Safety

Hydrogen has the potential to act as the energy carrier of the future. It will be then produced in large amounts and will certainly need to be transported for long distances. The safest way to transport hydrogen is through pipelines. Failure of pipelines carrying gaseous hydrogen can have several effects some of which can pose a significant threat of damage to people and buildings in the immediate proximity of the failure location. This paper presents a probabilistic risk assessment procedure for the estimation of damage to people and buildings endangered by high-pressure hydrogen pipeline explosions. The procedure provides evaluation of annual probability of damage to people and buildings under an extreme event as a combination of the conditional probability of damage triggered by an explosion and the probability of occurrence of the explosion as a consequence of the pipeline failure. Physical features such as the gas jet release process flammable cloud size blast generation and explosion effects on people and buildings are considered and evaluated through the SLAB integral model TNO model Probit equations and Pressure-Impulse diagrams. For people both direct and indirect effects of overpressure events are considered. For buildings a comparison of the damage to different types of buildings (i.e. reinforced concrete buildings and tuff stone masonry buildings) is made. The probabilistic procedure presented may be used for designing a new hydrogen pipeline network and will be an advantageous tool for safety management of hydrogen gas pipelines.

This paper presents results of an experimental investigation on detonation wave propagation in semi-confined geometries. Large scale experiments were performed in layers up to 0.6 m filled with uniform and non-uniform hydrogen–air mixtures in a rectangular channel (width 3 m; length 9 m) which is open from below. A semi confined driver section is used to accelerate hydrogen flames from weak ignition to detonation. The detonation propagation was observed in a 7 m long unobstructed part of the channel. Pressure measurements ionization probes soot-records and high speed imaging were used to observe the detonation propagation. Critical conditions for detonation propagation in different layer thicknesses are presented for uniform H2/air-mixtures as well as experiments with uniform H2/O2 mixtures in a down scaled transparent channel. Finally detail investigations on the detonation wave propagation in H2/air-mixtures with concentration gradients are shown.

A series of experiments in a thin layer geometry performed at the HYKA test site of the KIT. The experiments on different combustion regimes for lean and stoichiometric H2/air mixtures were performed in a rectangular chamber with dimensions of 20 x 90 x h cm3 where h is the thickness of the layer (h = 1 2 4 6 8 10 mm). Three different layer geometries:

• a smooth channel without obstructions;
• the channel with a metal grid filled 25% of length and
• a metal grid filled 100% of length. 

Detail measurement of H2/air combustion behaviour including flame acceleration (FA) and DDT in closed rectangular channel have been done. Five categories of flame propagation regimes were classified. Special attention was paid to the analysis of critical condition for different regimes of flame propagation as function of the layer thickness and roughness of the channel. It was found that thinner layer suppresses the detonation onset and even with a roughness the flame is available to accelerate to speed of sound. The detonation may occur only in a channel thicker than 6 mm.

Experiments were performed on the influence of oxidants (air pure oxygen O2 and pure nitrous oxide N2O at atmospheric pressure) in the straight expansion tube after the burst disk on the hydrogen spontaneous ignition. The lowest pressure at which the spontaneous ignition is observed has been researched for a 4 mm diameter tube with a length of 10 cm for the two oxidant gases. The ignition phenomenon is observed with a high speed camera and the external overpressures are measured. Numerical simulations have also been conducted with the high resolution CFD approach detailed chemistry formerly developed by Wen and co-workers. Comparison is made between the predictions and the experimental data.

The introduction of hydrogen to the commercial market as alternative fuel brings up safety concerns. Its storage in liquid or cryo-compressed state to achieve volumetric efficiency involves additional risks and their study is crucial. This work aims to investigate the behaviour of cryogenic hydrogen release and to study factors that affect the vapor dispersion. We focus on the effect of ambient humidity and air's components (nitrogen and oxygen) freezing in order to identify the conditions under which these factors have considerable influence. The study reveals that the level of influence depends highly on the release conditions and that humidity can reduce conspicuously the longitudinal distance of the Lower Flammability Limit (LFL). Low Froude (Fr) number (<1000) at the release allows the generated by the humidity phase change buoyancy to affect the dispersion while for higher Fr number - that usually are met in cryo-compressed releases - the momentum forces are the dominant forces and the buoyancy effect is trivial. Simulations with liquid methane release have been also performed and compared to the liquid hydrogen simulations in order to detect the differences in the behaviour of the two fuels as far as the humidity effect is concerned. It is shown that in methane spills the buoyancy effect in presence of humidity is smaller than in hydrogen spills and it can be considered almost negligible.

At the JRC-IET on-board hydrogen tanks have been subjected to filling–emptying cycles to investigate their long-term mechanical and thermal behaviour and their safety performance. The local temperature history inside the tanks has been measured and compared with the temperatures outside and at the tank metallic bosses which is the measurement location identified by some standards. The outcome of these activities is a set of experimental data which will be made publicly available as reference for safety studies and validation of computational fluid dynamics.

Hydrogen safety is a relevant topic for both nuclear fission and fusion power plants. Hydrogen generated in the course of a severe accident may endanger the integrity of safety barriers and may result in radioactive releases. In the case of the ITER fusion facility accident scenarios with water ingress consider the release of hydrogen into the suppression tank (ST) of the vacuum vessel pressure suppression system (VVPSS). Under the assumption of additional air ingress the formation of flammable gas mixtures may lead to explosions and safety component failure.<br/>The installation of passive auto-catalytic recombiners (PARs) inside the ST which are presently used as safety devices inside the containments of nuclear fission reactors is one option under consideration to mitigate such a scenario. PARs convert hydrogen into water vapor by means of passive mechanisms and have been qualified for operation under the conditions of a nuclear power plant accident since the 1990s.<br/>In order to support on-going hydrogen safety considerations simulations of accident scenarios using the CFD code ANSYS-CFX are foreseen. In this context the in-house code REKO-DIREKT is coupled to CFX to simulate PAR operation. However the operational boundary conditions for hydrogen recombination (e.g. temperature pressure gas mixture) of a fusion reactor scenario differ significantly from those of a fission reactor. In order to enhance the code towards realistic PAR operation a series of experiments has been performed in the REKO-4 facility with specific focus on ITER conditions. These specifically include operation under sub-atmospheric pressure (0.2–1.0 bar) gas compositions ranging from lean to rich H2/O2 mixtures and superposed flow conditions.<br/>The paper gives an overview of the experimental program presents results achieved and gives an outlook on the modelling approach towards accident scenario simulation.

This study is aimed at the validation of the pressure peaking phenomenon against laboratory-scale experiments. The phenomenon was discovered recently as a result of analytical and numerical studies performed at Ulster University. The phenomenon is characterized by the existence of a peak on the overpressure transient in an enclosure with vent(s) at some conditions. The peak overpressure can significantly exceed the steady-state pressure and jeopardise a civil structure integrity causing serious life safety and property protection problems. However the experimental validation of the phenomenon was absent until recently. The validation experiments were performed at Karlsruhe Institute of Technology within the framework of the HyIndoor project. Tests were carried out with release of three different gases (air helium and hydrogen) within a laboratory-scale enclosure of about 1 m3 volume with a vent of comparatively small size. The model of pressure peaking phenomenon reproduced closely the experimental pressure dynamics within the enclosure for all three used gases. The prediction of pressure peaking phenomenon consists of two steps which are explained in detail. Examples of calculation for typical hydrogen applications are presented.

Integral type models to describe stationary plumes and jets in cross-flows (wind) have been developed since about 1970. These models are widely used for risk analysis to describe the consequences of many different scenarios. Alternatively CFD codes are being applied but computational requirements still limit the number of scenarios that can be dealt with using CFD only. The integral models however are not suited to handle transient releases such as releases from pressurized equipment where the initially high release rate decreases rapidly with time. Further on gas ignition a second model is needed to describe the rapid combustion of the flammable part of the plume (flash fire) and a third model has to be applied for the remaining jet fire. The objective of this paper is to describe the first steps of the development of an integral-type model describing the transient development and decay of a jet of flammable gas after a release from a pressure container. The intention is to transfer the stationary models to a fully transient model capable to predict the maximum extension of short-duration high pressure jets. The model development is supported by conducting a set of transient ignited and unignited spontaneous releases at initial pressures between 25bar and 400bar. These data forms the basis for the presented model development approach.

A precise understanding of the flame turbulence induced by cellular instabilities is indispensable to perform an appropriate risk assessment of hydrogen fuelled gas explosion. In this research Darrieus Landau instability (DL instability) whose effect on gas explosion is  remarkable was experimentally examined. The DL instability is essentially caused by a volumetric expansion of burned gas at flame front. Therefore in order to examine the effects of volumetric expansion ratio the experiments were conducted using H2-O2-N2-Ar gas mixtures of various volumetric expansion ratio conditions by changing N2-Ar ratio. When Ar content ratio is increased the flame temperature becomes higher and volumetric expansion ratio is increased owing to lower specific heat of Ar. The experiments were conducted in nearly unconfined conditions of laboratory-scale and large-scale. Gas mixtures were filled in a 10 cm diameter soap bubble for the laboratory-scale and in a plastic tent of thin vinyl sheet of 1m3  for the large-scale. The gas mixtures were ignited by an electric spark and blast wave and flame speed were measured simultaneously by using a pressure sensor and a high-speed video camera. The DL instability owing to volumetric expansion accelerates flame propagation. In addition the intensity of blast wave was greatly raised depending on flame acceleration which can be explained by an acoustic theory. The effects of expansion ratio and experimental scales on flame propagation and blast wave were analyzed in detail. These results are quite important to perform an appropriate consequence analysis of accidental explosion of hydrogen.

Delayed explosions of accidental high pressure hydrogen releases are an important risk scenario in safety studies of production plants transportation pipelines and fuel cell vehicles charging stations. Such explosions were widely explored in multiple experimental and numerical investigations. Explosion of high pressure releases in highly obstructed geometries with high blockage ratio is a much more complicated phenomenon. This paper is dedicated to the experimental investigation of the influence of obstacles on a delayed deflagration of hydrogen jets. The computational fluid dynamics (CFD) code FLACS is used to reproduce experimental data. In the current study the computed overpressure signals are compared to the experimentally measured ones at different monitoring points. Simulations are in close agreement with experimental results and can be used to predict overpressure where experimental pressure detectors were saturated. For homogenous stationary clouds a new approach of equivalent mixture of H2/air (~16.5%) to stoichiometric mixture of CH4/air is suggested. This approach is validated versus experimental data from the literature in terms of overpressure maxima. A parametric study is performed using FLACS for various concentrations in the same geometry in order to identify a possible transition from deflagration to detonation.

Hydrogen-air mixtures are flammable in a wide range of compositions and have a low ignition energy compared to gaseous hydrocarbons. Due to its low density high buoyancy and diffusivity the mixing is strongly enhanced which supports distribution into large volumes if accidentally released. Economically valuable discontinuous transportation over large distances is only expected using liquid hydrogen (LH2). Releases of LH2 at its low temperature (20.3 K at 0.1 MPa) have additional hazards besides the combustible character of gaseous hydrogen (GH2). Hazard assessment requires simulation tools capable of calculating the pool spreading as well as the gas distribution for safety assessments of existing the future liquid hydrogen facilities. Evaluating possible risks the following process steps are useful:

• Possible accident release scenarios need to be identified for a given plant layout.
• Environmental boundary conditions such as wind conditions and humidity need to be identified and worst case scenarios have to be identified.
• A model approach based on this information which is capable of simulating LH2 releases vaporization rates and atmospheric dispersion of the gaseous hydrogen.
• Evaluate and verify safety distances identify new risks and/or extract certain design rules.

The process steps have been performed using the new validated 3D transient multiphase - multicomponent CFD model approach developed at Forschungszentrum Julich. A demonstration plant layout obtained from the IDEALHY project (Berstad et al.[1]) and two HAZID assessments (Hankinson et al.[2]) have been used for identifying a plant and a possible accident scenario. A general weather analysis at a possible location has been performed to identify weather conditions. Finally a full transient parameter calculation has been set up varying the LH2 release rate and the wind speed. The results have been analyzed and general conclusions have been derived.

To handle a hydrogen fuel cell vehicle (HFCV) safely after its involvement in an accident it is necessary to provide appropriate emergency response information to the first responder. In the present study a forced wind of 10 m/s or faster with and without a duct was applied to a vehicle leaking hydrogen gas at a rate of 2000 NL/min. Then hydrogen concentrations were measured around the vehicle and an ignition test was conducted to evaluate the effectiveness of forced winds and the safety of emergency response under forced wind conditions. The results: 1) Forced winds of 10 m/s or faster caused the hydrogen concentrations in the vicinity of the vehicle to decline to less than the lower flammability limit and the hydrogen gas in the various sections of the vehicles were so diluted that even if ignition occurred the blast-wave pressure was moderate. 2) When the first responder had located the hydrogen leakage point in the vehicle it was possible to lower the hydrogen concentrations around the vehicle by aiming the wind duct towards the leakage point and blowing winds at 10 m/s from the duct exit.

The paper present the work on PIV-measurements of reactant flow velocity in front of propagating flames in hydrogen-air explosions. The experiments was performed with hydrogen-air mixture at atmospheric pressure and room temperature. The experimental rig was a square channel with 45 × 20 mm2 cross section 300 mm long with a single cylindrical obstacle of blockage ratio 1/3. The equipment used for the PIV-measurements was a Firefly diode laser from Oxford lasers Photron SA-Z high-speed camera and a particle seeder producing 1 μm droplets of water. The gas concentrations used in the experiments was 14 and 17 vol% hydrogen in air. The resulting explosion can be characterized as slow since the maximum flow velocity of the reactants was 13 m/s in the 14% mixture and 23 m/s in the 17% mixture. The maximum flow velocities was measured during the flame-vortex interaction and at two obstacle diameters behind the obstacle. The flame-vortex interaction contributed to the flame acceleration by increasing the overall reaction rate and the flow velocity. The flame area as a function of position is the same for both concentrations as the flame passes the obstacle.

The development of the temperature field in hydrogen tanks during the filling process has been investigated with Computational Fluid Dynamics (CFD). Measurements from experiments undertaken at the JRC GasTef facility have been used to develop and validate the CFD modelling strategy; by means of the CFD calculations the effect of the injector direction on the temperature distribution has been analysed. It has been found that the dynamics of the temperature field including the development of potentially detrimental phenomena like thermal stratification and temperature inhomogeneity e.g. hot spots can be significantly affected by the injector orientation.

Laminar burning velocities (SL) of hydrogen/ammonia mixtures in air at atmospheric pressure were studied experimentally and numerically. The blending of hydrogen with ammonia two fuels that have been proposed as promising carriers for renewable energy causes the laminar flame speed of the mixture SL to decrease significantly. However details of this have not previously available. Systematic measurements were therefore performed for a series of hydrogen/ammonia mixtures with wide ranges of mole fractions of blended ammonia (XNH3) and equivalence ratio using a heat flux method based on heat flux of a flat flame transferred to the burner surface. It was found that the mixture of XNH3 = 40% has a value of SL close to that of methane which is the dominant component of natural gas. Using three chemical kinetic mechanisms available in the literature i.e. the well-known GRI-Mech 3.0 mechanism and two mechanisms recently released SL were also modelled for the cases studied. However the discrepancies between the experimental and numerical results can exceed 50% with the GRI-Mech 3.0 mechanism. Discrepancies were also found between the numerical results obtained with different mechanisms. These results can contribute to an increase in both the safety and efficiency of the coutilization of these two types of emerging renewable fuel and to guiding the development of better kinetic models.

Buoyancy effects and nozzle geometry can have a significant impact on turbulent jet dispersion. This work was motivated by applications involving hydrogen. Using helium as an experimental proxy buoyant horizontal jets issuing from a round orifice on the side wall of a circular tube were analyzed experimentally using particle image velocimetry (PIV) and planar laser-induced fluorescence (PLIF) techniques simultaneously to provide instantaneous and time-averaged flow fields of velocity and concentration. Effects of buoyancy and asymmetry on the resulting flow structure were studied over a range of Reynolds numbers and gas densities. Significant differences were found between the centreline trajectory spreading rate and velocity decay of conventional horizontal round axisymmetric jets issuing through flat plates and the pipeline leak-representative jets considered in the present study. The realistic pipeline jets were always asymmetric and found to deflect about the jet axis in the near field. In the far field it was found that the realistic pipeline leak geometry causes buoyancy effects to dominate much sooner than expected compared to horizontal round jets issuing through flat plates.

In order to face the coming shortage of fossil energies a number of alternative methods of energy production are being considered. One promising approach consists in using hydrogen in replacement of the conventional fossil fuels or as an additive to these fuels. In addition to conventional hydro-electric and fission-based nuclear plants electric energy could be obtained in the future using nuclear fusion as investigated within the framework of the ITER project International Thermonuclear Experimental Reactor. However the operation of ITER may rise safety problems including the formation of a flammable dust/hydrogen/air atmosphere. A first step towards the accurate assessment of accidental explosion in ITER consists in better characterizing the risk of explosion in gaseous hydrogen-containing mixtures. In the present study laminar burning speeds ignition delay-times behind reflected shock wave and detonation cell sizes were measured over wide ranges of composition and equivalence ratios. The performances of five detailed reaction models were evaluated with respect to the present data.

The growing number of hydrogen fillings stations and cars increases the need for accurate models to determine risk. The effect on hydrogen flame length was measured by varying the diameter of the spouting nozzle downstream from the chocked nozzle upstream. The results was compared with an existing model for flame length estimations. The experimental rig was setup with sensors that measured accurately temperature mass flow heat radiation and the pressure range from 0.1 to 11 MPa. The flame length was determined with an in-house developed image-processing tool which analyzed a high-speed film of the each experiment. Results show that the nozzle geometry can cause a deviation as high as 50% compared to estimated flame lengths by the model if wrong assumptions are made. Discharge coefficients for different nozzles has been calculated and presented.

The formation of hydrogen jets from pressurized sources and its ignition when hitting hot devices has been studied by many projects. The transient jets evolve with high turbulence depending on the configuration of the nozzle and especially the pressure in the hydrogen reservoir. In addition the length of the jets and the flames generated by ignition at a hot surface varies. Parameters to be varied were initial pressure of the source (2.5 10 20 and 40 MPa) distance between the nozzle and the hot surface (3 5 and 7 m) and temperature of the hot surface (between 400 and 1000 K). The interaction of the hydrogen jets is visualized by high-speed cinematography techniques which allow analysing the jet characteristics. By combination of various methods of image processing the visibility of the phenomena on the videos taken at 15 000 fps was improved. In addition high-speed NIR spectroscopy was used to obtain temperature profiles of the expanding deflagrations. The jets ignite already above 450 K for conditions mainly from the tubular source at 40 MPa. In addition the propagation of the flame front depends on all three varied parameters: temperature of the hot surface pressure in the reservoir and distance between nozzle and hot surface. In most cases also upstream propagation occurs. A high turbulence seems to lead to the strong deflagrations. At high temperatures of the ignition sources the interaction leads to fast deflagration and speeds up- and downstream of the jet. The deflagration velocity is close to velocity of sound and emission of pressure waves occurs.

Computational Fluid Dynamics (CFD) is applied to investigate the near exit jet behavior of high pressure hydrogen release into quiescent ambient air through different types of orifices. The size and geometry of the release hole can affect the possibility of auto-ignition. Therefore the effect of release geometry on the behavior and development of hydrogen jet issuing from non-axisymmetric (elliptical) and expanding orifices is investigated and compared with their equivalent circular orifices. A three-dimensional in-house code is developed using the MPI library for parallel computing to simulate the flow based on an inviscid approximation. Convection dominates viscous effects in strongly underexpanded supersonic jets in the vicinity of release exit justifying the use of the Euler equations. The transport (advection) equation is applied to calculate the concentration of hydrogen-air mixture. The Abel-Nobel equation of state is used because high pressure hydrogen flow deviates from the ideal gas assumption. This work effort is conducted to fulfill two objectives. First two types of circular and elliptic orifices with the same cross sectional area are simulated and the flow behavior of each case is studied and compared during the initial stage of release. Second the comparative study between expanding circular exit and its fixed counterpart is carried out. This evaluation is conducted for different sizes of nozzle with different aspect ratios.

Catastrophic rupture of onboard hydrogen storage in a fire is a safety concern. Different passive e.g. fireproofing materials the thermally activated pressure relief device (TPRD) and active e.g. initiation of TPRD by fire sensors safety systems are being developed to reduce hazards from and associated risks of high-pressure hydrogen storage tank rupture in a fire. The probability of such low-frequency highconsequences event is a function of fire resistance rating (FRR) i.e. the time before tank without TPRD ruptures in a fire the probability of TPRD failure etc. This safety issue is “confirmed” by observed recently cases of CNG tanks rupture due to blocked or failed to operate TPRD etc. The increase of FRR by any means decreases the probability of tank rupture in a fire particularly because of fire extinction by first responders on arrival at an accident scene.<br/>This study of socio-economic effects of safety applies a quantitative risk assessment (QRA) methodology to an example of hydrogen vehicles with passive tank protection system on roads in London.<br/>The risk is defined here through the cost of human loss per fuel cell hydrogen vehicle (FCHV) fire accident and fatality rate per FCHV per year. The first step in the methodology is the consequence analysis based on validated deterministic engineering tools to estimate the main identified hazards: overpressure in the blast wave at different distances and the thermal hazards from a fireball in the case of catastrophic tank rupture in a fire. The population can be exposed to slight injury serious injury and fatality after an accident. These effects are determined based on criteria by Health and Safety Executive (UK) and a cost metrics is applied to the number of exposed people in these three harm categories to estimate the cost per an accident. The second step in the methodology is either the frequency or the probability analysis. Probabilities of a vehicle fire and failure of the thermally activated pressure relief device are taken from published sources. A vulnerability probit function is employed to calculate the probability of emergency operations’ failure to prevent tank rupture as a function of a storage tank FRR and time of fire brigade arrival. These later results are integrated to estimate the tank rupture frequency and fatality rate. The risk is presented as a function of fire resistance rating.<br/>The QRA methodology allows to calculate the cost of human loss associated with an FCHV fire accident and demonstrates how the increase of FRR of onboard storage as a safety engineering measure would improve socio-economics of FCHV deployment and public acceptance of the technology.

Hydrogen sensors are recognized as an important technology for facilitating the safe implementation of hydrogen as an alternative fuel and there are numerous reports of a sensor alarm successfully preventing a potentially serious event. However gaps in sensor metrological specifications as well as in their performance for some applications exist. The U.S. Department of Energy (DOE) Fuel Cell Technologies Office published a short list of critical gaps in the 2007 and 2012 Multiyear Project Plans; more detailed gap analyses were independently performed by the Joint Research Centre (JRC) and the National Renewable Energy Laboratory (NREL). There have been however some significant advances in sensor technologies since these assessments including the commercial availability of hydrogen sensors with fast response times (t90 < 1 s which had been an elusive DOE target since 2007) improved robustness to chemical poisons improved selectivity and improved lifetime and stability. These improvements however have not been universal and typically pertain to select platforms or models. Moreover as hydrogen markets grow and new applications are being explored more demands will be imposed on sensor performance. The hydrogen sensor laboratories at NREL and the JRC are currently updating the hydrogen safety sensor gap analysis through direct interaction with international stakeholders in the hydrogen community especially end users. NREL and the JRC are currently organizing a series of workshops (in Europe and the United States) with sensor developers end-users and other stakeholders in 2017 to identify technology gaps and to develop a path forward to address them. One workshop was held on May 10 in Brussels Belgium at the Headquarters of the Fuel Cell and Hydrogen Joint Undertaking. A second workshop is planned at NREL in Golden CO USA. This paper reviews improvements in sensor technologies in the past 5 to 10 years identifies gaps in sensor performance and use requirements and identifies potential research strategies to address the gaps. The outcomes of the Hydrogen Sensors Workshops are also summarized.

Deflagration-to-Detonation Transition Ratio (DDTR) is an important parameter in measuring the hazard of hydrogen detonation at given thermodynamic conditions. It’s among the major tasks to evaluate DDTR in the study of hydrogen safety in a nuclear containment. With CFD tools detailed distribution of thermodynamic parameters at each instant can be simulated with considerable reliability. Then DDTR can be estimated using related CFD output. Forstochastic or epistemic reasons uncertainty always exists in input parameters during computations. This lack of accuracy can finally be reflected in the uncertainty of computation results e.g. DDTR in our consideration. The analysis of the influence of the input uncertainty is therefore a key step to understand the model’s response on the output and possibly to improve the accuracy. The increase of computational power makes it possible to perform statistics-based sensitivity and uncertainty (SU) analysis on CFD simulations. This paper aims at presenting some ideas on the procedure in safety analysis on hydrogen in nuclear containment. A hydrogen recombiner case is constructed and simulated with CFD method. DDTR at each instant is computed using a semi-empirical method. RBD-FAST based SU analysis is performed on the result.

Consequence modelling of high potential risks of usage and transportation of cryogenic liquids yet requires substantial improvements. Among the cryogenics liquid hydrogen (LH2) needs especial treatments and a comprehensive understanding of spill and spread of liquid and dispersion of vapor. Even though many of recent works have shed lights on various incidents such as spread dispersion and explosion of the liquid over land less focus was given on spill and spread of LH2 onto water. The growing trend in ship transportation has enhanced risks such as ships’ accidental releases and terrorist attacks which may ultimately lead to the release of the cryogenic liquid onto water. The main goal of the current study is to present a computational fluid dynamic (CFD) approach using OpenFOAM to model release and spread of LH2 over water substrate and discuss previous approaches. It also includes empirical heat transfer equations due to boiling and computation of evaporation rate through an energy balance. The results of the proposed model will be potentially used within another coupled model that predicts gas dispersion]. This work presents a good practice approach to treat pool dynamics and appropriate correlations to identify heat flux from different sources. Furthermore some of the previous numerical approaches to redistribute or in some extend manipulate the LH2 pool dynamic are brought up for discussion and their pros and cons are explained. In the end the proposed model is validated by modelling LH2 spill experiment carried out in 1994 at the Research Centre Juelich in Germany.

In the present study the diffusion process of hydrogen leaking from a FCV (Fuel Cell Vehicle) in an underground parking garage is analyzed by numerical simulations in order to assess the risk of a leakage accident. The temporal and spatial evolution of the hydrogen concentration as well as the flammable region in the parking garage was predicted numerically. The effects of the leakage flow rate and an additional ventilation fan were investigated to evaluate the ventilation performance to relieve the accumulation of the hydrogen gas. The volume of the flammable region shows a non-linear growth in time and rapidly increases eventually. The present numerical analysis can provide a physical insight and quantitative data for safety of various hydrogen applications.

The efficiency of gas sensor application for facilitating the safe use of hydrogen depends to a considerable extent on the response time of the sensor to change in hydrogen concentration. The response and recovery times have been measured for five different hydrogen sensors three commercially available and two promising prototypes which operate at room temperature. Experiments according to ISO 26142 show that most of the sensors surpass much for a concentration change from clean to hydrogen containing air the demands of the standard for the response times t(90) and values of 2 to 16 s were estimated. For an opposite shift to clean air the recovery times t(10) are from 7 to 70 s. Results of transient behaviour can be fitted with an exponential approach. It can be demonstrated that results on transient behaviour depend not only from investigation method and the experimental conditions like gas changing rate and concentration jump as well as from operating parameters of sensors. In comparison to commercial MOS and MIS-FET hydrogen sensors new sensor prototypes operating at room temperature possesses in particular longer recovery times.

This work presents a parametric study on the similitude between hydrogen and helium distribution when released in the air by a source located inside of a naturally ventilated enclosure with two vents. Several configurations were experimentally addressed in order to improve knowledge on dispersion. Parameters were chosen to mimic operating conditions of hydrogen energy systems. Thus the varying parameters of the study were mainly the source diameter the releasing flow rate the volume and the geometry of the enclosure. Two different experimental set-ups were used in order to vary the enclosure's height between 1 and 2 m. Experimental results obtained with helium and hydrogen were compared at equivalent flow rates determined with existing similitude laws. It appears for the plume release case that helium can suitably be used for predicting hydrogen dispersion in these operating designs. On the other hand – when the flow turns into a jet – non negligible differences between hydrogen and helium dispersion appear. In this case helium – used as a direct substitute to hydrogen – will over predict concentrations we would get with hydrogen. Therefore helium concentration read-outs should be converted to obtain correct predictions for hydrogen. However such a converting law is not available yet.

The aim of this study was to validate a model for predicting overpressure arising from accidental hydrogen releases in areas with limited ventilation. Experiments were performed in a large-scale setup that included a steel-reinforced container of volume 14.9 m³ and variable ventilation areas and mass flow rates. The pressure peaking phenomenon characterized as transient overpressure with a characteristic peak in a vented enclosure was observed during all the experiments. The model description presented the relationship between the ventilation area mass flow rate enclosure volume and discharge coefficient. The experimental results were compared with two prediction models representing a perfect mix and the real mix. The perfect mix assumed that all the released hydrogen was well stirred inside the enclosure during the releases. The real mix prediction s used the hydrogen concentration and temperature data measured during experiments. The prediction results with both perfect mix and real mix showed possible hazards during unignited hydrogen releases.

Unintended releases can occur during the production storage transportation and filling of liquid hydrogen which may cause devastating consequences. In the present work liquid hydrogen leak is modeled in ANSYS Fluent with the numerical model validated using the liquid hydrogen spill test data. A three-layer artificial neural network (ANN) model is built in which the wind speed ground temperature leakage time and leakage rate are taken as the inputs the horizontal diffusion distance and vertical diffusion distance of combustible gas as the outputs of the ANN. The representative sample data derived from the detailed calculation results of the numerical model are selected via the orthogonal experiment method to train and verify the back propagation (BP) neural network. Comparing the calculation results of the formula fitting with the sample data the results show that the established ANN model can quickly and accurately predict the horizontal and vertical diffusion distance of flammable vapor cloud relatively. The influences of four parameters on the horizontal hazard distance as well as vertical hazard height are predicted and analyzed in the case of continuous overflow of liquid hydrogen using the ANN model.

The NASA Safety Standard which establishes a uniform process for hydrogen system design materials selection operation storage and transportation is presented. The guidelines include suggestions for safely storing handling and using hydrogen in gaseous (GH2) liquid (LH2) or slush (SLH2) form whether used as a propellant or non-propellant. The handbook contains 9 chapters detailing properties and hazards facility design design of components materials compatibility detection and transportation. Chapter 10 serves as a reference and the appendices contained therein include: assessment examples; scaling laws explosions blast effects and fragmentation; codes standards and NASA directives; and relief devices along with a list of tables and figures abbreviations a glossary and an index for ease of use. The intent of the handbook is to provide enough information that it can be used alone but at the same time reference data sources that can provide much more detail if required.

If the hydrogen economy is to progress more hydrogen fuelling stations are required. In the short term in the absence of a hydrogen distribution network these fuelling stations will have to be supplied by liquid hydrogen road tanker. Such a development will increase the number of tanker offloading operations significantly and these may need to be performed in close proximity to the general public.<br/>The aim of this work is to identify and address hazards relating to the storage and transport of bulk liquid hydrogen (LH2) that are associated with hydrogen refuelling stations located in urban environments. Experimental results will inform the wider hydrogen community and contribute to the development of more robust modelling tools. The results will also help to update and develop guidance for codes and standards.<br/>The first phase of the project was to develop an experimental and modelling strategy for the issues associated with liquid hydrogen spills; this was documented in HSL report XS/10/06[1].<br/>The second phase of the project was to produce a position paper on the hazards of liquid hydrogen which was published in 2009 XS/09/72[2]. This was also published as a HSE research report RR769 in 2010[3].<br/>This report details experiments performed to investigate spills of liquid hydrogen at a rate of 60 litres per minute. Measurements were made on unignited releases which included concentration of hydrogen in air thermal gradient in the concrete substrate liquid pool formation and temperatures within the pool. Computational modelling of the unignited releases has been undertaken at HSL and reported in MSU/12/01 [4]. Ignited releases of hydrogen have also been performed as part of this project; the results and findings from this work are reported in XS/11/77[5].

Unlike four-wheel fuel-cell vehicles fuel-cell motorcycles have little semi-closure space corresponding to the engine compartment of four-wheel fuel-cell vehicles. Furthermore motorcycles may fall while parked or running. We conducted hydrogen concentration measurement and ignition tests to evaluate the feasibility of detecting leaks when hydrogen gas leaked from a fuel-cell motorcycle as well as the risk of ignition. We found that the installation of hydrogen leak detectors is effective because it is possible to detect minute hydrogen leaks by installing leak detectors at appropriate points on the fuel cell motorcycle and risks can be reduced by interrupting the hydrogen leak immediately after detection.

The uncertainty on the laminar flame speed extracted from spherically expanding flames can be minimized by using large flame radius data for the extrapolation to zero stretch-rate. However at large radii the hydrodynamic and thermo-diffusive instabilities induce the formation of a complex cellular flame front and limit the range of usable data. In the present study we have employed the flame stability theory of Matalon to optimize the properties of the initial mixture so that transition to cellularity may occur at a pre-determined large radius. This approach was employed to measure the laminar flame speeds of H2/O2/N2/He mixtures with equivalence ratios from 0.6 to 2.0 at pressures of 50/80/100 kPa and a temperature of 300 K. For all the performed experiments the uncertainty related to the extrapolation to zero stretch-rate (performed with the linear curvature model) was below 2% as shown by the position of the data points in the (Lb/Rf;U Lb/Rf;L) plan where Lb is the burned Markstein length; and Rf;L and Rf;U are the flame radii at the lower and upper bounds of the extrapolation range. Comparison of the predictions of four chemical mechanisms with the present unstretched laminar flame speed data indicated an error below 10% for most conditions. In addition unsteady 1-D simulations performed with A-SURF demonstrated that the flame dynamical response to stretch rate could not be captured by the mechanisms. The present work indicates that although the stability theory of Matalon provides a well defined framework to optimize the mixture properties for improved flame speed measurement the uncertainty of some of the required parameters can result in largely over-estimated critical radius for cellularity onset which compromise the accuracy of the optimization procedure.

The authors presented a basic mathematical model for estimating peak overpressure attained in vented explosions of hydrogen in a previous study (Sinha et al. [1]). The model focussed on idealized cases of hydrogen and was not applicable for realistic accidental scenarios like presence of obstacles initial turbulent mixture etc. In the present study the underlying framework of the model is reformulated to overcome these limitations. The flame shape computations are simplified. A more accurate and simpler formulation for venting is also introduced. Further by using simplifying assumptions and algebraic manipulations the detailed model consisting of several equations is reduced to a single equation with only four parameters. Two of these parameters depend only on fuel properties and a standard table provided in the Appendix can be used. Therefore to compute the overpressure only the two parameters based on enclosure geometry need to be evaluated. This greatly simplifies the model and calculation effort. Also since the focus of previous investigation was hydrogen properties of hydrocarbon fuels which are much more widely used were not accounted for. The present model also accounts for thermo-physical properties of hydrocarbons and provides table for fuel parameters to be used in the final equation for propane and methane. The model is also improved by addition of different sub-models to account for various realistic accidental scenarios. Moreover no adjustable parameters are used; the same equation is used for all conditions and all gases. Predictions from this simplified model are compared with experimentally measured values of overpressure for hydrogen and hydrocarbons and found to be in good agreement. First the results from experiments focussing on idealized conditions of uniformly mixed fuel in an empty enclosure under quiescent conditions are considered. Further the model applicability is also tested for realistic conditions of accidental explosion consisting of obstacles inside the enclosure non-uniform fuel distribution initial turbulent mixture etc. For all the cases tested the new simple model is found to produce reasonably good predictions.

In the present work CFD simulations of a hydrogen deflagration experiment are performed. The experiment carried out by KIT was conducted in a 1 m3 enclosure with a square vent of 0.5 m2 located in the center of one of its walls. The enclosure was filled with homogeneous hydrogen-air mixture of 18% v/v before ignition at its back-wall. As the flame propagates away from the ignition point unburned mixture is forced out through the vent. This mixture is ignited when the flame passes through the vent initiating a violent external explosion which leads to a rapid increase in pressure. The work focuses on the modeling of the external explosion phenomenon. A new approach is proposed in order to predict with accuracy the strength of external explosions using Large Eddy Simulation. The new approach introduces new relations to account for the interaction between the turbulence and the flame front. CFD predictions of the pressure inside and outside the enclosure and of the flame front shape are compared against experimental measurements. The comparison indicates a much better performance of the new approach compared to the initial model.

Adequate safety measures are crucial for preventing major accidents at hydrogen fuelling stations. In particular risk analysis of the domino effect at hydrogen fuelling stations is essential because knock-on accidents are likely to intensify the consequences of a relatively small incident. Several risk assessment studies have focused on hydrogen fuelling stations but none have investigated accidental scenarios related to the domino effect at such stations. Therefore the purpose of this study is to identify a domino effect scenario analyze the scenario by using simulations and propose safety measures for preventing and mitigating of the scenario. In this hazard identification study we identified the domino effect scenario of a hydrogen fuelling station with an on-site hydrogen production system involving methylcyclohexane and investigated through simulations of the scenario. The simulations revealed that a pool fire of methylcyclohexane or toluene can damage the process equipment and that thermal radiation may cause the pressurized hydrogen tanks to rupture. The rupture-type vent system can serve as a critical safety measure for preventing and mitigating the examined scenario.

The highly combustible nature of hydrogen poses a great hazard creating a number of problems with its safety and handling. As a part of safety studies related to the use of hydrogen in a confined environment it is extremely important to have a good knowledge of the dispersion mechanism.<br/>The present work investigates the concentration field and flammability envelope from a small scale leak. The hydrogen is released into a 0.47 m × 0.33 m x 0.20 m enclosure designed as a 1/15 – scale model of a room in a nuclear facility. The performed tests evaluates the influence of the initial conditions at the leakage source on the dispersion and mixing characteristics in a confined environment. The role of the leak location and the presence of obstacles are also analyzed. Throughout the test during the release and the subsequent dispersion phase temporal profiles of hydrogen concentration are measured using thermal conductivity gauges within the enclosure. In addition the BOS (Background Oriented Schlieren) technique is used to visualise the cloud evolution inside the enclosure. These instruments allow the observation and quantification of the stratification effects.

Hydrogen gas concentrations and jet velocities were measured downstream by a high response speed flame ionization detector and PIV (Particle Image Velocimetry) in order to investigate the characteristics of dispersion and ignitability for 40–82 MPa high-pressurized hydrogen jet discharged from a nozzle with 0.2 mm diameter. The light emitted from both OH radical and water vapor species yielded from hydrogen combustion ignited by an electric spark were recorded by two high speed cameras. From the results the empirical formula concerning the relationships for time-averaged concentrations concentration fluctuations and ignition probability were obtained to suggest that they would be independent of hydrogen discharge pressure.

If the hydrogen economy is to progress more hydrogen fuelling stations are required. In the short term in the absence of a hydrogen distribution network these fuelling stations will have to be supplied by liquid hydrogen (LH2) road tanker. Such a development will increase the number of tanker offloading operations significantly and these may need to be performed in close proximity to the general public.<br/>Several research projects have been undertaken already at HSL with the aim of identifying and addressing hazards relating to the storage and transport of bulk LH2 that are associated with hydrogen refuelling stations located in urban environments.<br/>The first phase of the research was to produce a position paper on the hazards of LH2 (Pritchard and Rattigan 2009). This was published as an HSE research report RR769 in 2010.  <br/>The second phase developed an experimental and modelling strategy for issues associated with LH2 spills and was published as an internal report HSL XS/10/06. The subsequent experimental work is a direct implementation of that strategy. LH2 was first investigated experimentally (Royle and Willoughby 2012 HSL XS/11/70) as large-scale spills of LH2 at a rate of 60 litres per minute. Measurements were made on unignited releases which included the concentration of hydrogen in air thermal gradients in the concrete substrate liquid pool formation and temperatures within the pool. Computational modelling on the un-ignited spills was also performed (Batt and Webber 2012 HSL MSU/12/01).<br/>The experimental work on ignited releases of LH2 detailed in this report is a direct continuation of the work performed by Royle and Willoughby.<br/>The aim of this work was to determine the hazards and severity of a realistic ignited spill of LH2 focussing on; flammability limits of an LH2 vapour cloud flame speeds through an LH2 vapour cloud and subsequent radiative heat and overpressures after ignition. The results of the experimentation will inform the wider hydrogen community and contribute to the development of more robust modelling tools. The results will also help to update and develop guidance for codes and standards.

The main objectives were to identify materials issues relating to the widespread use of hydrogen as a fuel.

MAIN FINDINGS

• Hydrogen is seen by many as the answer to the environmental problems of reliance on fossil fuels for energy needs. A great deal of effort is currently being invested in research into all areas of the hydrogen economy such as fuel cells hydrogen generation transportation and storage.
• Fuel cells have the potential to provide power for a very wide range of applications ranging from small portable electronics devices to large stationary electricity production and vehicles covering the whole range of road vehicles and possibly extending to rail marine and even aviation.
• The main obstacles to achieving a viable hydrogen economy are costs of producing hydrogen from renewable sources issues relating to transportation and storage due to the low energy density of hydrogen gas and the cost and reliability of fuel cells.
• The main material considerations relating to the use of hydrogen are hydrogen embrittlement material properties at cryogenic temperatures (due to use of liquid hydrogen) and permeability.
• A number of new materials are likely to come to prominence in a hydrogen economy; high performance composites are likely to be used extensively for high pressure hydrogen cylinders new materials or combinations of materials may be used for hydrogen pipelines and a range of new materials are currently being considered for hydrogen storage such as metal hydrides and carbon nanotubes.
• Due to the effect of hydrogen on materials it is important to test any materials in the environment in which they would be used. Depending on the type of test this could require the use of very specialist expensive equipment. 

A set of original experiments is presented covering the topic of hydrogen-air mixture ignition by a hot surface. The hot surface is a 30 mm long/10 mm diameter heated coil which temperature is controlled by IR techniques. The coil is placed into the flowing stream of hydrogen air mixtures. The variable parameters are the composition of the flammable atmosphere (4 to 75% H2 v/v) the flow speed (from 0.5 m/s to 30 m/s) and its temperature (from -110°C to ambient). The experimental techniques and results are presented and a tentative interpretation is proposed based on ignition theories and highspeed video recordings. It is shown that the ignition temperature (600°C) is insensitive to flowing conditions which is a very unexpected result.

To define a strategy of mitigation for containerized hydrogen systems (fuel cells for example) against explosion the main characteristics of flammable atmosphere (size concentration turbulence…) shall be well-known. This article presents an experimental study on accidental hydrogen releases and dispersion into an enclosure of 4 m3 (2 m x 2 m x 1 m). Different release points are studied: two circular releases of 1 and 3 mm and a system to create ring-shaped releases. The releases are operated with a pressure between 10 and 40 bars in order to be close to the process conditions. Different positions of the release inside the enclosure i.e. centred on the floor or along a wall are also studied. A specific effort is made to characterize the turbulence in the enclosure during the releases. The objectives of the experimental study are to understand and quantify the mechanisms of formation of the explosive atmosphere taking into account the geometry and position of the release point and the confinement. Those experimental data are analyzed and compared with existing models and could bring some new elements to improve them.

With the development of the hydrogen economy it requires a better understanding of the potential for fires and explosions associated with the unintended release of hydrogen within a partially confined space. In order to mitigate the hydrogen fire and explosion risks effectively accurate predictions of the hydrogen transport and mixing processes are crucial. It is well known that turbulence modelling is one of the key elements for a successful simulation of gas mixing and transport. GASFLOW-MPI is a scalable CFD software solution used to predict fluid dynamics conjugate heat and mass transfer chemical kinetics aerosol transportation and other related phenomena. In order to capture more turbulence information the Large Eddy Simulation (LES) model and LES/RANS hybrid model Detached Eddy Simulation (DES) have been implemented and validated in 3-D CFD code GASFLOW-MPI. The standard Smagorisky SGS model is utilized in LES turbulence model. And the k-epsilon based DES model is employed. This paper assesses the capability of algebraic k-epsilon DES and LES turbulence model to simulate the mixing and transport behavior of highly buoyant gases in a partially confined geometry. Simulation results agree well with the overall trend measured in experiments conducted in a reduced scale enclosure with idealized leaks which shows that all these four turbulent models are validated and suitable for the simulation of light gas behavior. Furthermore the numerical results also indicate that the LES and DES model could be used to analysis the turbulence behavior in the hydrogen safety problems.

Hydrogen as a future energy carrier is receiving a significant amount of attention in Japan. From the viewpoint of safety risk evaluation is required in order to increase the number of hydrogen refuelling stations (HRSs) implemented in Japan. Collecting data about accidents in the past will provide a hint to understand the trend in the possibility of accidents occurrence by identifying its operation time However in new technology; accident rate estimation can have a high degree of uncertainty due to absence of major accident direct data in the late operational period. The uncertainty in the estimation is proportional to the data unavailability which increases over long operation period due to decrease in number of stations. In this paper a suitable time correlation model is adopted in the estimation to reflect lack (due to the limited operation period of HRS) or abundance of accident data which is not well supported by conventional approaches. The model adopted in this paper shows that the uncertainty in the estimation increases when the operation time is long owing to the decreasing data.

Methane and hydrogen-enriched (25 vol% and 50 vol% H₂ -enriched CH₄) methane/air premixed flames were investigated in a gas turbine model combustor under atmospheric conditions. The flame operability ranges were mapped at different Reynold numbers (Re) showing the dependence on Re and H₂ concentrations. The effects of equivalence ratio (Φ) Re and H₂ enrichment on flame structure were examined employing OH-PLIF measurement. For CH₄/air cases the flame was stabilized with an M shape; while for H₂ -enriched cases the flame transitions to a П shape above a specific Φ. This transition was observed to influence significantly the flashback limits. The flame shape transition is most likely a result of H₂ enrichment occurring due to the increase in flame speed higher resistance of the flame to the strain rate and change in the inner recirculation zone. Flow fields of CH₄/air flames were compared between low and high Re cases employing high-speed PIV. The flashback events led by two mechanisms (combustion-induced vortex breakdown CIVB and boundary-layer flashback BLF) were observed and recorded using high-speed OH chemiluminescence imaging. It was found that the CIVB flashback occurred only for CH4 flames with M shape whereas the BLF occurs for all H₂ -enriched flames with П shape.

The UK Government signed legislation on 27th June 2019 committing the UK to a legally binding target of Net Zero emissions by 2050. Climate change is one of the most significant technical economic social and business challenges facing the world today.

The H21 NIC Phase 1 project delivered an optimally designed experimentation and testing programme supported by the HSE Science Division and DNV GL with the aim to collect quantifiable evidence to support that the UK distribution network of 2032 will be comparably as safe operating on 100% hydrogen as it currently is on

natural gas. This innovative project begins to fill critical safety evidence gaps surrounding the conversion of the UK gas network to 100% hydrogen. This will facilitate progression towards H21 Phase 2 Operational Safety Demonstrations and the H21 Phase 3 Live Trials to promote customer acceptability and ultimately aid progress towards a government policy decision on heat.

DNV GL and HSE Science Division were engaged to undertake the experimentation testing and QRA update programme of work. DNV GL and HSE Science Division also peer reviewed each other’s programme of work at various stages throughout the project undertaking a challenge and review of the experimental data and results to provide confidence in the conclusions.

A strategic set of tests was designed to cover the range of assets represented across the Great Britain gas distribution networks. The assets used in the testing were mostly recovered from the distribution network as part of the ongoing Iron Mains Risk Reduction Replacement Programme. Controlled testing against a well-defined master testing plan with both natural gas and 100% hydrogen was then undertaken to provide the quantitative evidence to forecast any change to background leakage levels in a 100% hydrogen network.

Key Findings from Phase 1a:

• Of the 215 assets tested 41 of them were found to leak 19 of them provided sufficient data to be able to compare hydrogen and methane leak rates.
• The tests showed that assets that were gas tight on methane were also gas tight on hydrogen. Assets that leaked on hydrogen also leaked
• on methane including repaired assets.
• The ratio of the hydrogen to methane volumetric leak rates varied between 1.1 and 2.2 which is largely consistent with the bounding values expected for laminar and turbulent (or inertial) flow which gave ratios of 1.2 and 2.8 respectively.
• None of the PE assets leaked; cast ductile and spun iron leaked to a similar degree (around 26-29% of all iron assets leaked) and the proportion of leaking steel assets was slightly less (14%).
• Four types of joint were responsible for most of the leaks on joints: screwed lead yarn bolted gland and hook bolts.
• All of the repairs that sealed methane leaks also were effective when tested with hydrogen.

As the energy crisis becomes worse hydrogen as a clean energy source is more and more widely used in industrial production and people’s daily life. However there are hidden dangers in hydrogen storage and transportation because of its flammable and explosive features. Gas detection is the key to solving this problem. High quality sensors with more practical and commercial value must be able to accurately detect target gases in the environment. Emerging porous metal-organic framework (MOF) materials can effectively improve the selectivity of sensors as a result of high surface area and coordinated pore structure. The application of MOFs for surface modification to improve the selectivity and sensitivity of metal oxides sensors to hydrogen has been widely investigated. However the influence of MOF modified film thickness on the selectivity of hydrogen sensors is seldom studied. Moreover the mechanism of the selectivity improvement of the sensors with MOF modified film is still unclear. In this paper we prepared nano-sized ZnO particles by a homogeneous precipitation method. ZnO nanoparticle (NP) gas sensors were prepared by screen printing technology. Then a dense ZIF-8 film was grown on the surface of the gas sensor by hydrothermal synthesis. The morphology the composition of the elements and the characters of the product were analyzed by X-ray diffraction analysis (XRD) transmission electron microscope (TEM) scanning electron microscope (SEM) energy dispersive spectrometer (EDS) Brunauer-Emmett-Teller (BET) and differential scanning calorimetry (DSC). It is found that the ZIF-8 film grown for 4 h cannot form a dense core-shell structure. The thickness of ZIF-8 reaches 130 nm at 20 h. Through the detection and analysis of hydrogen (1000 ppm) ethanol (100 ppm) and acetone (50 ppm) from 150 °C to 290 °C it is found that the response of the ZnO@ZIF-8 sensors to hydrogen has been significantly improved while the response to ethanol and acetone was decreased. By comparing the change of the response coefficient when the thickness of ZIF-8 is 130 nm the gas sensor has a significantly improved selectivity to hydrogen at 230 °C. The continuous increase of the thickness tends to inhibit selectivity. The mechanism of selectivity improvement of the sensors with different thickness of the ZIF-8 films is discussed.

After nearly 25 years of service some of the wires of the tendons of “La Arena” bridge (Spain) started to exhibit the effects of environmental degradation processes. “La Arena” is cable-stayed bridge with 6 towers and a reference span between towers of about 100 meters. After a maintenance inspection of the bridge evidences of corrosion were detected in some of the galvanized wires of the cables. A more in-deep analysis of these wires revealed that many of them exhibited loss of section due to the corrosion process. In order to clarify the causes of this degradation event and to suggest some remedial actions an experimental program was designed. This program consisted of tensile and fatigue tests on some strand samples of the bridge together with a fractographic analysis of the fracture surfaces of the wires its galvanized layer thickness and some hydrogen measurements (hydrogen embrittlement could be another effect of the environmental degradation process).Once the type and extension of the flaws in the wires was characterized a structural integrity assessment of the strands was performed with the aim of quantifying the margins until failure and establishing some maintenance recommendations.

In situ electrochemical microcantilever bending tests were conducted in this study to investigate the role of grain boundaries (GBs) in hydrogen embrittlement (HE) of Alloy 725. Specimens were prepared under three different heat treatment conditions and denoted as solution-annealed (SA) aged (AG) and over-aged (OA) samples. For single-crystal beams in an H-containing environment all three heat-treated samples exhibited crack formation and propagation; however crack propagation was more severe in the OA sample. The anodic extraction of H presented similar results as those under the H-free condition indicating the reversibility of the H effect under the tested conditions. Bi-crystal micro-cantilevers bent under H-free and H-charged conditions revealed the significant role of the GB in the HE of the beams. The results indicated that the GB in the SA sample facilitated dislocation dissipation whereas for the OA sample it caused the retardation of crack propagation. For the AG sample testing in an H-containing environment led to the formation of a sharp severe crack along the GB path.