Germany
Review and Assessment of the Effect of Hydrogen Gas Pressure on the Embrittlement of Steels in Gaseous Hydrogen Environment
Apr 2021
Publication
Hydrogen gas pressure is an important test parameter when considering materials for high-pressure hydrogen applications. A large set of data on the effect of hydrogen gas pressure on mechanical properties in gaseous hydrogen experiments was reviewed. The data were analyzed by converting pressures into fugacities (f) and by fitting the data using an f|n| power law. For 95% of the data sets |n| was smaller than 0.37 which was discussed in the context of (i) rate-limiting steps in the hydrogen reaction chain and (ii) statistical aspects. This analysis might contribute to defining the appropriate test fugacities (pressures) to qualify materials for gaseous hydrogen applications.
Mechanism of Action of Polytetrafluoroethylene Binder on the Performance and Durability of High-temperature Polymer Electrolyte Fuel Cells
Feb 2021
Publication
In this work new insights into impacts of the polytetrafluoroethylene (PTFE) binder on high temperature polymer electrolyte fuel cells (HT-PEFCs) are provided by means of various characterizations and accelerated stress tests. Cathodes with PTFE contents from 0 wt% to 60 wt% were fabricated and compared using electrochemical measurements. The results indicate that the cell with 10 wt% PTFE in the cathode catalyst layer (CCL) shows the best performance due to having the lowest mass transport resistance and cathode protonic resistance. Moreover cyclic voltammograms show that Pt (100) edge and corner sites are significantly covered by PTFE and phosphate anions when the PTFE content is higher than 25 wt%. Open-circuit and low load-cycling conditions are applied to accelerate degradation processes of the HT-PEFCs. The PTFE binder shows a network structure in the pores of the catalyst layer which reduces phosphoric acid leaching during the aging tests. In addition the high binder HT-PEFCs more easily suffer from a mass transport problem leading to more severe performance degradation.
Can Industry Keep Gas Distribution Networks Alive? Future Development of the Gas Network in a Decarbonized World: A German Case Study
Dec 2022
Publication
With the growing need for decarbonization the future gas demand will decrease and the necessity of a gas distribution network is at stake. A remaining industrial gas demand on the distribution network level could lead to industry becoming the main gas consumer supplied by the gas distribution network leading to the question: can industry keep the gas distribution network alive? To answer this research question a three-stage analysis was conducted starting from a rough estimate of average gas demand per production site and then increasing the level of detail. This paper shows that about one third of the German industry sites investigated are currently supplied by the gas distribution network. While the steel industry offers new opportunities the food and tobacco industry alone cannot sustain the gas distribution network by itself.
Synthesis and Characterisation of Platinum-cobalt-manganese Ternary Alloy Catalysts Supported on Carbon Nanofibers: An Alternative Catalyst for Hydrogen Evolution Reaction
Mar 2020
Publication
A systematic method for obtaining a novel electrode structure based on PtCoMn ternary alloy catalyst supported on graphitic carbon nanofibers (CNF) for hydrogen evolution reaction (HER) in acidic media is proposed. Ternary alloy nanoparticles (Co0.6Mn0.4 Pt) with a mean crystallite diameter under 10 nm were electrodeposited onto a graphitic support material using a two-step pulsed deposition technique. Initially a surface functionalisation of the carbon nanofibers is performed with the aid of oxygen plasma. Subsequently a short galvanostatic pulse electrodeposition technique is applied. It has been demonstrated that if pulsing current is employed compositionally controlled PtCoMn catalysts can be achieved. Variations of metal concentration ratios in the electrolyte and main deposition parameters such as current density and pulse shape led to electrodes with relevant catalytic activity towards HER. The samples were further characterised using several physico-chemical methods to reveal their morphology structure chemical and electrochemical properties. X-ray diffraction confirms the PtCoMn alloy formation on the graphitic support and energy dispersive X-ray spectroscopy highlights the presence of the three metallic components from the alloy structure. The preliminary tests regarding the electrocatalytic activity of the developed electrodes display promising results compared to commercial Pt/C catalysts. The PtCoMn/CNF electrode exhibits a decrease in hydrogen evolution overpotential of about 250 mV at 40 mA cm−2 in acidic solution (0.5 M H2SO4) when compared to similar platinum based electrodes (Pt/CNF) and a Tafel slope of around 120 mV dec−1 indicating that HER takes place under the Volmer-Heyrovsky mechanismm
The Limitations of Hydrogen Blending in the European Gas Grid
Jan 2022
Publication
In recent years various studies have put forward the prospect of relying on low-carbon or renewable gases such as green hydrogen (H2) or biomethane to replace the supply of natural gas. Hydrogen in particular is receiving much attention as a versatile energy carrier that could complement direct electrification in a plethora of end-uses and questions over its production and deployment play an important part in the ongoing discussions around the energy chapters of the European Commission’s Green Deal agenda.
The aim of the short study was to assess the technical feasibility emission savings and cost impacts of the addition of hydrogen to the existing gas transport network the so-called practice of “hydrogen blending” which is currently being discussed as a deployment pathway in the context of the review of the EU Gas Market Regulation (GMR) and the Trans-European Networks for Energy (TEN-E) regulation.
The document can be downloaded from their website
The aim of the short study was to assess the technical feasibility emission savings and cost impacts of the addition of hydrogen to the existing gas transport network the so-called practice of “hydrogen blending” which is currently being discussed as a deployment pathway in the context of the review of the EU Gas Market Regulation (GMR) and the Trans-European Networks for Energy (TEN-E) regulation.
The document can be downloaded from their website
A Review on the Properties of Iron Aluminide Intermetallics
Jan 2016
Publication
Iron aluminides have been among the most studied intermetallics since the 1930s when their excellent oxidation resistance was first noticed. Their low cost of production low density high strength-to-weight ratios good wear resistance ease of fabrication and resistance to high temperature oxidation and sulfurization make them very attractive as a substitute for routine stainless steel in industrial applications. Furthermore iron aluminides allow for the conservation of less accessible and expensive elements such as nickel and molybdenum. These advantages have led to the consideration of many applications such as brake disks for windmills and trucks filtration systems in refineries and fossil power plants transfer rolls for hot-rolled steel strips and ethylene crackers and air deflectors for burning high-sulfur coal. A wide application for iron aluminides in industry strictly depends on the fundamental understanding of the influence of (i) alloy composition; (ii) microstructure; and (iii) number (type) of defects on the thermo-mechanical properties. Additionally environmental degradation of the alloys consisting of hydrogen embrittlement anodic or cathodic dissolution localized corrosion and oxidation resistance in different environments should be well known. Recently some progress in the development of new micro- and nano-mechanical testing methods in addition to the fabrication techniques of micro- and nano-scaled samples has enabled scientists to resolve more clearly the effects of alloying elements environmental items and crystal structure on the deformation behavior of alloys. In this paper we will review the extensive work which has been done during the last decades to address each of the points mentioned above.
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
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.
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
Hydrogen Tank Rupture in Fire in the Open Atmosphere: Hazard Distance Defined by Fireball
Feb 2021
Publication
The engineering correlations for assessment of hazard distance defined by a size of fireball after either liquid hydrogen spill combustion or high-pressure hydrogen tank rupture in a fire in the open atmosphere (both for stand-alone and under-vehicle tanks) are presented. The term “fireball size” is used for the maximum horizontal size of a fireball that is different from the term “fireball diameter” applied to spherical or semi-spherical shape fireballs. There are different reasons for a fireball to deviate from a spherical shape e.g. in case of tank rupture under a vehicle the non-instantaneous opening of tank walls etc. Two conservative correlations are built using theoretical analysis numerical simulations and experimental data available in the literature. The theoretical model for hydrogen fireball size assumes complete isobaric combustion of hydrogen in air and presumes its hemispherical shape as observed in the experiments and the simulations for tank rupturing at the ground level. The dependence of the fireball size on hydrogen mass and fireball’s diameter-to-height ratio is discussed. The correlation for liquid hydrogen release fireball is based on the experiments by Zabetakis (1964). The correlations can be applied as engineering tools to access hazard distances for scenarios of liquid or gaseous hydrogen storage tank rupture in a fire in the open atmosphere
Influence of Synthesis Gas Components on Hydrogen Storage Properties of Sodium Aluminium Hexahydride
Feb 2021
Publication
A systematic study of different ratios of CO CO2 N2 gas components on the hydrogen storage properties of the Na3AlH6 complex hydride with 4 mol% TiCl3 8 mol% aluminum and 8 mol% activated carbon is presented in this paper. The different concentrations of CO and CO2in H2 and CO CO2 N2 in H2 mixture were investigated. Both CO and CO2gas react with the complex hydride forming Al oxy-compounds NaOH and Na2CO3 that consequently cause serious decline in hydrogen storage capacity. These reactions lead to irreversible damage of complex hydride under the current experimental condition. Thus after 10 cycles with 0.1 vol % CO + 99.9 vol %H2 and 1 vol % CO + 99 vol %H2 the dehydrogenation storage capacity of the composite material decreased by 17.2% and 57.3% respectively. In the case of investigation of 10 cycles with 1 vol % CO2 + 99 vol % H2 gas mixture the capacity degradation was 53.5%. After 2 cycles with 10 vol % CO +90 vol % H2 full degradation was observed whereas after 6 cycles with 10 vol % CO2+ 90 vol % H2 degradation of 86.8% was measured. While testing with the gas mixture of 1.5 vol % CO + 10 vol % CO2+ 27 vol % H2 + 61.5 vol % N2 the degradation of 94% after 6 cycles was shown. According to these results it must be concluded that complex aluminum hydrides cannot be used for the absorption of hydrogen from syngas mixtures without thorough purification.
Market Segmentation of Domestic and Commercial Natural Gas Appliances
Jan 2021
Publication
The main goal of the project is to enable the wide adoption of H2NG (hydrogen in natural gas) blends by closing knowledge gaps regarding technical impacts on residential and commercial gas appliances. The project consortium will identify and recommend appropriate codes and standards that should be adapted to answer the needs and develop a strategy for addressing the challenges for new and existing appliances.<br/>This deliverable on market segmentation is part of work package 2 and provides a quantitative segmentation of the gas appliance market in terms of appliance population numbers. It therefore prepares the project partners to perform the subsequent selection of the most representative product types to be tested in the laboratories of the THyGA partners.<br/>The classification is developed to categorise appliances installed in the field based on available statistics calculation methods and estimations. As a result appliance populations are provided for each technology segment that draw a representative picture of the installed end-use appliances within the European Union in 2020.
Interaction of Hydrogen Jets with Hot Surfaces of Various Sizes and Temperatures
Sep 2019
Publication
The formation of hydrogen jets from pressurized sources and ignition has been studied by many projects also when hitting hot devices. In the paper presented at the conference 2 years ago the ignition was caused by glow plug a “point like source” at various temperatures distances of igniter and source and source pressures. In continuation of that work ignition now occurred by 1 or 3 platelets of size 45 x 18 mm at a temperatures of 1223 K. When hitting these hot platelets the resulting flame explosions and flame jets show interesting characteristics in contrast to the point like ignition where the explosions drifts downstream with the jet. Parameters of the experiments vary in initial pressure of the tubular source (10 20 and 40 MPa) distance between the nozzle and the hot surface (3 5 and 7 m) and temperature of the hot surface (1223 K). The initial explosions stabilize already at the stagnation point or the wake of the hot platelets. Furthermore flames propagate upstream and downstream depending on the pressure of the hydrogen reservoir and the distance. The achieved flame velocities vary strongly from 30 to 240 m/s. With all investigated hydrogen pressures strong reactions v > 40 m/s occur at platelet distances of 3 and 5 m. The higher values are mainly achieved with jets with 40 MPa pressure at 3 m distance. In these cases the initial explosion contours show irregular shapes. Various effects are found like explosion separation further independently initiated explosions and two parallel flame jets upstream as well as downstream.
Validation of a 3d Multiphase-multicomponent CFD Model for Accidental Liquid and Gaseous Hydrogen Releases
Sep 2017
Publication
As hydrogen-air mixtures are flammable in a wide range of concentrations and the minimum ignition energy is low compared to hydrocarbon fuels the safe handling of hydrogen is of utmost importance. Additional hazards may arise with the accidental spill of liquid hydrogen. Such a release of LH2 leads to a formation of a cryogenic pool a dynamic vaporization process and consequently a dispersion of gaseous hydrogen into the environment. Several LH2 release experiments as well as modelling approaches address this phenomenology. In contrast to existing approaches a new CFD model capable of simulating liquid and gaseous distribution was developed at Forschungszentrum Jülich. It is validated against existing experiments and yields no substantial lacks in the physical model and reveals a qualitatively consistent prediction. Nevertheless the deviation between experiment and simulation raises questions on the completeness of the database in particular with regard to the boundary conditions and available measurements.
Hydrogen Storage: Thermodynamic Analysis of Alkyl-Quinolines and Alkyl-Pyridines as Potential Liquid Organic Hydrogen Carriers (LOHC)
Dec 2021
Publication
The liquid organic hydrogen carriers (LOHC) are aromatic molecules which can be considered as an attractive option for the storage and transport of hydrogen. A considerable amount of hydrogen up to 7–8% wt. can be loaded and unloaded with a reversible chemical reaction. Substituted quinolines and pyridines are available from petroleum coal processing and wood preservation or they can be synthesized from aniline. Quinolines and pyridines can be considered as potential LOHC systems provided they have favorable thermodynamic properties which were the focus of this current study. The absolute vapor pressures of methyl-quinolines were measured using the transpiration method. The standard molar enthalpies of vaporization of alkyl-substituted quinolines and pyridines were derived from the vapor pressure temperature dependencies. Thermodynamic data on vaporization and formation enthalpies available in the literature were collected evaluated and combined with our own experimental results. The theoretical standard molar gas-phase enthalpies of formation of quinolines and pyridines calculated using the quantum-chemical G4 methods agreed well with the evaluated experimental data. Reliable standard molar enthalpies of formation in the liquid phase were derived by combining high-level quantum chemistry values of gas-phase enthalpies of formation with experimentally determined enthalpies of vaporization. The liquid-phase hydrogenation/dehydrogenation reaction enthalpies of alkyl-substituted pyridines and quinolines were calculated and compared with the data for other potential liquid organic hydrogen carriers. The comparatively low enthalpies of reaction make these heteroaromatics a seminal LOHC system.
Hydrogen Release from a High-Pressure Gh2 Reservoir in Case of a Small Leak
Sep 2009
Publication
High-pressure GH2 systems are of interest for storage and distribution of hydrogen. The dynamic blow-down process of a high-pressure GH2 reservoir in case of a small leak is a complex process involving a chain of distinct flow regimes and gas states which needs to be understood for safety investigations.<br/>This paper presents models to predict the hydrogen concentration and velocity field in the vicinity of a postulated small leak. An isentropic expansion model with a real gas equation of state for normal hydrogen is used to calculate the time dependent gas state in the reservoir and at the leak position. The subsequent gas expansion to 0.1 MPa is predicted with a zero-dimensional model. The gas conditions after expansion serve as input to a newly developed integral model for a round free turbulent H2-jet into ambient air. The model chain was evaluated by jet experiments with sonic hydrogen releases from different reservoir pressures and temperatures.<br/>Predictions are made for the blow-down of hydrogen reservoirs with 10 30 and 100 MPa initial pressure. The evolution of the pressure in the reservoir and of the H2 mass flux at the orifice are presented in dimensionless form which allows scaling to other system dimensions and initial gas conditions. Computed hydrogen concentrations and masses in the jet are given for the 100 MPa case. A normalized hydrogen concentration field in the free jet is presented which allows for a given leak scenario the prediction of the axial and radial range of burnable H2-air mixtures.
Molecular Transport Effects of Hydrocarbon Addition on Turbulent Hydrogen Flame Propagation
Sep 2007
Publication
We analytically investigated the influence of light hydrocarbons on turbulent premixed H2/air atmospheric flames under lean conditions in view of safe handling of H2 systems applications in H2 powered IC engines and gas turbines and also with an orientation towards modelling of H2 combustion. For this purpose an algebraic flame surface wrinkling model included with pressure and fuel type effects is used. The model predictions of turbulent premixed flames are compared with the set of corresponding experimental data of Kido et al. (Kido Nakahara et al. 2002). These expanding spherical flame data include H2–air mixtures doped with CH4 and C3H8 while the overall equivalence ratio of all the fuel/air mixtures is fixed at 0.8 for constant unstretched laminar flame speed of 25 cm/s by varying N2 composition. The model predictions show that there is little variation in turbulent flame speed ST for C3H8 additions up to 20-vol%. However for 50 vol% doping flame speed decreases by as much as 30 % from 250 cm/s that of pure H2–air mixtures for turbulence intensity of 200 cm/s. With respect to CH4 for 50 vol% doping ST reduces by only 6 % cf. pure H2/air mixture. In the first instance the substantial decrease of ST with C3H8 addition may be attributed to the increase in the Lewis number of the dual-fuel mixture and proportional restriction of molecular mobility of H2. That is this decrease in flame speed can be explained using the concept of leading edges of the turbulent flame brush (Lipatnikov and Chomiak 2005). As these leading edges have mostly positive curvature (convex to the unburned side) preferential-diffusive-thermal instabilities cause recognizable impact on flame speed at higher levels of turbulence with the effect being very strong for lean H2 mixtures. The lighter hydrocarbon substitutions tend to suppress the leading flame edges and possibly transition to detonation in confined structures and promote flame front stability of lean turbulent premixed flames. Thus there is a necessity to develop a predictive reaction model to quantitatively show the strong influence of molecular transport coefficients on ST.
Hytunnel Project to Investigate the Use of Hydrogen Vehicles in Road Tunnels
Sep 2009
Publication
Hydrogen vehicles may emerge as a leading contender to replace today’s internal combustion engine powered vehicles. A Phenomena Identification and Ranking Table exercise conducted as part of the European Network of Excellence on Hydrogen Safety (HySafe) identified the use of hydrogen vehicles in road tunnels as a topic of important concern. An internal project called HyTunnel was duly established within HySafe to review identify and analyse the issues involved and to contribute to the wider activity to establish the true nature of the hazards posed by hydrogen vehicles in the confined space of a tunnel and their relative severity compared to those posed by vehicles powered by conventional fuels including compressed natural gas (CNG). In addition to reviewing current hydrogen vehicle designs tunnel design practice and previous research a programme of experiments and CFD modelling activities was performed for selected scenarios to examine the dispersion and explosion hazards potentially posed by hydrogen vehicles. Releases from compressed gaseous hydrogen (CGH2) and liquid hydrogen (LH2) powered vehicles have been studied under various tunnel geometries and ventilation regimes. The findings drawn from the limited work done so far indicate that under normal circumstances hydrogen powered vehicles do not pose a significantly higher risk than those powered by petrol diesel or CNG but this needs to be confirmed by further research. In particular obstructions at tunnel ceiling level have been identified as a potential hazard in respect to fast deflagration or even detonation in some circumstances which warrants further investigation. The shape of the tunnel tunnel ventilation and vehicle pressure relief device (PRD) operation are potentially important parameters in determining explosion risks and the appropriate mitigation measures.
Laser Powder Bed Fusion of WE43 in Hydrogen-argon-gas Atmosphere
Sep 2020
Publication
Growing demand for individual and especially complex parts with emphasis on biomedical or lightweight applications enhances the importance of laser powder bed fusion. Magnesium alloys offer both biocompatibility and low density but feature a very high melting point of oxide layers while the evaporation temperature of pure magnesium is much lower. This impedes adequate part quality and process reproducibility. To weaken this oxide layer and enhance processability a 2 %-hydrogen-argon-gas atmosphere was investigated. A machine system was modified to the use of the novel inert gas to determine the influence of gas atmosphere on hollow cuboids and solid cubes. While processing a 20.3 % decrease in structure width and 20.6 % reduction in standard deviation of the cuboids was determined. There was no significate influence on relative density of solid cubes although eight of the ten highest density specimen were fabricated with the hydrogen addition.
Analysis of Transient Hydrogen Release, Dispersion and Explosion in a Tunnel with Fuel Cell Vehicles using All-Speed CFD Code
Sep 2019
Publication
Hydrogen energy is expanding world wide in recent years while hydrogen safety issues have drawn considerable attention. It is widely accepted that accidental hydrogen release in an open air environment will disperse quickly hence not causing significant hydrogen hazards. A hydrogen hazard is more likely to occur when hydrogen is accidentally released in a confined place i.e. parking garages and tunnels. Prediction the consequences of hydrogen detonation is important for hydrogen safety assessment and for ensuring the safety of installations during accidents. Hence an accident scenario of hydrogen release nd detonation in a tunnel is analysed with GASFLOW-MPI in this paper. GASFLOW-MPI is a well validated parallel CFD code focusing on hydrogen transport combustion and detonation. GASFLOWMPI solves compressible Navier-Stokes equations with a powerful all-speed Arbitrary-Lagrangian-Eulerian (ALE) method hence it can cover both the non-compressible flow during the hydrogen relesase and dispersion phases and the compressible flow during combustion and detonation. A 3D model of a tunnel including eight cars is modelled. Firstly the hydrogen dispersion in the tunnel is calculated. Then the detonation in the tunnel is calculated by manually igniting the hydrogen at the top of the tunnel when the λ criterion is maximum. The pressure loads are calculated to evaluate the consequence of the hazard.
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