compression for Decentralized Hydrogen Facilities
Jun 2020
Publication
The cost of the hydrogen value chain needs to be reduced to allow the widespread development of hydrogen applications. Mechanical compressors widely used for compressing hydrogen to date account for more than 50% of the CAPEX (capital expenditure) in a hydrogen refuelling station. Moreover mechanical compressors have several disadvantages such as the presence of many moving parts hydrogen embrittlement and high consumption of energy. Non-mechanical hydrogen compressors have proven to be a valid alternative to mechanical compressors. Among these electrochemical compressors allow isothermal and therefore highly efficient compression of hydrogen. On the other hand adsorption-desorption compressors allow hydrogen to be compressed through cooling/heating cycles using highly microporous materials as hydrogen adsorbents. A non-mechanical hybrid hydrogen compressor consisting of a first electrochemical stage followed by a second stage driven by adsorption-desorption of hydrogen on activated carbons allows hydrogen to be produced at 70 MPa a value currently required for the development of hydrogen automotive applications. This system has several advantages over mechanical compressors such as the absence of moving parts and high compactness. Its use in decentralized hydrogen facilities such as hydrogen refuelling stations can be considered
The Effect of Hydrogen Content and Yield Strength on the Distribution of Hydrogen in Steel a Diffusion Coupled Micromechanical FEM Study
Mar 2021
Publication
In this study we investigate the effect of the heterogeneous micromechanical stress fields resulting from the grain-scale anisotropy on the redistribution of hydrogen using a diffusion coupled crystal plasticity model. A representative volume element with periodic boundary conditions was used to model a synthetic microstructure. The effect of tensile loading initial hydrogen content and yield strength on the redistribution of lattice (CL) and dislocation trapped (Cx) hydrogen was studied. It was found that the heterogeneous micromechanical stress fields resulted in the accumulation of both populations primarily at the grain boundaries. This shows that in addition to the well-known grain boundary trapping the interplay of the heterogeneous micromechanical hydrostatic stresses and plastic strains contribute to the accumulation of hydrogen at the grain boundaries. Higher yield strength reduced the amount of Cx due to the resulting lower plastic deformation levels. On the other side the resulting higher hydrostatic stresses increased the depletion of CL from the compressive regions and its diffusion toward the tensile ones. These regions with increased CL are expected to be potential damage initiation zones. This aligns with the observations that high-strength steels are more susceptible to hydrogen embrittlement than those with lower-strength.
Hydrogen-Assisted Brittle Fracture Behavior of Low Alloy 30CrMo Steel Based on the Combination of Experimental and Numerical Analyses
Jul 2021
Publication
Compact-tension (CT) specimens made of low alloy 30CrMo steels were hydrogen-charged and then subjected to the fracture toughness test. The experimental results revealed that the higher crack propagation and the lower crack growth resistance (CTOD-R curve) are significantly noticeable with increasing hydrogen embrittlement (HE) indexes. Moreover the transition in the microstructural fracture mechanism from ductile (microvoid coalescence (MVC)) without hydrogen to a mixed quasi-cleavage (QC) fracture and QC + intergranular (IG) fracture with hydrogen was observed. The hydrogen-enhanced decohesion (HEDE) mechanism was characterized as the dominant HE mechanism. According to the experimental testing the coupled problem of stress field and hydrogen diffusion field with cohesive zone stress analysis was employed to simulate hydrogen-assisted brittle fracture behavior by using ABAQUS software. The trapezoidal traction-separation law (TSL) was adopted and the initial TSL parameters from the best fit to the load-displacement and J-integral experimental curves without hydrogen were calibrated for the critical separation of 0.0393 mm and the cohesive strength of 2100 MPa. The HEDE was implemented through hydrogen influence in the TSL and to estimate the initial hydrogen concentration based on matching numerical and experimental load-line displacement curves with hydrogen. The simulation results show that the general trend of the computational CTOD-R curves corresponding to initial hydrogen concentration is almost the same as that obtained from the experimental data but in full agreement the computational CTOD values being slightly higher. Comparative analysis of numerical and experimental results shows that the coupled model can provide design and prediction to calculate hydrogen-assisted fracture behavior prior to extensive laboratory testing provided that the material properties and properly calibrated TSL parameters are known.
Blue Hydrogen as an Enabler of Green Hydrogen: The Case of Germany
Jun 2020
Publication
In Germany decarbonization of the electricity sector by fostering renewables and now phasing out coal-fired power is on track to reach the 2050 de-carbonisation targets while decarbonising non-electric energy consumption is proving to be more difficult. The present discussion of a national hydrogen strategy has run into strong political opposition against carbon sequestration as a necessary element in the use of decarbonized natural gas (blue hydrogen) and is aiming at the use of green hydrogen only (from renewable electricity and electrolysis). This paper shows that as long as the power sector is not decarbonized – not likely before 2040 – only marginal volumes of renewable electricity will be available to produce green hydrogen. To meet the decarbonization target by 2050 blue hydrogen has to fill that gap paving the way for green hydrogen at a later stage. The paper discusses the elements needed for an expedient development of blue hydrogen. It also points at the need and instruments to decarbonize core industries like the steel and chemical industry so that they can become future proof in competition with the US which is more advanced with a decarbonization strategy for its industry based on carbon sequestration.
Current Research Trends and Perspectives on Solid-State Nanomaterials in Hydrogen Storage
Jan 2021
Publication
Hydrogen energy with environment amicable renewable efficiency and cost-effective advantages is the future mainstream substitution of fossil-based fuel. However the extremely low volumetric density gives rise to the main challenge in hydrogen storage and therefore exploring effective storage techniques is key hurdles that need to be crossed to accomplish the sustainable hydrogen economy. Hydrogen physically or chemically stored into nanomaterials in the solid-state is a desirable prospect for effective large-scale hydrogen storage which has exhibited great potentials for applications in both reversible onboard storage and regenerable off-board storage applications. Its attractive points include safe compact light reversibility and efficiently produce sufficient pure hydrogen fuel under the mild condition. This review comprehensively gathers the state-of-art solid-state hydrogen storage technologies using nanostructured materials involving nanoporous carbon materials metal-organic frameworks covalent organic frameworks porous aromatic frameworks nanoporous organic polymers and nanoscale hydrides. It describes significant advances achieved so far and main barriers need to be surmounted to approach practical applications as well as offers a perspective for sustainable energy research.
Materials for Hydrogen-based Energy Storage - Past, Recent Progress and Future Outlook
Dec 2019
Publication
Michael Hirscher,
Volodymyr A. Yartys,
Marcello Baricco,
José Bellosta von Colbe,
Didier Blanchard,
Robert C. Bowman Jr.,
Darren P. Broom,
Craig Buckley,
Fei Chang,
Ping Chen,
Young Whan Cho,
Jean-Claude Crivello,
Fermin Cuevas,
William I. F. David,
Petra E. de Jongh,
Roman V. Denys,
Martin Dornheim,
Michael Felderhoff,
Yaroslav Filinchuk,
George E. Froudakis,
David M. Grant,
Evan MacA. Gray,
Bjørn Christian Hauback,
Teng He,
Terry D. Humphries,
Torben R. Jensen,
Sangryun Kim,
Yoshitsugu Kojima,
Michel Latroche,
Hai-wen Li,
Mykhaylo V. Lototskyy,
Joshua W. Makepeace,
Kasper T. Møller,
Lubna Naheed,
Peter Ngene,
Dag Noreus,
Magnus Moe Nygård,
Shin-ichi Orimo,
Mark Paskevicius,
Luca Pasquini,
Dorthe B. Ravnsbæk,
M. Veronica Sofianos,
Terrence J. Udovic,
Tejs Vegge,
Gavin Walker,
Colin Webb,
Claudia Weidenthaler and
Claudia Zlotea
Globally the accelerating use of renewable energy sources enabled by increased efficiencies and reduced costs and driven by the need to mitigate the effects of climate change has significantly increased research in the areas of renewable energy production storage distribution and end-use. Central to this discussion is the use of hydrogen as a clean efficient energy vector for energy storage. This review by experts of Task 32 “Hydrogen-based Energy Storage” of the International Energy Agency Hydrogen TCP reports on the development over the last 6 years of hydrogen storage materials methods and techniques including electrochemical and thermal storage systems. An overview is given on the background to the various methods the current state of development and the future prospects. The following areas are covered; porous materials liquid hydrogen carriers complex hydrides intermetallic hydrides electro-chemical storage of energy thermal energy storage hydrogen energy systems and an outlook is presented for future prospects and research on hydrogen-based energy storage
Hydrogen vs. Battery in the Long-term Operation. A Comparative Between Energy Management Strategies for Hybrid Renewable Microgrids
Apr 2020
Publication
The growth of the world’s energy demand over recent decades in relation to energy intensity and demography is clear. At the same time the use of renewable energy sources is pursued to address decarbonization targets but the stochasticity of renewable energy systems produces an increasing need for management systems to supply such energy volume while guaranteeing at the same time the security and reliability of the microgrids. Locally distributed energy storage systems (ESS) may provide the capacity to temporarily decouple production and demand. In this sense the most implemented ESS in local energy districts are small–medium-scale electrochemical batteries. However hydrogen systems are viable for storing larger energy quantities thanks to its intrinsic high mass-energy density. To match generation demand and storage energy management systems (EMSs) become crucial. This paper compares two strategies for an energy management system based on hydrogen-priority vs. battery-priority for the operation of a hybrid renewable microgrid. The overall performance of the two mentioned strategies is compared in the long-term operation via a set of evaluation parameters defined by the unmet load storage efficiency operating hours and cumulative energy. The results show that the hydrogen-priority strategy allows the microgrid to be led towards island operation because it saves a higher amount of energy while the battery-priority strategy reduces the energy efficiency in the storage round trip. The main contribution of this work lies in the demonstration that conventional EMS for microgrids’ operation based on battery-priority strategy should turn into hydrogen-priority to keep the reliability and independence of the microgrid in the long-term operation.
Potential Liquid-Organic Hydrogen Carrier (LOHC) Systems: A Review on Recent Progress
Nov 2020
Publication
The depletion of fossil fuels and rising global warming challenges encourage to find safe and viable energy storage and delivery technologies. Hydrogen is a clean efficient energy carrier in various mobile fuel-cell applications and owned no adverse effects on the environment and human health. However hydrogen storage is considered a bottleneck problem for the progress of the hydrogen economy. Liquid-organic hydrogen carriers (LOHCs) are organic substances in liquid or semi-solid states that store hydrogen by catalytic hydrogenation and dehydrogenation processes over multiple cycles and may support a future hydrogen economy. Remarkably hydrogen storage in LOHC systems has attracted dramatically more attention than conventional storage systems such as high-pressure compression liquefaction and absorption/adsorption techniques. Potential LOHC media must provide fully reversible hydrogen storage via catalytic processes thermal stability low melting points favorable hydrogenation thermodynamics and kinetics large-scale availability and compatibility with current fuel energy infrastructure to practically employ these molecules in various applications. In this review we present various considerable aspects for the development of ideal LOHC systems. We highlight the recent progress of LOHC candidates and their catalytic approach as well as briefly discuss the theoretical insights for understanding the reaction mechanism.
Sustainability Indicators for the Manufacturing and Use of a Fuel Cell Prototype and Hydrogen Storage for Portable Uses
Oct 2021
Publication
A sustainability assessment regarding the manufacturing process and the use of a new proton exchange membrane fuel cell (PEMFC) specially designed for portable hydrogen applications is presented. The initial fuel cell prototype has been configured by taking into account exclusively technical issues. However a life cycle analysis considering environmental and socioeconomic impacts is crucial to improve the model to develop a more sustainable product. From the environ‐ mental perspective the durability of the system and its efficiency are key elements required to de‐ crease the potential overall impacts. High electricity consumption for manufacturing requires a commitment to the use of renewable energies due to the high current value of the projected impact of climate change (42.5 tonnes of CO2 eq). From the socioeconomic point of view the dependence of imported components required for the synthesis of some materials displaces the effects of value added and employment in Spain potentially concentrating the largest impact on countries such as Singapore Japan and the UK whereas the cell assembly would have a greater benefit for the country of fabrication. These results provide a basis for new research strategies since they can be considered standard values for improving future upgrades of the fuel cell in terms of sustainability.
Recent Progress and New Perspectives on Metal Amide and Imide Systems for Solid-State Hydrogen Storage
Apr 2018
Publication
Hydrogen storage in the solid state represents one of the most attractive and challenging ways to supply hydrogen to a proton exchange membrane (PEM) fuel cell. Although in the last 15 years a large variety of material systems have been identified as possible candidates for storing hydrogen further efforts have to be made in the development of systems which meet the strict targets of the Fuel Cells and Hydrogen Joint Undertaking (FCH JU) and U.S. Department of Energy (DOE). Recent projections indicate that a system possessing: (i) an ideal enthalpy in the range of 20–50 kJ/mol H2 to use the heat produced by PEM fuel cell for providing the energy necessary for desorption; (ii) a gravimetric hydrogen density of 5 wt. % H2 and (iii) fast sorption kinetics below 110 ◦C is strongly recommended. Among the known hydrogen storage materials amide and imide-based mixtures represent the most promising class of compounds for on-board applications; however some barriers still have to be overcome before considering this class of material mature for real applications. In this review the most relevant progresses made in the recent years as well as the kinetic and thermodynamic properties experimentally measured for the most promising systems are reported and properly discussed.
A Review of the MSCA ITN ECOSTORE—Novel Complex Metal Hydrides for Efficient and Compact Storage of Renewable Energy as Hydrogen and Electricity
Mar 2020
Publication
Hydrogen as an energy carrier is very versatile in energy storage applications. Developments in novel sustainable technologies towards a CO2-free society are needed and the exploration of all-solid-state batteries (ASSBs) as well as solid-state hydrogen storage applications based on metal hydrides can provide solutions for such technologies. However there are still many technical challenges for both hydrogen storage material and ASSBs related to designing low-cost materials with low-environmental impact. The current materials considered for all-solid-state batteries should have high conductivities for Na+ Mg2+ and Ca2+ while Al3+-based compounds are often marginalised due to the lack of suitable electrode and electrolyte materials. In hydrogen storage materials the sluggish kinetic behaviour of solid-state hydride materials is one of the key constraints that limit their practical uses. Therefore it is necessary to overcome the kinetic issues of hydride materials before discussing and considering them on the system level. This review summarizes the achievements of the Marie Skłodowska-Curie Actions (MSCA) innovative training network (ITN) ECOSTORE the aim of which was the investigation of different aspects of (complex) metal hydride materials. Advances in battery and hydrogen storage materials for the efficient and compact storage of renewable energy production are discussed.
Tetrahydroborates: Development and Potential as Hydrogen Storage Medium
Oct 2017
Publication
The use of fossil fuels as an energy supply becomes increasingly problematic from the point of view of both environmental emissions and energy sustainability. As an alternative hydrogen is widely regarded as a key element for a potential energy solution. However differently from fossil fuels such as oil gas and coal the production of hydrogen requires energy. Alternative and intermittent renewable energy sources such as solar power wind power etc. present multiple advantages for the production of hydrogen. On the one hand the renewable sources contribute to a remarkable reduction of pollutants released to the air and on the other hand they significantly enhance the sustainability of energy supply. In addition the storage of energy in form of hydrogen has a huge potential to balance an effective and synergetic utilization of renewable energy sources. In this regard hydrogen storage technology is a key technology towards the practical application of hydrogen as “energy carrier”. Among the methods available to store hydrogen solid-state storage is the most attractive alternative from both the safety and the volumetric energy density points of view. Because of their appealing hydrogen content complex hydrides and complex hydride-based systems have attracted considerable attention as potential energy vectors for mobile and stationary applications. In this review the progresses made over the last century on the synthesis and development of tetrahydroborates and tetrahydroborate-based systems for hydrogen storage purposes are summarized.
Optimal Design of Multi-energy Systems with Seasonal Storage
Oct 2017
Publication
Optimal design and operation of multi-energy systems involving seasonal energy storage are often hindered by the complexity of the optimization problem. Indeed the description of seasonal cycles requires a year-long time horizon while the system operation calls for hourly resolution; this turns into a large number of decision variables including binary variables when large systems are analyzed. This work presents novel mixed integer linear program methodologies that allow considering a year time horizon with hour resolution while significantly reducing the complexity of the optimization problem. First the validity of the proposed techniques is tested by considering a simple system that can be solved in a reasonable computational time without resorting to design days. Findings show that the results of the proposed approaches are in good agreement with the full-scale optimization thus allowing to correctly size the energy storage and to operate the system with a long-term policy while significantly simplifying the optimization problem. Furthermore the developed methodology is adopted to design a multi-energy system based on a neighborhood in Zurich Switzerland which is optimized in terms of total annual costs and carbon dioxide emissions. Finally the system behavior is revealed by performing a sensitivity analysis on different features of the energy system and by looking at the topology of the energy hub along the Pareto sets.
Onboard Compressed Hydrogen Storage: Fast Filling Experiments and Simulations
Nov 2021
Publication
Technology safety represents a key enabling factor for the commercial use of hydrogen within the automotive industry. In the last years considerable pre-normative and normative research effort has produced regulations at national European and global level as well as international standards. Their validation is at the moment on going internationally. Additional research is required to improve this regulatory and standardization frame which is also expected to have a beneficial effect on cost and product optimization. The present paper addresses results related to the experimental assessment and modeling of safety performance of high pressure onboard storage. To simulate the lifetime of onboard hydrogen tanks commercial tanks have been subjected to filling-emptying cycles encompassing a fast-filling phase as prescribed by the European regulation on type-approval of hydrogen vehicles. The local temperature history inside the tanks has been measured and compared with the temperature outside at the tank metallic bosses which is the measurement location identified by the regulation. Experimental activities are complemented by computational fluid-dynamics (CFD) modeling of the fast-filling process by means of a numerical model previously validated. The outcome of these activities is a set of scientifically based data which will serve as input to future regulations and standards improvement.
Quaternary Hydrides Pd1-y-zAgyCuzHx Embedded Atom Method Potentials for Hydrogen Energy Applications
Jan 2021
Publication
The Pd-H system has attracted extensive attention. Pd can absorb considerable amount of H at room temperature this ability is reversible so it is suitable for multiple energy applications. Pd-Ag alloys possess higher H permeability solubility and narrower miscibility gap with better mechanical properties than pure Pd but sulfur poisoning remains an issue. Pd-Cu alloys have excellent resistance to sulfur and carbon monoxide poisoning and hydrogen embrittlement good mechanical properties and broader temperature working environments over pure Pd but relatively lower hydrogen permeability and solubility than pure Pd and Pd-Ag alloys. This suggests that alloying Pd with Ag and Cu to create Pd-Ag-Cu ternary alloys can optimize the overall performance and substantially lowers the cost. Thus in this paper we provide the first embedded atom method potentials for the quaternary hydrides Pd1-y-zAgyCuzHx. The fully analytical potentials are fitted utilizing the central atom method without performing time-consuming molecular dynamics simulations.
Solid State Hydrogen Storage in Alanates and Alanate-Based Compounds: A Review
Jul 2018
Publication
The safest way to store hydrogen is in solid form physically entrapped in molecular form in highly porous materials or chemically bound in atomic form in hydrides. Among the different families of these compounds alkaline and alkaline earth metals alumino-hydrides (alanates) have been regarded as promising storing media and have been extensively studied since 1997 when Bogdanovic and Schwickardi reported that Ti-doped sodium alanate could be reversibly dehydrogenated under moderate conditions. In this review the preparative methods; the crystal structure; the physico-chemical and hydrogen absorption-desorption properties of the alanates of Li Na K Ca Mg Y Eu and Sr; and of some of the most interesting multi-cation alanates will be summarized and discussed. The most promising alanate-based reactive hydride composite (RHC) systems developed in the last few years will also be described and commented on concerning their hydrogen absorption and desorption performance.
Hydrogen - A Sustainable Energy Carrier
Jan 2017
Publication
Hydrogen may play a key role in a future sustainable energy system as a carrier of renewable energy to replace hydrocarbons. This review describes the fundamental physical and chemical properties of hydrogen and basic theories of hydrogen sorption reactions followed by the emphasis on state-of-the-art of the hydrogen storage properties of selected interstitial metallic hydrides and magnesium hydride especially for stationary energy storage related utilizations. Finally new perspectives for utilization of metal hydrides in other applications will be reviewed.
Effect of Defects and Hydrogen on the Fatigue Limit of Ni-based Superalloy 718
Dec 2019
Publication
Tension-compression fatigue tests were performed on two types of Ni-based superalloy 718 with different microstructures to which small artificial defects of various shapes and sizes were introduced. Similar tests were also conducted on hydrogen-charged specimens with defects with a solute hydrogen content ranging from 26.3 to 91.0 mass ppm. In the non-charged specimens in particular the fatigue strength susceptibility to defects varied significantly according to the type of microstructural morphology i.e. a smaller grain size made the alloy more vulnerable to defects. The fatigue limit as a small-crack threshold was successfully predicted using the √area parameter model. Depending on the size of defects the fatigue limit was calculated in relation to three phases: (i) harmless-defect regime (ii) small-crack regime and (iii) large-crack regime. Such a classification enabled comprehensive fatigue limit evaluation in a wide array of defects taking into consideration (a) the defect size over a range of small crack and large crack and (b) the characteristics of the matrix represented by grain size and hardness. In addition the effect of defects and hydrogen on fatigue strength will be comprehensively discussed based on a series of experimental results.
Hydrogen Enhanced Fatigue Crack Growth Rates in a Ferritic Fe-3wt%Si Alloy
Dec 2018
Publication
It is well known that ferrous materials can be damaged by absorption of hydrogen. If a sufficient quantity of hydrogen penetrates into the material static fracture and the material's fatigue performances can be affected negatively in particular causing an increase in the material crack growth rates. The latter is often referred as Hydrogen Affected-Fatigue Crack Growth Rate (HA-FCGR). It is therefore of paramount importance to quantify the impact in terms of hydrogen induce fatigue crack growth acceleration in order to determine the life of components exposed to hydrogen and avoid unexpected catastrophic failures. In this study in-situ fatigue crack growth rate testing on Compact Tension (CT) specimens were carried out to determine the fatigue crack growth behaviour for a Fe-3 wt%Si alloy and X70 pipeline steel. Tests were carried out in two environmental conditions i.e. laboratory air and in-situ electrochemically charged hydrogen and different mechanical conditions in terms of load ratio (R = 0.1 and R = 0.5 for the Fe-3 wt%Si R = 0.1 for the X70 steel) and test frequency (f = 0.1 Hz 1 Hz and 10 Hz) were adopted under electrochemically charged hydrogen conditions. The results show a clear detrimental effect of H for the specimens tested in hydrogen when compared to the specimens tested in air for both materials and that the impact of hydrogen is test frequency-dependent: the hydrogen induced acceleration is more prominent as the frequency is decreased. Post-mortem surface investigations consistently relate the global crack growth acceleration to a shift from transgranular to Quasi-cleavage fracture mechanism. Despite such consistency the acceleration factor strongly depends on the material: Fe-3wt%Si features acceleration up to 1000 times while X70 accelerates up to 76 times when compare to the material fatigue crack growth rate recorded in air. Observation of the deformation activities in the crack wake in relation to the transition into hydrogen accelerated regime in fatigue crack growth show a tendency toward restricted plastic activity in presence of hydrogen.
Tracking Hydrogen Embrittlement Using Short Fatigue Crack Behavior of Metals
Dec 2018
Publication
Understanding hydrogen embrittlement phenomenon that leads to deterioration of mechanical properties of metallic components is vital for applications involving hydrogen environment. Among these understanding the influence of hydrogen on the fatigue behaviour of metals is of great interest. Total fatigue life of a material can be divided into fatigue crack initiation and fatigue crack growth phase. While fatigue crack initiation can be linked with the propagation of short fatigue cracks the size of which is of the order of grain size (few tens of microns) that are generally not detectable by conventional crack detection techniques applicable for the long fatigue crack growth behaviour using conventional CT specimens. Extensive literature is available on hydrogen effect on long fatigue crack growth behaviour of metals that leads to the change in crack growth rate and the threshold stress intensity factor range (ΔKth). However it is the short fatigue crack growth behaviour that provides the fundamental understanding and correlation of the metallic microstructure with hydrogen embrittlement phenomenon. Short fatigue crack growth behaviour is characteristically different from long crack growth behaviour showing high propagation rate at much lower values than threshold stress intensity factor range as well as a strong dependency on the microstructural features such as grain boundaries phase boundaries and inclusions. To this end a novel experimental framework is developed to investigate the short fatigue crack behaviour of hydrogen charged materials involving in-situ observation of propagating short cracks coupled with image processing to obtain their da/dN vs a curves. Various metallic materials ranging from austenitic stainless steel (AISI 316L) to reactor pressure vessel steel (SA508 Grade 3 Class I low alloy steel) and line pipe steels (API 5L X65 & X80) are studied in this work.
Effects of Hydrogen Pressure, Test Frequency and Test Temperature on Fatigue Crack Growth Properties of Low-carbon Steel in Gaseous Hydrogen
Jul 2016
Publication
Fatigue crack growth (FCG) tests for compact tension (CT) specimens of an annealed low-carbon steel JIS-SM490B were performed under various combinations of hydrogen pressures ranging from 0.1 to 90 MPa test frequencies from 0.001 to 10 Hz and test temperatures of room temperature (RT) 363 K and 423 K. In the hydrogen pressures of 0.1 0.7 and 10 MPa at RT the FCG rate increased with a decrease in the test frequency; then peaked out. In the lower test frequency regime the FCG rate decreased and became nearly equivalent to the FCG rate in air. Also in hydrogen pressure of 45 MPa at RT the hydrogen-assisted FCG acceleration showed an upper limit around the test frequencies of 0.01 to 0.001 Hz. On the other hand in the hydrogen pressure of 90 MPa at RT the FCG rate monotonically increased with a decrease in the test frequency and eventually the upper limit of FCG acceleration was not confirmed down to the test frequency of 0.001 Hz. In the hydrogen pressure of 0.7 MPa at the test frequency of 1 Hz and temperatures of 363 K and 423 K the stress intensity factor range ΔK for the onset of the FCG acceleration in hydrogen gas was shifted to a higher ΔK with an increase in the test temperature. The laser-microscope observation at specimen surface revealed that the hydrogen-assisted FCG acceleration always accompanied a localization of plastic deformation near crack tip. These results infer that the influencing factor dominating the hydrogen-assisted FCG acceleration is not the presence or absence of hydrogen in material but is how hydrogen localizes near the crack tip. Namely a steep gradient of hydrogen concentration can result in the slip localization at crack tip which enhances the Hydrogen Enhanced Successive Fatigue Crack Growth (HESFCG) proposed by the authors. It is proposed that such a peculiar dependence of FCG rate on hydrogen pressure test frequency and test temperature can be unified by using a novel parameter representing the gradient of hydrogen concentration near crack tip.
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.
Environmental Degradation Effect of High-Temperature Water and Hydrogen on the Fracture Behavior of Low-Alloy Reactor Pressure Vessel Steels
Dec 2019
Publication
Structural integrity of reactor pressure vessel (RPV) in light water reactors (LWR) is of highest importance regarding operation safety and lifetime. The fracture behaviour of low-alloy RPV steels with different dynamic strain aging (DSA) & environmental assisted cracking (EAC) susceptibilities in simulated LWR environments was evaluated by elastic plastic fracture mechanics tests (EPFM) and by metallo- and fractographic post-test analysis. Exposure to high temperature water (HTW) environments at LWR temperatures revealed only moderated reductions in the fracture initiation and tearing resistance of low alloy RPV steels with high DSA or EAC susceptibility accompanied with a moderate but clear change in fracture morphology which indicates the potential synergies of hydrogen/HTW embrittlement with DSA and EAC under suitable conditions. The most pronounced degradation effects occurred in a) RPV steels with high DSA susceptibility where the fracture initiation and tearing resistance reduction increased with decreasing loading rate and were most pronounced in hydrogenated HTW and b) high sulphur steels with high EAC susceptibility in aggressive occluded crevice environment and with preceding fast EAC crack growth in oxygenated HTW. The moderate effects are due to the low hydrogen availability in HTW together with high density of fine-dispersed hydrogen traps in RPV steels. Stable ductile transgranular tearing by microvoid coalescence was the dominant failure mechanism in all environments with additional varying few % of secondary cracks macrovoids and quasi-cleavage in HTW. The observed behavior suggests a combination of plastic strain localisation by the Hydrogen-enhanced Local Plasticity (HELP) mechanism in synergy with DSA and Hydrogen-enhanced Strain-induced Vacancies (HESIV) mechanism with additional minor contributions of Hydrogen-enhanced Decohesion Embrittlement (HEDE) mechanism.
Modelling of Fatigue Crack Initiation in Hydrogen Charged Polycrystalline Nickel
Jun 2019
Publication
Hydrogen Embrittlement (HE) leads to deterioration of the fracto-mechanical properties of metals. In spite of vast literature it is still not clearly understood and demands significant research on this topic. For better understanding of the hydrogen effect on fatigue behaviour of metals present work focuses on developing a computational framework for fatigue crack initiation studies in metals in the presence of hydrogen. The developed framework consists of a nonlocal crystal plasticity model coupled with hydrogen transport model to study the fatigue behaviour of hydrogen charged metals. The nonlocal crystal plasticity model accounts for the statistically stored dislocations (SSDs) and geometrically necessary dislocations (GNDs) in polycrytalline metal. Hydrogen transport model on the other hand accounts for diffusion and trapping behavior of hydrogen due to concentration gradient pressure gradient plastic strain-rate with dislocations as the only trapping sites along the slip systems. A polycrystalline representative volume element (RVE) with periodic boundary conditions is used in this study. Fatigue crack initiation criterion is proposed for the simulated RVE with controlled microstructure by considering a critical value of the fatigue indicator parameter (FIP). FIP is formulated based on the experimental observations of several crack initiation sites along the grain boundaries their normal direction with respect to loading direction and the accumulated plastic strain in nickel polycrystalline samples. Developed simulation framework correctly accounts cyclic stress-strain behavior and multiple fatigue crack initiation sites observed experimentally in the presence of hydrogen.
A New Design Concept for Prevention of Hydrogen-induced Mechanical Degradation: Viewpoints of Metastability and High Entropy
Dec 2018
Publication
‟How crack growth is prevented” is key to improve both fatigue and monotonic fracture resistances under an influence of hydrogen. Specifically the key points for the crack growth resistance are hydrogen diffusivity and local ductility. For instance type 304 austenitic steels show high hydrogen embrittlement susceptibility because of the high hydrogen diffusivity of bcc (α´) martensite. In contrast metastability in specific austenitic steels enables fcc (γ) to hcp (ε) martensitic transformation which decreases hydrogen diffusivity and increases strength simultaneously. As a result even if hydrogen-assisted cracking occurs during monotonic tensile deformation the ε-martensite acts to arrest micro-damage evolution when the amount of ε-martensite is limited. Thus the formation of ε-martensite can decrease hydrogen embrittlement susceptibility in austenitic steels. However a considerable amount of ε-martensite is required when we attempt to have drastic improvements of work hardening capability and strength level with respect to transformation-induced plasticity effect. Since the hcp structure contains a less number of slip systems than fcc and bcc the less stress accommodation capacity often causes brittle-like failure when the ε-martensite fraction is large. Therefore ductility of ε-martensite is another key when we maximize the positive effect of ε-martensitic transformation. In fact ε-martensite in a high entropy alloy was recently found to be extraordinary ductile. Consequently the metastable high entropy alloys showed low fatigue crack growth rates in a hydrogen atmosphere compared with conventional metastable austenitic steels with α´-martensitic transformation. We here present effects of metastability to ε-phase and configurational entropy on hydrogen-induced mechanical degradation including monotonic tension properties and fatigue crack growth resistance.
The Hydrogen Trapping Ability of TiC and V4C3 by Thermal Desorption Spectroscopy and Permeation Experiments
Dec 2018
Publication
Hydrogen (H) presence in metals is detrimental as unpredictable failure might occur. Recent developments in material’s design indicated that microstructural features such as precipitates play an essential role in potentially increasing the resistance against H induced failure. This work evaluates the H trapping characteristics for TiC and V4C3 by thermal desorption spectroscopy and permeation experiments. Two microstructural conditions are compared: as quenched vs. quenched and tempered in which the carbides are introduced. The tempered induced precipitates are able to deeply trap a significant amount of H which decreases the H diffusivity in the materials and removes some of the detrimental H from the microstructure. For microstructural design purposes it is important to know the position of H. Here H is demonstrated to be trapped at the carbide/matrix interface by modifying the tempering treatment.
Hydrogen Assisted Crack Initiation and Propagation in Nickel-cobalt Heat Resistant Superalloys
Aug 2019
Publication
It has been investigated the Ni-Co alloys (obtained from powder 0.1...0.3 mm under hot gaseous (in argon) isostatic pressure (up to 300 MPa) (Ni60Co15Cr8W8Al2Mo3) (Firth Rixon Metal Ltd Sheffield) and deformed (obtained by vacuum induced remealting) materials (Ni62Cr14Co10Mo5Nb3Al3Ti3) for gaseous turbine discs. Investigation has performed in the range of temperature 25…800°С and hydrogen pressure up to 70 MPa. By the 3D visualization of crack morphology it has been discovered the structure of fatigue crack surface and established the refer points on crack path including the boundary between the matrix and intermetallic particles (400×200 μm) crack opening structural elements distributions on the surface for selection of next local areas for more precision fracture surface and TEM examinations. Hydrogen influence on cyclic crack resistance parameters appears in the decreasing of loading cycles number (with amplitudes 15 MPa) in hydrogenated specimens of both alloys and increase with hydrogen concentration. At the highest hydrogen saturation regimes of Ni60Co15Cr8W8Al2Mo3 alloy (800°С 35 MPa Н2 36 hours СН = 32.7 ppm) number of cycles which necessary for crack initiation is 3 times less in comparison with specimen in initial state. At crack initiation step in hydrogenated Ni56Cr14Co15Mo5Al3Ti3 alloy it has been established that before intermetallic inclusion (400×200 μm) local stresses increased after its passing – has decreased. By fracture surface investigation it has been found the micro cracks up to 40 μm. Thin structure of heat resistant superalloys has characterises by disperse phase agglomeration with dimensions from 5 to 30 nm and crack propagation has a jumping character with no less then 50…70 nm steps.
Requirements for Hydrogen Resistance of Materials in CI Engine Toxic Substances Powered by Biofuels
Aug 2019
Publication
It has been described the conception of using platinum catalytic layer in multi hole fuel injector atomizer. The catalytic layer has been placed on not working part of atomizer needle. The aim of modification was activation of dehydrogenation reaction paraffin to olefin hydrocarbons with escape hydrogen molecule in CI engine bio fuel. The modification of atomizer with catalytic layer and reaction process leads to the presence of hydrogen and its influence on structural materials properties after the catalysis which requires the high hydrogen and crack resistance of used materials. There is used high speed steel as material. Article describes how hydrogen and combustion gases influence on thermal friction processes on this material. First of all the investigations were conduct 359 engine with biodiesel. During test had been observed nitrogen oxides carbon monoxide and particles emission. The obtained results show that there is possibility to lower toxic substances emission in exhaust gases CI engine powered by biodiesel. On the second it has been described the influence of biodiesel (including hydrogen) on fuel injector components and their influence on structural materials characteristics. There has been presented how biodiesel with hydrogen influences on precision elements and injection and return discharges. The investigation has been made by using engine test bench and fuel injector and pumps test equipment.
Strain Rate Sensitivity of Microstructural Damage Evolution in a Dual-Phase Steel Pre-Charged with Hydrogen
Dec 2018
Publication
We evaluated the strain rate sensitivity of the micro-damage evolution behavior in a ferrite/martensite dual-phase steel. The micro-damage evolution behavior can be divided into three regimes: damage incubation damage arrest and damage growth. All regimes are associated with local deformability. Thus the total elongation of DP steels is determined by a combination of plastic damage initiation resistance and damage growth arrestability. This fact implies that hydrogen must have a critical effect on the damage evolution because hydrogen enhances strain localization and lowers crack resistance. In this context the strain rate must be an important factor because it affects the time for microstructural hydrogen diffusion/segregation at a specific microstructural location or at the damage tip. In this study tensile tests were carried out on a DP steel with different strain rates of 10− 2 and 10− 4 s−1. We performed the damage quantification microstructure characterization and fractography. Specifically the quantitative data of the damage evolution was analyzed using the classification of the damage evolution regimes in order to separately elucidate the effects of the hydrogen on damage initiation resistance and damage arrestability. In this study we obtained the following conclusions with respect to the strain rate. Lowering the strain rate increased the damage nucleation rate at martensite and reduced the critical strain for fracture through shortening the damage arrest regime. However the failure occurred via ductile modes regardless of strain rate.
Hydrogen Storage in Depleted Gas Reservoirs: A Comprehensive Review
Nov 2022
Publication
Hydrogen future depends on large-scale storage which can be provided by geological formations (such as caverns aquifers and depleted oil and gas reservoirs) to handle demand and supply changes a typical hysteresis of most renewable energy sources. Amongst them depleted natural gas reservoirs are the most cost-effective and secure solutions due to their wide geographic distribution proven surface facilities and less ambiguous site evaluation. They also require less cushion gas as the native residual gases serve as a buffer for pressure maintenance during storage. However there is a lack of thorough understanding of this technology. This work aims to provide a comprehensive insight and technical outlook into hydrogen storage in depleted gas reservoirs. It briefly discusses the operating and potential facilities case studies and the thermophysical and petrophysical properties of storage and withdrawal capacity gas immobilization and efficient gas containment. Furthermore a comparative approach to hydrogen methane and carbon dioxide with respect to well integrity during gas storage has been highlighted. A summary of the key findings challenges and prospects has also been reported. Based on the review hydrodynamics geochemical and microbial factors are the subsurface’s principal promoters of hydrogen losses. The injection strategy reservoir features quality and operational parameters significantly impact gas storage in depleted reservoirs. Future works (experimental and simulation) were recommended to focus on the hydrodynamics and geomechanics aspects related to migration mixing and dispersion for improved recovery. Overall this review provides a streamlined insight into hydrogen storage in depleted gas reservoirs.
Effect of Hydrogen on Very High Cycle Fatigue Behavior of a Low-strength Cr-Ni-Mo-V Steel Containing Micro-defects
Dec 2017
Publication
The role of hydrogen in fatigue failure of low strength steels is not as well understood as of high strength steels in very high cycle fatigue regime. In this work axially cyclic tests on a low strength Cr-Ni-Mo-V steel with charged hydrogen were carried out up to the very high cycle fatigue regime under ultrasonic frequency to examine the degradation of fatigue strength and associated failure mechanisms. Results show that the S-N curves show a continuously decreasing mode and hydrogen-charged specimens have lower fatigue strength and shorter fatigue lifetime as compared with as-received specimens. It is concluded that the hydrogen trapped by inclusions drives interior micro-defects as dominant crack initiation site and has a clear link to the initiation and early growth of interior fatigue cracks.
Environmentally-Assisted Cracking of Type 316L Austenitic Stainless Steel in Low Pressure Hydrogen Steam Environments
Aug 2019
Publication
A low pressure superheated hydrogen-steam system has been used to accelerate the oxidation kinetics while keeping the electrochemical conditions similar to those of the primary water in a pressurized water reactor. The initiation has been investigated using a Constant Extension Rate Tensile (CERT) test. Tests were performed on flat tapered specimens made from Type 316L austenitic stainless steel with strain rates of 2×10-6 and 2×10-8 ms-1 at room temperature and at an elevated temperature of 350 °C. R = 1/6 was chosen as a more oxidizing environment and R = 6 was selected as a more reducing environment where the parameter R represents the ratio between the oxygen partial pressure at the Ni/NiO transition and the oxygen partial pressure. Different exposures (1 day and 5 days) prior to loading were investigated post-test evaluation by scanning electron microscopy.
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