Transmission, Distribution & Storage
Complex Hydrides for Hydrogen Storage – New Perspectives
Apr 2014
Publication
Since the 1970s hydrogen has been considered as a possible energy carrier for the storage of renewable energy. The main focus has been on addressing the ultimate challenge: developing an environmentally friendly successor for gasoline. This very ambitious goal has not yet been fully reached as discussed in this review but a range of new lightweight hydrogen-containing materials has been discovered with fascinating properties. State-of-the-art and future perspectives for hydrogen-containing solids will be discussed with a focus on metal borohydrides which reveal significant structural flexibility and may have a range of new interesting properties combined with very high hydrogen densities.
Heat Transfer Analysis of High Pressure Hydrogen Tank Fillings
Jun 2022
Publication
Fast fillings of hydrogen vehicles require proper control of the temperature to ensure the integrity of the storage tanks. This study presents an analysis of heat transfer during filling of a hydrogen tank. A conjugate heat transfer based on energy balance is introduced. The numerical model is validated against fast filling experiments of hydrogen in a Type IV tank by comparing the gas temperature evolution. The impact of filling parameters such as initial temperature inlet nozzle diameter and filling time is then assessed. For the considered Type IV tank the results show that both a higher and lower tank shell thermal conductivity results in lower inner wall peak temperatures. The presented model provides an analytical description of the temperature evolution in the gas and in the tank shell and is thus a useful tool to explore a broad range of parameters e.g. to determine new hydrogen filling protocols.
Liquid Hydrogen: A Review on Liquefaction, Storage, Transportation, and Safety
Sep 2021
Publication
Decarbonization plays an important role in future energy systems for reducing greenhouse gas emissions and establishing a zero-carbon society. Hydrogen is believed to be a promising secondary energy source (energy carrier) that can be converted stored and utilized efficiently leading to a broad range of possibilities for future applications. Moreover hydrogen and electricity are mutually converted creating high energy security and broad economic opportunities toward high energy resilience. Hydrogen can be stored in various forms including compressed gas liquid hydrogen hydrides adsorbed hydrogen and reformed fuels. Among these liquid hydrogen has advantages including high gravimetric and volumetric hydrogen densities and hydrogen purity. However liquid hydrogen is garnering increasing attention owing to the demand for long storage periods long transportation distances and economic performance. This paper reviews the characteristics of liquid hydrogen liquefaction technology storage and transportation methods and safety standards to handle liquid hydrogen. The main challenges in utilizing liquid hydrogen are its extremely low temperature and ortho- to para-hydrogen conversion. These two characteristics have led to the urgent development of hydrogen liquefaction storage and transportation. In addition safety standards for handling liquid hydrogen must be updated regularly especially to facilitate massive and large-scale hydrogen liquefaction storage and transportation.
Mapping Geological Hydrogen Storage Capacity and Regional Heating Demands: An Applied UK Case Study
Feb 2021
Publication
Hydrogen is considered as a low-carbon substitute for natural gas in the otherwise difficult to decarbonise domestic heating sector. This study presents for the first time a globally applicable source to sink methodology and analysis that matches geological storage capacity with energy demand. As a case study it is applied to the domestic heating system in the UK with a focus on maintaining the existing gas distribution network. To balance the significant annual cyclicity in energy demand for heating hydrogen could be stored in gas fields offshore and transported via offshore pipelines to the existing gas terminals into the gas network. The hydrogen energy storage demand in the UK is estimated to be ~77.9 terawatt-hour (TWh) which is approximately 25 % of the total energy from natural gas used for domestic heating. The total estimated storage capacity of the gas fields included in this study is 2661.9 TWh. The study reveals that only a few offshore gas fields are required to store enough energy as hydrogen to balance the entire seasonal demand for UK domestic heating. It also demonstrates that as so few fields are required hydrogen storage will not compete for the subsurface space required for other low-carbon subsurface applications such as carbon storage or compressed air energy storage.
Recent Development in Nanoconfined Hydrides for Energy Storage
Jun 2022
Publication
Hydrogen is the ultimate vector for a carbon-free sustainable green-energy. While being the most promising candidate to serve this purpose hydrogen inherits a series of characteristics making it particularly difficult to handle store transport and use in a safe manner. The researchers’ attention has thus shifted to storing hydrogen in its more manageable forms: the light metal hydrides and related derivatives (ammonia-borane tetrahydridoborates/borohydrides tetrahydridoaluminates/alanates or reactive hydride composites). Even then the thermodynamic and kinetic behavior faces either too high energy barriers or sluggish kinetics (or both) and an efficient tool to overcome these issues is through nanoconfinement. Nanoconfined energy storage materials are the current state-of-the-art approach regarding hydrogen storage field and the current review aims to summarize the most recent progress in this intriguing field. The latest reviews concerning H2 production and storage are discussed and the shift from bulk to nanomaterials is described in the context of physical and chemical aspects of nanoconfinement effects in the obtained nanocomposites. The types of hosts used for hydrogen materials are divided in classes of substances the mean of hydride inclusion in said hosts and the classes of hydrogen storage materials are presented with their most recent trends and future prospects.
Hybrid Energy System Model in Matlab/Simulink Based on Solar Energy, Lithium‐Ion Battery and Hydrogen
Mar 2022
Publication
In this work a model of an energy system based on photovoltaics as the main energy source and a hybrid energy storage consisting of a short‐term lithium‐ion battery and hydrogen as the long‐term storage facility is presented. The electrical and the heat energy circuits and resulting flows have been modelled. Therefore the waste heat produced by the electrolyser and the fuel cell have been considered and a heat pump was considered to cover the residual heat demand. The model is designed for the analysis of a whole year energy flow by using a time series of loads weather and heat profile as input. This paper provides the main set of equations to derive the component properties and describes the implementation into MATLAB/Simulink. The novel model was created for an energy flow simulation over one year. The results of the simulation have been verified by comparing them with well‐established simulation results from HOMER Energy. It turns out that the novel model is well suited for the analysis of the dynamic system behaviour. Moreover different characteristics to achieve an energy balance an ideal dimensioning for the particular use case and further research possibilities of hydrogen use in the residential sector are covered by the novel model.
Everything About Hydrogen Podcast: Envisioning the Hydrogen Revolution
May 2021
Publication
For our 40th episode of the Everything About Hydrogen podcast the gang are joined by hydrogen luminary Marco Alverà the CEO of Snam. Founded in 1941 and listed on the Italian stock exchange since 2001 Snam is a leader in the European gas market and operator of over 41000km of transport networks. Hailed as a visionary who has led the pivot of the world’s 2nd largest gas distribution company towards a clean gas trajectory Marco is widely recognized as a thought leader and a key figure driving the transition towards hydrogen. On the show the team discuss why Marco decided to lead Snam's pivot towards hydrogen what he sees as the role of hydrogen in the energy transition and how blue hydrogen can sit alongside green hydrogen as part of the solution to a decarbonized gas network.
The podcast can be found on their website
The podcast can be found on their website
Hydrogen Storage Behavior of Mg-based Alloy Catalyzed by Carbon-cobalt Composites
Feb 2021
Publication
The composites comprised of Co nanoparticle and C nanosheet were prepared though a high-temperature carbonization reaction. The catalysis of Co@C composites on the hydrogen storage behavior of Mg90Ce5Y5 alloy was investigated in detail by XRD SEM TEM PCI and DSC method. Because of the synergistic catalytic function of C and Co in C@Co nanocomposites the Mg90Ce5Y5 alloy with 10 wt.% C@Co shows the excellent hydrogen absorption and desorption performances. Time for releasing hydrogen reduces from 150 min to 11 min with the addition of the C@Co composites at the temperature of 300 °C. Meanwhile the dehydrogenation activation energy also declines from 130.3 to 81.9 kJ mol−1 H2 after the addition of the C@Co composites. This positive effect attributes to the C layer with the high defect density and the Co nanoparticles which reduces the energy barriers for the nucleation of Mg/MgH2 phase and the recombination of hydrogen molecule. Besides the C@Co composites also improve the activation property of the Mg90Ce5Y5 alloy which was fully activated in the first cycle. Moreover the temperature for initial dehydrogenation and the endothermic peak of the alloy hydride were also decreased. Although the addition of the C@Co composites increases the plateau pressures and decreases the value of the decomposition enthalpy these differences are so small that the improvement on thermodynamics can hardly be seen.
Hydrogen Storage Behavior of TiFe Alloy Activated by Different Methods
Feb 2021
Publication
TiFe activation for hydrogen uptake was conducted through different methods and ball milling with ethanol proved to be the most effective one. TiFe alloy after activation could absorb 1.2 wt% hydrogen at room temperature with absorption and desorption plateaus of 0.5 MPa and 0.2 MPa respectively. Investigation on microstructure and chemical state of TiFe sample after milled with ethanol suggested that the well spread metallic Ti and Fe elements helped hydrogen uptake and release. The activation of TiFe alloy by milling with ethanol was achieved at ambient conditions with ease successfully and possibly can be used for large scale production
A New Model For Hydrogen-Induced Crack (HIC) Growth in Metal Alloy Pipelines Under Extreme Pressure
Dec 2020
Publication
Pipeline failure caused by Hydrogen-Induced Cracking (HIC) also known as Hydrogen Embrittlement (HE) is a pressing issue for the oil and natural gas industry. Bursts in pipelines are devastating and extremely costly. The explosive force of a bursting pipe can inflict fatal injuries to workers while the combined loss of product and effort to repair are highly costly to producers. Further pipeline failures due to HIC have a long lasting impact on the surrounding environment. Safe use and operation of such pipelines depend on a good understanding of the underlying forces that cause HIC. Specifically a reliable way to predict the growth rate of hydrogen-induced cracks is needed to establish a safe duration of service for each length of pipeline. Pipes that have exceeded or are near the end of their service life can then be retired before the risk of HIC-related failures becomes too high. However little is known about the mechanisms that drive HIC. To date no model has been put forth that accurately predicts the growth rate of fractures due to HIC under extreme pressures such as in the context of natural gas and petroleum pipelines. Herein a mathematical model for the growth of fractures by HIC under extreme pressures is presented. This model is derived from first principles and the results are compared with other models. The implications of these findings are discussed and a description of future work based on these findings is presented.
Hydrogen Assisted Cracking in Pearlitic Steel Rods: The Role of Residual Stresses Generated by Fatigue Precracking
May 2017
Publication
Stress corrosion cracking (SCC) of metals is an issue of major concern in engineering since this phenomenon causes many catastrophic failures of structural components in aggressive environments. SCC is even more harmful under cathodic conditions promoting the phenomenon known as hydrogen assisted cracking (HAC) hydrogen assisted fracture (HAF) or hydrogen embrittlement (HE). A common way to assess the susceptibility of a given material to HAC HAF or HE is to subject a cracked rod to a constant extension rate tension (CERT) test until it fractures in this harsh environment. This paper analyzes the influence of a residual stress field generated by fatigue precracking on the sample’s posterior susceptibility to HAC. To achieve this goal numerical simulations were carried out of hydrogen diffusion assisted by the stress field. Firstly a mechanical simulation of the fatigue precracking was developed for revealing the residual stress field after diverse cyclic loading scenarios and posterior stress field evolution during CERT loading. Afterwards a simulation of hydrogen diffusion assisted by stress was carried out considering the residual stresses after fatigue and the superposed rising stresses caused by CERT loading. Results reveal the key role of the residual stress field after fatigue precracking in the HAC phenomena in cracked steel rods as well as the beneficial effect of compressive residual stress.
Evaluation of Hydrogen Permeation Characteristics in Rubbery Polymers
Oct 2020
Publication
To find suitable sealing material with low permeability against hydrogen the elaborated evaluation techniques for hydrogen transport properties are necessary. We developed two techniques determining the permeability of hydrogen including software for diffusion behavior analysis. The techniques contain gas chromatography and volumetric collection of hydrogen gas. By measuring the hydrogen released from polymer samples with respect to the elapsed time after being decompressed from the high pressure total amount of adsorption and diffusivity (D) of hydrogen are evaluated with self-developed program of Fick's diffusion equation specified to a sample shape. The solubility (S) and permeability (P) of the polymers are determined through Henry's law and a relation of P=SD respectively. Developed techniques were applied to three kinds of spherical-shaped sealing rubbers NBR EPDM and FKM. The D S and P have been measured as function of pressure. The permeability obtained by both methods are discussed with Comsol simulation.
Internal and Surface Damage after Electrochemical Hydrogen Charging for Ultra Low Carbon Steel with Various Degrees of Recrystallization
Jul 2016
Publication
An ultra low carbon (ULC) steel was subjected to electrochemical hydrogen charging to provoke hydrogen induced damage in the material. The damage characteristics were analyzed for recrystallized partially recrystallized and cold deformed material. The goal of the study is to understand the effect of cold deformation on the hydrogen induced cracking behavior of a material which is subjected to cathodic hydrogen charging. Additionally charging conditions i.e. charging time and current density were varied in order to identify correlations between on the one hand crack initiation and propagation and on the other hand the charging conditions. The obtained hydrogen induced cracks were studied by optical microscopy scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD). Hydrogen induced cracks were observed to propagate transgranularly independently of the state of the material. Deformed samples were considerably more sensitive to hydrogen induced cracking which implies the important role of dislocations in hydrogen induced damage mechanisms.
Influence of Microstructural Morphology on Hydrogen Embrittlement in a Medium-Mn Steel Fe-12Mn-3Al-0.05C
Aug 2019
Publication
The ultrafine-grained (UFG) duplex microstructure of medium-Mn steel consists of a considerable amount of austenite and ferrite/martensite achieving an extraordinary balance of mechanical properties and alloying cost. In the present work two heat treatment routes were performed on a cold-rolled medium-Mn steel Fe-12Mn-3Al-0.05C (wt.%) to achieve comparable mechanical properties with different microstructural morphologies. One heat treatment was merely austenite-reverted-transformation (ART) annealing and the other one was a successive combination of austenitization (AUS) and ART annealing. The distinct responses to hydrogen ingression were characterized and discussed. The UFG martensite colonies produced by the AUS + ART process were found to be detrimental to ductility regardless of the amount of hydrogen which is likely attributed to the reduced lattice bonding strength according to the H-enhanced decohesion (HEDE) mechanism. With an increase in the hydrogen amount the mixed microstructure (granular + lamellar) in the ART specimen revealed a clear embrittlement transition with the possible contribution of HEDE and H-enhanced localized plasticity (HELP) mechanisms.
Hydrogen Embrittlement Behavior of 18Ni 300 Maraging Steel Produced by Selective Laser Melting
Jul 2019
Publication
A study was performed to investigate the hydrogen embrittlement behavior of 18-Ni 300 maraging steel produced by selective laser melting and subjected to different heat treatment strategies. Hydrogen was pre-charged into the tensile samples by an electro-chemical method at the constant current density of 1 A m−2 and 50 A m−2 for 48 h at room temperature. Charged and uncharged specimens were subjected to tensile tests and the hydrogen concentration was eventually analysed using quadrupole mass spectroscopy. After tensile tests uncharged maraging samples showed fracture surfaces with dimples. Conversely in H-charged alloys quasi-cleavage mode fractures occurred. A lower concentration of trapped hydrogen atoms and higher elongation at fracture were measured in the H-charged samples that were subjected to solution treatment prior to hydrogen charging compared to the as-built counterparts. Isothermal aging treatment performed at 460 °C for 8 h before hydrogen charging increased the concentration of trapped hydrogen giving rise to higher hydrogen embrittlement susceptibility.
Experimental Investigation of the Effect of Hydrogen on Fracture Toughness of 2.25Cr-1Mo-0.25V Steel and Welds after Annealing
Mar 2018
Publication
Hydrogen embrittlement (HE) is a critical issue that hinders the reliability of hydrogenation reactors. Hence it is of great significance to investigate the effect of hydrogen on fracture toughness of 2.25Cr-1Mo-0.25V steel and weld. In this work the fracture behavior of 2.25Cr-1Mo-0.25V steel and welds was studied by three-point bending tests under hydrogen-free and hydrogen-charged conditions. The immersion charging method was employed to pre-charge hydrogen inside specimen and the fracture toughness of these joints was evaluated quantitatively. The microstructure and grain size of the specimens were observed by scanning electron microscopy (SEM) and by metallurgical microscopy to investigate the HE mechanisms. It was found that fracture toughness for both the base metal (BM) and the weld zone (WZ) significantly decreased under hydrogen-charged conditions due to the coexistence of the hydrogen-enhanced decohesion (HEDE) and hydrogen-enhanced localized plasticity (HELP) mechanisms. Moreover the formation and growth of primary voids were observed in the BM leading to a superior fracture toughness. In addition the BM compared to the WZ shows superior resistance to HE because the finer grain size in the BM leads to a larger grain boundary area thus distributing more of the diffusive hydrogen trapped in the grain boundary and reducing the hydrogen content.
Hydrogen Trapping Behavior in Vanadium Microalloyed TRIP-Assisted Annealed Martensitic Steel
Jun 2019
Publication
Transformation induced plasticity (TRIP)-assisted annealed martensitic (TAM) steel combines higher tensile strength and elogangtion and has been increasingly used but appears to bemore prone to hydrogen embrittlement (HE). In this paper the hydrogen trapping behavior and HE of TRIP-assisted annealed martensitic steels with different vanadium additions had been investigated by means of hydrogen charging and slow strain rate tensile tests (SSRT) microstructral observartion and thermal desorption mass spectroscope (TDS). Hydrogen charging test results indicates that apparent hydrogen diffusive index Da is 1.94 × 10−7/cm2·s−1 for 0.21 wt.% vanadium steel while the value is 8.05 × 10−7/cm2·s−1 for V-free steel. SSRT results show that the hydrogen induced ductility loss ID is 76.2% for 0.21 wt.%V steel compared with 86.5% for V-free steel. The trapping mechanism of the steel containing different V contents is analyzed by means of TDS and Transmission electron microscope (TEM) observations. It is found out that the steel containing 0.21 wt.%V can create much more traps for hydrogen trapping compared with lower V steel which is due to vanadium carbide (VC) precipitates acting as traps capturing hydrogen atoms.The relationship between hydrogen diffusion and hydrogentrapping mechanism is discussed in details.
Investigation of Hydrogen Embrittlement Susceptibility and Fracture Toughness Drop after in situ Hydrogen Cathodic Charging for an X65 Pipeline Steel
Apr 2020
Publication
The present research focuses on the investigation of an in situ hydrogen charging effect during Crack Tip Opening Displacement testing (CTOD) on the fracture toughness properties of X65 pipeline steel. This grade of steel belongs to the broader category of High Strength Low Alloy Steels (HSLA) and its microstructure consists of equiaxed ferritic and bainitic grains with a low volume fraction of degenerated pearlite islands. The studied X65 steel specimens were extracted from pipes with 19.15 mm wall thickness. The fracture toughness parameters were determined after imposing the fatigue pre-cracked specimens on air on a specific electrolytic cell under a slow strain rate bending loading (according to ASTM G147-98 BS7448 and ISO12135 standards). Concerning the results of this study in the first phase the hydrogen cations’ penetration depth the diffusion coefficient of molecular and atomic hydrogen and the surficial density of blisters were determined. Next the characteristic parameters related to fracture toughness (such as J KQ CTODel CTODpl) were calculated by the aid of the Force-Crack Mouth Open Displacement curves and the relevant analytical equations.
Baking Effect on Desorption of Diffusible Hydrogen and Hydrogen Embrittlement on Hot-Stamped Boron Martensitic Steel
Jun 2019
Publication
Recently hot stamping technology has been increasingly used in automotive structural parts with ultrahigh strength to meet the standards of both high fuel efficiency and crashworthiness. However one issue of concern regarding these martensitic steels which are fabricated using a hot stamping procedure is that the steel is highly vulnerable to hydrogen delayed cracking caused by the diffusible hydrogen flow through the surface reaction of the coating in a furnace atmosphere. One way to make progress in understanding hydrogen delayed fractures is to elucidate an interaction for desorption with diffusible hydrogen behavior. The role of diffusible hydrogen on delayed fractures was studied for different baking times and temperatures in a range of automotive processes for hot-stamped martensitic steel with aluminum- and silicon-coated surfaces. It was clear that the release of diffusible hydrogen is effective at higher temperatures and longer times making the steel less susceptible to hydrogen delayed fractures. Using thermal desorption spectroscopy the phenomenon of the hydrogen delayed fracture was attributed to reversible hydrogen in microstructure sites with low trapping energy.
Hydrogen Storage Using a Hot Pressure Swing Reactor
Jun 2017
Publication
Our contribution demonstrates that hydrogen storage in stationary Liquid Organic Hydrogen Carrier (LOHC) systems becomes much simpler and significantly more efficient if both the LOHC hydrogenation and the LOHC dehydrogenation reaction are carried out in the same reactor using the same catalyst. The finding that the typical dehydrogenation catalyst for hydrogen release from perhydro dibenzyltoluene (H18-DBT) Pt on alumina turns into a highly active and very selective dibenzyltoluene hydrogenation catalyst at temperatures above 220 °C paves the way for our new hydrogen storage concept. Herein hydrogenation of H0-DBT and dehydrogenation of H18-DBT is carried out at the same elevated temperature between 290 and 310 °C with hydrogen pressure being the only variable for shifting the equilibrium between hydrogen loading and release. We demonstrate that the heat of hydrogenation can be provided at a temperature level suitable for effective dehydrogenation catalysis. Combined with a heat storage device of appropriate capacity or a high pressure steam system this heat could be used for dehydrogenation.
Effects of Thermomechanical Processing on Hydrogen Embrittlement Properties of Ultrahigh-Strength TRIP-Aided Bainitic Ferrite Steels
Jan 2022
Publication
The effects of thermomechanical processing on the microstructure and hydrogen embrittlement properties of ultrahigh-strength low-alloy transformation-induced plasticity (TRIP)-aided bainitic ferrite (TBF) steels were investigated to apply to automobile forging parts such as engine and drivetrain parts. The hydrogen embrittlement properties were evaluated by conducting conventional tensile tests after hydrogen charging and constant load four-point bending tests with hydrogen charging. The 0.4 mass%C-TBF steel achieved refinement of the microstructure improved retained austenite characteristics and strengthening owing to thermomechanical processing. This might be attributed to dynamic and static recrystallizations during thermomechanical processing in TBF steels. Moreover the hydrogen embrittlement resistances were improved by the thermomechanical processing in TBF steels. This might be caused by the refinement of the microstructure an increase in the stability of the retained austenite and low hydrogen absorption of the thermomechanically processed TBF steels.
Alloy and Composition Dependence of Hydrogen Embrittlement Susceptibility in High-strength Steel Fasteners
Jun 2017
Publication
High-strength steel fasteners characterized by tensile strengths above 1100 MPa are often used in critical applications where a failure can have catastrophic consequences. Preventing hydrogen embrittlement (HE) failure is a fundamental concern implicating the entire fastener supply chain. Research is typically conducted under idealized conditions that cannot be translated into know-how prescribed in fastener industry standards and practices. Additionally inconsistencies and even contradictions in fastener industry standards have led to much confusion and many preventable or misdiagnosed fastener failures. HE susceptibility is a function of the material condition which is comprehensively described by the metallurgical and mechanical properties. Material strength has a first-order effect on HE susceptibility which increases significantly above 1200 MPa and is characterized by a ductile--brittle transition. For a given concentration of hydrogen and at equal strength the critical strength above which the ductile–brittle transition begins can vary due to second-order effects of chemistry tempering temperature and sub-microstructure. Additionally non-homogeneity of the metallurgical structure resulting from poorly controlled heat treatment impurities and non-metallic inclusions can increase HE susceptibility of steel in ways that are measurable but unpredictable. Below 1200 MPa non-conforming quality is often the root cause of real-life failures.
Link to document download on Royal Society Website
Link to document download on Royal Society Website
Stress Corrosion Behavior of AM50Gd Magnesium Alloy in Different Environments
May 2019
Publication
A new type of high strength corrosion-resistant magnesium alloy was prepared by adding 1% rare earth Gd to AM50 and then treated with hot extrusion method. The stress corrosion properties of the new materials in air pure water 0.5 mol/L NaCl and 0.5 mol/L Na2SO4 solution were studied by the slow strain rate tensile (SSRT) test in situ open circuit potential test Tafel curve test stereomicroscope SEM and EDS. The results showed the following. The stress corrosion sensitivity of the material in different environments was Na2SO4> NaCl > distilled water > air. According to the Tafel curves measured at 0 and 100 MPa the corrosion voltage decreased little and the corrosion current density increased rapidly under 100 Pa. This was because the film of the corrosion product ruptured to form a large cathode and a small anode which resulted in a large instantaneous corrosion current. The mechanism of hydrogen embrittlement and anodic dissolution together affected the stress corrosion behavior of the alloy. In distilled water hydrogen embrittlement played a major role while in NaCl and Na2SO4solution hydrogen embrittlement and anodic dissolution were both affected. The direct reason of the stress corrosion crack (SCC) samples’ failure was the cracks expanding rapidly at the bottom of pit which was caused by corrosion.
A Panoramic Analysis of Hydrogen Utilization Systems Using an Input-output Table for Next Generation Energy Systems
Apr 2017
Publication
The objective of this study is to analyze a government proposal from a panoramic perspective concerning the economic and environmental effects associated with the construction and operation of hydrogen utilization systems by the year 2030. We focused on a marine transport system for hydrogen produced offshore hydrogen gas turbine power generation fuel cell vehicles (FCVs) and hydrogen stations as well as residential fuel cell systems (RFCs). In this study using an Input-Output Table for Next Generation Energy Systems (IONGES) we evaluated the induced output labor and CO2 emissions from the construction and operation of these hydrogen technologies using a uniform approach. This may be helpful when considering future designs for the Japanese energy system. In terms of per 1 t-H2 of hydrogen use CO2 reductions from the use of FCVs are considerably higher than the additional CO2 emissions from foreign production and transportation of hydrogen. Because new construction of a hydrogen pipeline network is not considered to be realistic RFCs is assumed to consume hydrogen generated by refining town gas. In this case the CO2 reductions from using RFCs will decline under the electricity composition estimated for 2030 on the condition of a substantial expansion of electricity generation from renewable energy sources. However under the present composition of electricity production we can expect a certain amount of CO2 reductions from using RFCs. If hydrogen is directly supplied to RFCs CO2 reductions increase substantially. Thus we can reduce a significant amount of CO2 emissions if various unused energy sources dispersed around local areas or unharnessed renewable energies such as solar and wind power can be converted into hydrogen to be supplied to FCVs and RFCs.
Effect of Relative Humidity on Mechanical Degradation of Medium Mn Steels
Mar 2020
Publication
Medium Mn steels have been considered as the next-generation materials for use in the automotive industry due to their excellent strength and ductility balance. To reduce the total weight and improve the safety of vehicles medium Mn steels look forward to a highly promising future. However hydrogen-induced delayed cracking is a concern for the use of high strength steels. This work is focused on the service characteristics of two kinds of medium Mn steels under different relative humidity conditions (40% 60% 80% and 100%). Under normal relative humidity (about 40%) at 25 °C the hydrogen concentration in steel is 0.4 ppm. When exposed to higher relative humidity the hydrogen concentration in steel increases slowly and reaches a stable value about 0.8 ppm. In slow strain rate tensile tests under different relative humidity conditions the tensile strength changed the hydrogen concentration increased and the elongation decreased as well thereby increasing the hydrogen embrittlement sensitivity. In other words the smaller the tensile rate applied the greater the hydrogen embrittlement sensitivity. In constant load tests under different relative humidity conditions the threshold value of the delayed cracking of M7B (‘M’ referring to Mn ‘7’ meaning the content of Mn ‘B’ denoting batch annealing) steel maintains a steady value of 0.82 σb (tensile strength). The threshold value of the delayed cracking of M10B significantly changed along with relative humidity. When relative humidity increased from 60% to 80% the threshold dropped sharply from 0.63 σb to 0.52 σb. We define 80% relative humidity as the ‘threshold humidity’ for M10B.
Modelling a Kinetic Deviation of the Magnesium Hydrogenation Reaction at Conditions Close to Equilibrium
May 2019
Publication
A model has been derived for the magnesium hydrogenation reaction at conditions close to equilibrium. The reaction mechanism involves an adsorption element where the model is an extension of the Langmuir adsorption model. The concept of site availability (σs) is introduced whereby it has the capability to reduce the reaction rate. To improve representation of σs an adaptable semi-empirical equation has been developed. Supplement to the surface reaction a rate equation has been derived considering resistance effects. It was found that close to equilibrium surface resistance dominated the reaction.
NanoSIMS Analysis of Hydrogen and Deuterium in Metallic Alloys: Artefacts and Best Practice
Apr 2021
Publication
Hydrogen embrittlement can cause catastrophic failure of high strength alloys yet determining localised hydrogen in the microstructure is analytically challenging. NanoSIMS is one of the few techniques that can map hydrogen and deuterium in metal samples at microstructurally relevant length scales. Therefore it is essential to understand the artefacts and determine the optimum methodology for its reliable detection. An experimental methodology/protocol for NanoSIMS analysis of deuterium (as a proxy for hydrogen) has been established uncovering unreported artefacts and a new approach is presented to minimise these artefacts in mapping hydrogen and deuterium in alloys. This method was used to map deuterium distributions in electrochemically charged austenitic stainless steel and precipitation hardened nickel-based alloys. Residual deuterium contamination was detected in the analysis chamber as a result of deuterium outgassing from the samples and the impact of this deuterium contamination was assessed by a series of NanoSIMS experiments. A new analysis protocol was developed that involves mapping deuterium in the passive oxide layer thus mitigating beam damage effects that may prevent the detection of localised deuterium signals when the surface is highly deuterated.
Influence of Hydrogen for Crack Formation during Mechanical Clinching
Jan 2018
Publication
Hydrogen intrudes into the steel during pickling process which is a pre-processing before a joining process promoting crack formation. In a mechanical clinching which is one of joining method in the automotive industry cracks due to large strain sometimes forms. In order to guarantee reliability it is important to clarify the influence of hydrogen on crack formation of the joint. In this study we clarified the influence of hydrogen for the crack formation on the mechanical clinching. Hydrogen charge was carried out using an electrolytic cathode charge. After the charging mechanical clinching was performed. Mechanical clinching was carried out with steel plate and aluminium alloy plate. To clarify the influence of hydrogen mechanical clinching was conducted without hydrogen charring. To investigate the crack formation the test piece was cut and the cut surface was observed. When the joint was broken during the clinching the fracture surface was observed using an optical microscope and an electron microscope. The load-displacement diagram showed that without hydrogen charging the compressive load increased as the displacement increased. On the other hand the compressive load temporarily decreased with high hydrogen charging suggesting that cracks formed at the time. The cut surface observation showed that interlock was formed in both cases with low hydrogen charging and without hydrogen charging. With low hydrogen charging no cracks were formed in the joint. When high hydrogen charging was performed cracks were formed at the joining point. Fracture analysis showed brittle-like fracture surface. These results indicate that hydrogen induces crack formation in the mechanical clinching.
Validation of Selected Optical Methods for Assessing Polyethylene (PE) Liners Used in High Pressure Vessels for Hydrogen Storage
Jun 2021
Publication
A polyethylene (PE) liner is the basic element in high-pressure type 4 composite vessels designed for hydrogen or compressed natural gas (CNG) storage systems. Liner defects may result in the elimination of the whole vessel from use which is very expensive both at the manufacturing and exploitation stage. The goal is therefore the development of efficient non-destructive testing (NDT) methods to test a liner immediately after its manufacturing before applying a composite reinforcement. It should be noted that the current regulations codes and standards (RC&S) do not specify liner testing methods after manufacturing. It was considered especially important to find a way of locating and assessing the size of air bubbles and inclusions and the field of deformations in liner walls. It was also expected that these methods would be easily applicable to mass-produced liners. The paper proposes the use of three optical methods namely visual inspection digital image correlation (DIC) and optical fiber sensing based on Bragg gratings (FBG). Deformation measurements are validated with finite element analysis (FEA). The tested object was a prototype of a hydrogen liner for high-pressure storage (700 bar). The mentioned optical methods were used to identify defects and measure deformations.
Quantification of Hydrogen in Nanostructured Hydrogenated Passivating Contacts for Silicon Photovoltaics Combining SIMS-APT-TEM: A Multiscale Correlative Approach
Mar 2021
Publication
Multiscale characterization of the hydrogenation process of silicon solar cell contacts based on c-Si/SiOx/nc-SiCx(p) has been performed by combining dynamic secondary ion mass-spectrometry (D-SIMS) atom probe tomography (APT) and transmission electron microscopy (TEM). These contacts are formed by high-temperature firing which triggers the crystallization of SiCx followed by a hydrogenation process to passivate remaining interfacial defects. Due to the difficulty of characterizing hydrogen at the nm-scale the exact hydrogenation mechanisms have remained elusive. Using a correlative TEM-SIMS-APT analysis we are able to locate hydrogen trap sites and quantify the hydrogen content. Deuterium (D) a heavier isotope of hydrogen is used to distinguish hydrogen introduced during hydrogenation from its background signal. D-SIMS is used due to its high sensitivity to get an accurate deuterium-to-hydrogen ratio which is then used to correct deuterium profiles extracted from APT reconstructions. This new methodology to quantify the concentration of trapped hydrogen in nm-scale structures sheds new insights on hydrogen distribution in technologically important photovoltaic materials.
Analysis of Environmentally Assisted Cracking Processes in Notched Steels Using the Point Method
Sep 2019
Publication
This paper proposes the use of the Point Method (PM) to analyse Environmentally Assisted Cracking (EAC) processes in steels containing U-shaped notches. The PM a methodology included within the Theory of Critical Distances (TCD) has been extensively validated by many authors for the analysis of fracture and fatigue phenomena of different types of materials containing notches. However it has never been applied to other critical or subcritical cracking processes such as EAC or creep crack propagation.<br/>This work provides a PM-based analysis of EAC emanating from notches which is validated by testing CT notched specimens of X80 and S420 steels subjected to aggressive environments under hydrogen embrittlement conditions.<br/>The results reveal that the PM accurately predicts the crack propagation onset condition as well as the evolution of the material’s apparent EAC resistance.
Interaction of Hydrogen with the Bulk, Surface and Subsurface of Crystalline RuO2 from First Principles
Feb 2021
Publication
Hydrogen and its interaction with metal oxide surfaces is of major importance for a wide range of research and applied fields spanning from catalysis energy storage microelectronics to metallurgy. This paper reviews state of the art of first principles calculations on the well-known ruthenium oxide (RuO2) surface in its (110) orientation and its interaction with hydrogen. In addition to it the paper also fills gaps in knowledge with new calculations and results on the (001) surface. Bulk and surface interactions are thoroughly reviewed. This includes systematic analysis of adsorption sites local agglomeration propensity of hydrogen and migration pathways in which literature data and their potential deviations are explained. We notably discuss novel results on propensity for agglomeration of hydrogen within bulk channels [001] oriented in which the proton-like behavior of adsorbed hydrogen hinders further agglomeration in adjacent channels. The paper brings new insights into the migration pathways on the surface and in bulk both exhibiting preferential diffusion paths along the [001] direction. The paper finally investigates the subsurface region. We show that while the subsurface has more stable sites for adsorption compared to bulk its accessibility from the surface shows prohibitive activation barriers inhibiting penetration into subsurface and bulk. We further calculate and discuss adsorption and penetration processes on the alternative RuO2 (001) surface.
New Insights into Hydrogen Uptake on Porous Carbon Materials via Explainable Machine Learning
Apr 2021
Publication
To understand hydrogen uptake in porous carbon materials we developed machine learning models to predict excess uptake at 77 K based on the textural and chemical properties of carbon using a dataset containing 68 different samples and 1745 data points. Random forest is selected due to its high performance (R2 > 0.9) and analysis is performed using Shapley Additive Explanations (SHAP). It is found that pressure and Brunauer-Emmett-Teller (BET) surface area are the two strongest predictors of excess hydrogen uptake. Surprisingly this is followed by a positive correlation with oxygen content contributing up to ∼0.6 wt% additional hydrogen uptake contradicting the conclusions of previous studies. Finally pore volume has the smallest effect. The pore size distribution is also found to be important since ultramicropores (dp < 0.7 nm) are found to be more positively correlated with excess uptake than micropores (dp < 2 nm). However this effect is quite small compared to the role of BET surface area and total pore volume. The novel approach taken here can provide important insights in the rational design of carbon materials for hydrogen storage applications.
Reversible Hydrogenation of AB2-type Zr–Mg–Ni–V Based Hydrogen Storage Alloys
Feb 2021
Publication
The development of hydrogen energy is hindered by the lack of high-efficiency hydrogen storage materials. To explore new high-capacity hydrogen storage alloys reversible hydrogen storage in AB2-type alloy is realized by using A or B-side elemental substitution. The substitution of small atomic-radius element Zr and Mg on A-side of YNi2 and partial substitution of large atomic-radius element V on B-side of YNi2 alloy was investigated in this study. The obtained ZrMgNi4 ZrMgNi3V and ZrMgNi2V2 alloys remained single Laves phase structure at as-annealed hydrogenated and dehydrogenated states indicating that the hydrogen-induced amorphization and disproportionation was eliminated. From ZrMgNi4 to ZrMgNi2V2 with the increase of the degree of vanadium substitution the reversible hydrogen storage capacity increased from 0.6 wt% (0.35H/M) to 1.8 wt% (1.0H/M) meanwhile the lattice stability gradually increased. The ZrMgNi2V2 alloy could absorb 1.8 wt% hydrogen in about 2 h at 300 K under 4 MPa H2 pressure and reversibly desorb the absorbed hydrogen in approximately 30 min at 473 K without complicated activation process. The prominent properties of ZrMgNi2V22 elucidate its high potential for hydrogen storage application.
Irreversible Hydrogen Embrittlement Study of B1500HS High Strength Boron Steel
Dec 2020
Publication
The reversible/irreversible recovery of mechanical properties and the microstructure characteristics of a typical hot-stamped steel B1500HS have been studied under different conditions of hydrogen permeation. Initially all tested specimens were permeated by hydrogen atoms through an electrochemical hydrogen charging scheme. Then the comparisons between different currents and charging time were performed. The influence of different storage time was compared as well. Additionally the effect of the plastic strain introduced by pre-stretching was also investigated. The experimental results showed that the negative impact of hydrogen embrittlement was altered from reversible to irreversible as the magnitude of the charging current increased. The hydrogen blistering and the hydrogen charging-induced cracks were both observed and inspected in the tested samples regarding the irreversible situation. Moreover the adverse influence of hydrogen embrittlement was enhanced by plastic pre-straining or extending the charging period. At the micro-level hydrogen charging-induced cracks generally were generated at defect locations such as the prior austenite grain boundaries and lath martensite interfaces. Particularly crack direction occurred perpendicular to the orientation of lath martensite and transgranular fracture occurred at the prior austenite grains.
Quantitative Monitoring of the Environmental Hydrogen Embrittlement of Al-Zn-Mg-based Aluminum Alloys via Dnyamic Hydrogen Detection and Digital Image Correlation
Mar 2021
Publication
In this study a novel analytical system was developed to monitor the environmental hydrogen embrittlement of Al-Zn-Mg-based aluminum alloys dynamically and quantitatively under atmospheric air pressure. The system involves gas chromatography using a SnO2-based semiconductor hydrogen sensor a digital image correlation step and the use of a slow strain rate testing machine. Use of this system revealed that hydrogen atoms are generated during the plastic deformation of Al-Zn-Mg alloys caused by the chemical reaction between the water vapor in air and the alloy surface without oxide films. Digital image correlation also clarified that the generated hydrogen atoms caused numerous localized grain boundary cracks on the specimen surface resulting in a localized grain boundary fracture. The amount of hydrogen atoms evolved from the embrittled fracture surface was 2.7 times as high as that from the surface without embrittlement.
Influence of Microstructural Anisotropy on the Hydrogen-assisted Fracture of Notched Samples of Progressively Drawn Pearlitic Steel
Dec 2020
Publication
In this study fracture surfaces of notched specimens of pearlitic steels subjected to constant extension rate tests (CERTs) are analyzed in an environment causing hydrogen assisted fracture. In order to obtain general results both different notched geometries (to generate quite distinct stress triaxiality distributions in the vicinity of the notch tip) and diverse loading rates were used. The fracture surfaces were classified in relation to four micromechanical models of hydrogen-assisted micro-damage. To this end fractographic analysis in each fracture surface was carried out with a scanning electron microscopy. Generated results increase the number of micromechanical models found in the scientific literature.
Evaluation of Strength and Fracture Toughness of Ferritic High Strength Steels Under Hydrogen Environments
Sep 2017
Publication
The susceptibility of high strength ferritic steels to hydrogen-assisted fracture in hydrogen gas is usually evaluated by mechanical testing in high-pressure hydrogen gas or testing in air after pre-charging the specimens with hydrogen. We have used this second methodology conventionally known as internal hydrogen. Samples were pre-charged in an autoclave under 195 bar of pure hydrogen at 450ºC for 21 hours.<br/>Different chromium-molybdenum steels submitted to diverse quenching and tempering heat treatments were employed. Diverse specimens were also used: small cylindrical samples to measure hydrogen contents and the kinetics of hydrogen egression at room temperature tensile specimens notched tensile specimens with a sharp notch and also compact fracture toughness specimens. Fractographic examination in SEM was finally performed in order to know the way hydrogen modify fracture micromechanisms.<br/>The presence of hydrogen barely affects the conventional tensile properties of the steels but it clearly alters their notched tensile strength and fracture toughness. This is due to the strong effect that stress triaxiality (dependent also on the steel yield strength) has on the accumulation of hydrogen on the notch/crack front region being the displacement rate used in the test another important variable to be controlled due to its influence on hydrogen diffusion to the embrittled process zone. Moreover the modification of fracture micromechanisms was finally determined being ductile (initiation growth and coalescence of microvoids) in the absence of hydrogen and brittle and intergranular under the material conditions of maximum embrittlement.
Dislocation and Twinning Behaviors in High Manganese Steels in Respect to Hydrogen and Aluminum Alloying
Dec 2018
Publication
The dislocation and twinning evolution behaviors in high manganese steels Fe-22Mn-0.6C and Fe-17Mn-1.5Al-0.6C have been investigated under tensile deformation with and without diffusive hydrogen. The notched tensile tests were interrupted once primary cracks were detected using the applied direct current potential drop measurement. In parallel the strain distribution in the vicinity of the crack was characterized by digital image correlation using GOM optical system. The microstructure surrounding the crack was investigated by electron backscatter diffraction. Electron channeling contrast imaging was applied to reveal the evolution of dislocations stacking faults and deformation twins with respect to the developed strain gradient and amount of hydrogen. The results show that the diffusive hydrogen at the level of 26 ppm has a conspicuous effect on initiating stacking faults twin bundles and activating multiple deformation twinning systems in Fe-22Mn-0.6C. Eventually the interactions between deformation twins and grain boundaries lead to grain boundary decohesion in this material. In comparison hydrogen does not obviously affect the microstructure evolution namely the twinning thickness and the amount of activated twinning systems in Fe-17Mn-1.5Al-0.6C. The Al-alloyed grade reveals a postponed nucleation of deformation twins delayed onset of the secondary twinning system and develops finer twinning lamellae in comparison to the Al-free material. These observations explain the improved resistance to hydrogen-induced cracking in Al-alloyed TWIP steels.
Effect of Hydrogen on Short Crack Propagation in SA508 Grade 3 Class I Low Alloy Steel Under Cyclic Loading
Aug 2019
Publication
The effect of hydrogen on short crack propagation under cyclic loading in SA508 Grade 3 Class I low alloy steel is investigated. This low alloy steel is used in manufacturing of pressure vessel installed in Indian nuclear power plants. During operation these pressure vessels are subjected to continuous supply of pressurized hot water at 600 K and hence are susceptible to hydrogen embrittlement. In past research has been conducted on the effect of hydrogen embrittlement on long fatigue crack propagation in this material but the mechanistic understanding and correlation of hydrogen embrittlement with microstructural features in the material can be understood well by studying the effect of hydrogen embrittlement on short fatigue crack propagation. Short fatigue cracks are of the order of 10 µm to 1 mm and unlike long cracks these short cracks strongly interact with the microstructural features in the material such as grain/phase boundaries. The effect of hydrogen embrittlement on short crack propagation is studied by artificial hydrogen charging of the material through electrochemical process. The single edge notch tension (SENT) specimens with an initial notch of the order of 85 to 90 µm are used to study the short crack propagation. The short cracks in hydrogen charged samples initiated from the notch at lower number of loading cycles as compared to the uncharged notched samples for the same value of applied stress range (Δσ). After initiation the short fatigue crack in hydrogen charged samples propagated at higher rate as compared to uncharged samples. This dissimilarity in crack propagation behavior is due to the difference in the interaction of short fatigue crack with the microstructural features for a hydrogen charged and uncharged samples.
Reversible Hydrogen Storage Using Nanocomposites
Jul 2020
Publication
In the field of energy storage recently investigated nanocomposites show promise in terms of high hydrogen uptake and release with enhancement in the reaction kinetics. Among several carbonaceous nanovariants like carbon nanotubes (CNTs) fullerenes and graphitic nanofibers reveal reversible hydrogen sorption characteristics at 77 K due to their van der Waals interaction. The spillover mechanism combining Pd nanoparticles on the host metal-organic framework (MOF) show room temperature uptake of hydrogen. Metal or complex hydrides either in the nanocomposite form and its subset nanocatalyst dispersed alloy phases illustrate the concept of nanoengineering and nanoconfinement of particles with tailor-made properties for reversible hydrogen storage. Another class of materials comprising polymeric nanostructures such as conducting polyaniline and their functionalized nanocomposites are versatile hydrogen storage materials because of their unique size high specific surface-area pore-volume and bulk properties. The salient features of nanocomposite materials for reversible hydrogen storage are reviewed and discussed.
Hydrogen Embrittlement in Advanced High Strength Steels and Ultra High Strength Steels: A New Investigation Approach
Dec 2018
Publication
In order to reduce CO2 emissions and fuel consumption and to respect current environmental norms the reduction of vehicles weight is a primary target of the automotive industry. Advanced High Strength Steels (AHSS) and Ultra High Strength Steel (UHSS) which present excellent mechanical properties are consequently increasingly used in vehicle manufacturing. The increased strength to mass ratio compensates the higher cost per kg and AHSS and UHSS are proving to be cost-effective solutions for the body-in-white of mass market products.
In particular aluminized boron steel can be formed in complex shapes with press hardening processes acquiring high strength without distortion and increasing protection from crashes. On the other hand its characteristic martensitic microstructure is sensitive to hydrogen delayed fracture phenomena and at the same time the dew point in the furnace can produce hydrogen consequently to the high temperature reaction between water and aluminum. The high temperature also promotes hydrogen diffusion through the metal lattice under the aluminum-silicon coating thus increasing the diffusible hydrogen content. However after cooling the coating acts as a strong barrier preventing the hydrogen from going out of the microstructure. This increases the probability of delayed fracture. As this failure brings to the rejection of the component during production or even worse to the failure in its operation diffusible hydrogen absorbed in the component needs to be monitored during the production process.
For fast and simple measurements of the response to diffusible hydrogen of aluminized boron steel one of the HELIOS innovative instruments was used HELIOS II. Unlike the Devanathan cell that is based on a double electrochemical cell HELIOS II is based on a single cell coupled with a solid-state sensor. The instrument is able to give an immediate measure of diffusible hydrogen content in sheet steels semi-products or products avoiding time-consuming specimen palladium coating with a guided procedure that requires virtually zero training.
Two examples of diffusible hydrogen analyses are given for Usibor®1500-AS one before hot stamping/ quenching and one after hot stamping suggesting that the increase in the number of dislocations during hot stamping could be the main responsible for the lower apparent diffusivity of hydrogen.
In particular aluminized boron steel can be formed in complex shapes with press hardening processes acquiring high strength without distortion and increasing protection from crashes. On the other hand its characteristic martensitic microstructure is sensitive to hydrogen delayed fracture phenomena and at the same time the dew point in the furnace can produce hydrogen consequently to the high temperature reaction between water and aluminum. The high temperature also promotes hydrogen diffusion through the metal lattice under the aluminum-silicon coating thus increasing the diffusible hydrogen content. However after cooling the coating acts as a strong barrier preventing the hydrogen from going out of the microstructure. This increases the probability of delayed fracture. As this failure brings to the rejection of the component during production or even worse to the failure in its operation diffusible hydrogen absorbed in the component needs to be monitored during the production process.
For fast and simple measurements of the response to diffusible hydrogen of aluminized boron steel one of the HELIOS innovative instruments was used HELIOS II. Unlike the Devanathan cell that is based on a double electrochemical cell HELIOS II is based on a single cell coupled with a solid-state sensor. The instrument is able to give an immediate measure of diffusible hydrogen content in sheet steels semi-products or products avoiding time-consuming specimen palladium coating with a guided procedure that requires virtually zero training.
Two examples of diffusible hydrogen analyses are given for Usibor®1500-AS one before hot stamping/ quenching and one after hot stamping suggesting that the increase in the number of dislocations during hot stamping could be the main responsible for the lower apparent diffusivity of hydrogen.
Enhanced Hydrogen Storage of Alanates: Recent Progress and Future Perspectives
Feb 2021
Publication
The global energy crisis and environmental pollution have caused great concern. Hydrogen is a renewable and environmentally friendly source of energy and has potential to be a major alternative energy carrier in the future. Due to its high capacity and relatively low cost of raw materials alanate has been considered as one of the most promising candidates for hydrogen storage. Among them LiAlH4 and NaAlH4 as two representative metal alanates have attracted extensive attention. Unfortunately the high desorption temperature and sluggish kinetics restrict its practical application. In this paper the basic physical and chemical properties as well as the hydrogenation/dehydrogenation reaction mechanism of LiAlH4 and NaAlH4 are briefly reviewed. The recent progress on strategic optimizations toward tuning the thermodynamics and kinetics of the alanate including nanoscaling doping catalysts and compositing modification are emphatically discussed. Finally the coming challenges and the development prospects are also proposed in this review.
Investigation of the Hydrogen Embrittlement Susceptibility of T24 Boiler Tubing in the Context of Stress Corrosion Cracking of its Welds
Dec 2018
Publication
For the membrane and spiral walls of the new USC boilers the advanced T24 material was developed. In 2010 however extensive T24 tube weld cracking during the commissioning phase of several newly built boilers was observed. As the dominant root cause Hydrogen Induced - Stress Corrosion Cracking was reported. An investigation into the interaction of the T24 material with hydrogen was launched in order to compare its hydrogen embrittlement susceptibility with that of the T12 steel commonly used for older boiler evaporators. Both base materials and simulated Heat Affected Zone (HAZ) microstructures were tested. Total and diffusible hydrogen in the materials after electrochemical charging were measured. Thermo Desorption Spectrometry was used to gain insights into the trapping behaviour and the apparent diffusion coefficient at room temperature was determined. Based on the hardness and the diffusible hydrogen pick-up capacity of the materials it was concluded that T12 is less susceptible to hydrogen embrittlement than T24 as base material as well as in the HAZ condition and that the HAZ of T24 is more susceptible to hydrogen embrittlement than the base material both in the as welded and in the Post Weld Heat Treated (PWHT) condition. However based on the results of this investigation it could not be determined if the T24 HAZ is less susceptible to hydrogen embrittlement after PWHT.
Detection, Characterization and Sizing of Hydrogen Induced Cracking in Pressure Vessels Using Phased Array Ultrasonic Data Processing
Jul 2016
Publication
Pressure vessels operating in sour service conditions in refinery environments can be subject to the risk of H₂S cracking resulting from the hydrogen entering into the material. This risk which is related to the specific working conditions and to the quality of the steel used shall be properly managed in order to maintain the highest safety at a cost-effective level.<br/>Nowadays the typical management strategy is based on a risk based inspection (RBI) evaluation to define the inspection plan used in conjunction with a fitness for service (FFS) approach in defining if the vessel although presenting dangerous defects such as cracks can still be considered “fit for purpose” for a given time window based on specific fracture mechanics analysis.<br/>These vessels are periodically subject to non-destructive evaluation typically ultrasonic testing. Phased Array (PA) ultrasonic is the latest technology more and more used for this type of application.<br/>This paper presents the design and development of an optimized Phased Array ultrasonic inspection technique for the detection and sizing of hydrogen induced cracking (HIC) type flaws used as reference for comparison. Materials used containing natural operational defects were inspected in “as-service” conditions.<br/>Samples have then been inspected by means of a “full matrix capture” (FMC) acquisition process followed by “total focusing method” (TFM) data post processing. FCM-TFM data have been further post-processed and then used to create a 3D geometrical reconstruction of the volume inspected. Results obtained show the significant improvement that FMC/TFM has over traditional PA inspection techniques both in terms of sensitivity and resolution for this specific type of defect. Moreover since the FMC allows for the complete time domain signal to be captured from every element of a linear array probe the full set of data is available for post-processing.<br/>Finally the possibility to reconstruct the geometry of the component from the scans including the defects present in its volume represents the ideal solution for a reliable data transferring process to the engineering function for the subsequent FFS analysis.
Energy Transition: Measurement Needs Within the Hydrogen Industry
Dec 2017
Publication
Hydrogen in the UK is beginning to shift from hypothetical debates to practical demonstration projects. An ever-growing evidence base has showcased how the costs of hydrogen and its barriers to entry are reducing such that it now has practical potential to contribute to the decarbonisation of the UK's energy sector.
Despite this hydrogen has yet to have wide commercial uptake due in part to a number of barriers where measurement plays a critical role. To accelerate the shift towards the hydrogen economy these challenges have been identified and prioritised by NPL.
The report Energy transition: Measurement needs within the hydrogen industry outlines the challenges identified. The highest priority issues are:
This Document can be downloaded from their website
Despite this hydrogen has yet to have wide commercial uptake due in part to a number of barriers where measurement plays a critical role. To accelerate the shift towards the hydrogen economy these challenges have been identified and prioritised by NPL.
The report Energy transition: Measurement needs within the hydrogen industry outlines the challenges identified. The highest priority issues are:
- Material development for fuel cells and electrolysers to reduce costs and assess critical degradation mechanisms – extending lifetime and durability is key to the commercialisation of these technologies.
- Impact assessment of added odorant to hydrogen to aid leak detection. Measurement of its impact during pipeline transportation and on the end-use application (particularly fuel cell technology) will be important to provide assurance that it will not affect lifetime and durability.
- Determination of the blend ratio when hydrogen is mixed with natural gas in the gas grid. Accurate flow rate measurement and validated metering methods are needed to ensure accurate billing of the consumer.
- Measurement of the combustion properties of hydrogen including flame detection and propagation temperature and nitrogen oxides (NOx) emissions should it be used for heat applications to ensure existing and new appliances are suitable for hydrogen.
- Assessment of the suitability of existing gas infrastructure and materials for hydrogen transportation. Building an understanding of what adaptations might need to be made to avoid for example air permeation metal embrittlement and hydrogen leakage.
- Validated techniques for hydrogen storage which will require measurement of the efficiency and capacity of each mechanism through robust metering leakage detection and purity analysis to ensure they are optimised for the storage of hydrogen gas.
This Document can be downloaded from their website
Criticality and Life-Cycle Assessment of Materials Used in Fuel-Cell and Hydrogen Technologies
Mar 2021
Publication
The purpose of this paper is to obtain relevant data on materials that are the most commonly used in fuel-cell and hydrogen technologies. The focus is on polymer-electrolyte-membrane fuel cells solid-oxide fuel cells polymer-electrolyte-membrane water electrolysers and alkaline water electrolysers. An innovative methodological approach was developed for a preliminary material assessment of the four technologies. This methodological approach leads to a more rapid identification of the most influential or critical materials that substantially increase the environmental impact of fuel-cell and hydrogen technologies. The approach also assisted in amassing the life-cycle inventories—the emphasis here is on the solid-oxide fuel-cell technology because it is still in its early development stage and thus has a deficient materials’ database—that were used in a life-cycle assessment for an in-depth material-criticality analysis. All the listed materials—that either are or could potentially be used in these technologies—were analysed to give important information for the fuel-cell and hydrogen industries the recycling industry the hydrogen economy as well as policymakers. The main conclusion from the life-cycle assessment is that the polymer-electrolyte membrane water electrolysers have the highest environmental impacts; lower impacts are seen in polymer-electrolyte-membrane fuel cells and solid-oxide fuel cells while the lowest impacts are observed in alkaline water electrolysers. The results of the material assessment are presented together for all the considered materials but also separately for each observed technology.
Controllable H2 Generation by Formic Acid Decomposition on a Novel Pd/Templated Carbon Catalyst
Nov 2020
Publication
A novel Pd/templated carbon catalyst (Pd/TC) was developed characterized and tested in the dehydrogenation of formic acid (FA) under mild conditions with the possibility to control the H2 generation rate in the absence or presence of HCOONa (SF) by adjusting the Pd:FA and/or FA:SF ratios. The characterization results of the templated carbon obtained by the chemical vapor deposition of acetylene on NaY zeolite revealed different structural and morphological properties compared to other C-based supports. Therefore it was expected to induce a different catalytic behavior for the Pd/TC catalyst. Indeed the TC-supported Pd catalyst exhibited superior activity in the decomposition of FA even at room temperature with turnover frequencies (TOFs) of up to 143.7 and 218.8 h−1 at 60 °C. The H2 generation rate increased with an increasing temperature while the H2 yield increased with a decreasing FA concentration. Constant generation of gaseous flow (H2 + CO2) was achieved for 11 days by the complete dehydrogenation of FA at room temperature using a 2 M FA solution and Pd:FA = 1:2100. The presence of SF in the reaction medium significantly enhanced the H2 generation rate (535 h−1 for FA:SF = 3:1 and 60 °C).
Techno-Economics Optimization of H2 and CO2 Compression for Renewable Energy Storage and Power-to-Gas Applications
Nov 2021
Publication
The decarbonization of the industrial sector is imperative to achieve a sustainable future. Carbon capture and storage technologies are the leading options but lately the use of CO2 is also being considered as a very attractive alternative that approaches a circular economy. In this regard power to gas is a promising option to take advantage of renewable H2 by converting it together with the captured CO2 into renewable gases in particular renewable methane. As renewable energy production or the mismatch between renewable production and consumption is not constant it is essential to store renewable H2 or CO2 to properly run a methanation installation and produce renewable gas. This work analyses and optimizes the system layout and storage pressure and presents an annual cost (including CAPEX and OPEX) minimization. Results show the proper compression stages need to achieve the storage pressure that minimizes the system cost. This pressure is just below the supercritical pressure for CO2 and at lower pressures for H2 around 67 bar. This last quantity is in agreement with the usual pressures to store and distribute natural gas. Moreover the H2 storage costs are higher than that of CO2 even with lower mass quantities; this is due to the lower H2 density compared with CO2 . Finally it is concluded that the compressor costs are the most relevant costs for CO2 compression but the storage tank costs are the most relevant in the case of H2.
Hydrogen Stress Cracking Behaviour in Dissimilar Welded Joints of Duplex Stainless Steel and Carbon Steel
Jun 2021
Publication
As the need for duplex stainless steel (DSS) increases it is necessary to evaluate hydrogen stress cracking (HSC) in dissimilar welded joints (WJs) of DSS and carbon steel. This study aims to investigate the effect of the weld microstructure on the HSC behaviour of dissimilar gas-tungsten arc welds of DSS and carbon steel. In situ slow-strain rate testing (SSRT) with hydrogen charging was conducted for transverse WJs which fractured in the softened heat-affected zone of the carbon steel under hydrogen-free conditions. However HSC occurred at the martensite band and the interface of the austenite and martensite bands in the type-II boundary. The band acted as an HSC initiation site because of the presence of a large amount of trapped hydrogen and a high strain concentration during the SSRT with hydrogen charging. Even though some weld microstructures such as the austenite and martensite bands in type-II boundaries were harmless under normal hydrogen-free conditions they had a negative effect in a hydrogen atmosphere resulting in the premature rupture of the weld. Eventually a premature fracture occurred during the in situ SSRT in the type-II boundary because of the hydrogen-enhanced strain-induced void (HESIV) and hydrogen-enhanced localised plasticity (HELP) mechanisms.
No more items...