United States

The H2@Scale program of the U.S. Department of Energy (DOE) Fuel Cell Technologies Office is supporting work on the hydrogen compatibility of polymers to improve the durability and reliability of materials for hydrogen infrastructure. The hydrogen compatibility program (H-Mat) seeks “to address the challenges of hydrogen degradation by elucidating the mechanisms of hydrogen-materials interactions with the goal of providing science-based strategies to design materials (micro)structures and morphology with improved resistance to hydrogen degradation.” This research has found hydrogen and pressure interactions with model rubber-material compounds demonstrating volume change and compression-set differences in the materials. The research leverages state-of-the-art capabilities of the DOE national labs. The materials were investigated using helium-ion microscopy which revealed significant morphological changes in the plasticizer incorporating compounds after exposure as evidenced by time-of-flight secondary ion mass spectrometry. Additional studies using transmission electron microscopy and nuclear magnetic resonance revealed that nanosized inclusions developed after gas decompression in rubber- and plasticizer-only materials; this is an indication of void formation at the nanometer level.

Contrary to several reports in the recent literature the use of oxygen sensors for indirectly monitoring ambient hydrogen concentration has serious drawbacks. This method is based on the assumption that a hydrogen release will displace oxygen which is quantified using oxygen sensors. Despite its shortcomings the draft Hydrogen Vehicle Global Technical Regulation lists this method as a means to monitor hydrogen leaks to verify vehicle fuel system integrity. Experimental evaluations that were designed to impartially compare the ability of commercial oxygen and hydrogen sensors to reliably measure and report hydrogen concentration changes are presented. Numerous drawbacks are identified and discussed.

The Department of Energy (DOE) Hydrogen Program Plan (the Program Plan or Plan) outlines the strategic high-level focus areas of DOE’s Hydrogen Program (the Program). The term Hydrogen Program refers not to any single office within DOE but rather to the cohesive and coordinated effort of multiple offices that conduct research development and demonstration (RD&D) activities on hydrogen technologies. This terminology and the coordinated efforts on hydrogen among relevant DOE offices have been in place since 2004 and provide an inclusive and strategic view of how the Department coordinates activities on hydrogen across applications and sectors. This version of the Plan updates and expands upon previous versions including the Hydrogen Posture Plan and the DOE Hydrogen and Fuel Cells Program Plan and provides a coordinated high-level summary of hydrogen related activities across DOE.



The 2006 Hydrogen Posture Plan fulfilled the requirement in the Energy Policy Act of 2005 (EPACT 2005) that the Energy Secretary transmit to Congress a coordinated plan for DOE’s hydrogen and fuel cell activities. For historical context the original Posture Plan issued in 2004 outlined a coordinated plan for DOE and the U.S. Department of Transportation to meet the goals of the Hydrogen Fuel Initiative (HFI) and implement the 2002 National Hydrogen Energy Technology Roadmap. The HFI was launched in 2004 to accelerate research development and demonstration (RD&D) of hydrogen and fuel cell technologies for use in transportation electricity generation and portable power applications. The Roadmap provided a blueprint for the public and private efforts required to fulfill a long-term national vision for hydrogen energy as outlined in A National Vision of America’s Transition to a Hydrogen Economy—to 2030 and Beyond. Both the Roadmap and the Vision were developed out of meetings involving DOE industry academia non-profit organizations and other stakeholders. The Roadmap the Vision the Posture Plans the 2011 Program Plan and the results of key stakeholder workshops continue to form the underlying basis for this current edition of the Program Plan.



This edition of the Program Plan reflects the Department’s focus on conducting coordinated RD&D activities to enable the adoption of hydrogen technologies across multiple applications and sectors. It includes content from the various plans and documents developed by individual offices within DOE working on hydrogen-related activities including: the Office of Fossil Energy's Hydrogen Strategy: Enabling a Low Carbon Economy the Office of Energy Efficiency and Renewable Energy’s Hydrogen and Fuel Cell Technologies Office Multi-year RD&D Plan the Office of Nuclear Energy’s Integrated Energy Systems 2020 Roadmap and the Office of Science’s Basic Research Needs for the Hydrogen Economy. Many of these documents are also in the process of updates and revisions and will be posted online.



Through this overarching document the reader will gain information on the key RD&D needs to enable the largescale use of hydrogen and related technologies—such as fuel cells and turbines—in the economy and how the Department’s various offices are addressing those needs. The Program will continue to periodically revise the Plan along with all program office RD&D plans to reflect technological progress programmatic changes policy decisions and updates based on stakeholder input and reviews.

This paper introduces the 3D risk management (3DRM) concept with particular emphasis on hydrogen installations (Hy3DRM). The 3DRM framework entails an integrated solution for risk management that combines a detailed site-specific 3D geometry model a computational fluid dynamics (CFD) tool for simulating flow-related accident scenarios methodology for frequency analysis and quantitative risk assessment (QRA) and state-of-the-art visualization techniques for risk communication and decision support. In order to reduce calculation time and to cover escalating accident scenarios involving structural collapse and projectiles the CFD-based consequence analysis can be complemented with empirical engineering models reduced order models or finite element analysis (FEA). The paper outlines the background for 3DRM and presents a proof-of-concept risk assessment for a hypothetical hydrogen filling station. The prototype focuses on dispersion fire and explosion scenarios resulting from loss of containment of gaseous hydrogen. The approach adopted here combines consequence assessments obtained with the CFD tool FLACS-Hydrogen from Gexcon and event frequencies estimated with the Hydrogen Risk Assessment Models (HyRAM) tool from Sandia to generate 3D risk contours for explosion pressure and radiation loads. For a given population density and set of harm criteria it is straightforward to extend the analysis to include personnel risk as well as risk-based design such as detector optimization. The discussion outlines main challenges and inherent limitations of the 3DRM concept as well as prospects for further development towards a fully integrated framework for risk management in organizations.

In this paper we present a detailed design study of a novel apparatus for safely generating hydrogen (H2) on demand according to a novel method using a controlled chemical reaction between water (H2O) and sodium (Na) metal that yields hydrogen gas of sufficient purity for direct use in fuel cells without risk of contaminating sensitive catalysts. The apparatus consists of a first pressure vessel filled with liquid H2O with an overpressure of nitrogen (N2) gas above the H2O reactant and a second pressure vessel that stores solid Na reactant. Hydrogen gas is generated above the solid Na when H2O reactant is introduced using a regulator that senses when the downstream pressure of H2 gas above the solid Na reactant has dropped below a threshold value. The sodium hydroxide (NaOH) byproduct of the hydrogen producing reaction is collected within the apparatus for later reprocessing by electrolysis to recover the Na reactant.

We investigated hydrogen embrittlement in Fe20Mn20Ni20Cr20Co and Fe30Mn10Cr10Co (at.%) alloys pre-charged with 100 MPa hydrogen gas by tensile testing at three initial strain rates of 10⁻⁴ 10⁻³ and 10⁻² s⁻¹ at ambient temperature. The alloys are classified as stable and metastable austenite-based high-entropy alloys (HEAs) respectively. Both HEAs showed the characteristic hydrogen-induced degradation of tensile ductility. Electron backscatter diffraction analysis indicated that the reduction in ductility by hydrogen pre-charging was associated with localized plasticity-assisted intergranular crack initiation. It should be noted as an important finding that hydrogen-assisted cracking of the metastable HEA occurred not through a brittle mechanism but through localized plastic deformation in both the austenite and ε-martensite phases.

Determining the risk of accidental ignition of flammable mixtures is a topic of tremendous importance in industry and aviation safety. The concept of minimum ignition energy (MIE) has traditionally formed the basis for studying ignition hazards of fuels. In recent years however the viewpoint of ignition as a statistical phenomenon has formed the basis for studying ignition as this approach appears to be more consistent with the inherent variability in engineering test data. We have developed a very low energy capacitive spark ignition system to produce short sparks with fixed lengths of 1 to 2 mm. The ignition system is used to perform spark ignition tests in lean hydrogen oxygen-argon test mixtures over a range of spark energies. The test results are analyzed using statistical tools to obtain probability distributions for ignition versus spark energy demonstrating the statistical nature of ignition. The results also show that small changes in the hydrogen concentration lead to large changes in the ignition energy and dramatically different flame characteristics. A second low-energy spark ignition system is also developed to generate longer sparks with varying lengths up to 10 mm. A second set of ignition tests is performed in one of the test mixtures using a large range of park energies and lengths. The results are analyzed to obtain a probability distribution for ignition versus the spark energy per unit spark length. Preliminary results show that a single threshold MIE value does not exist and that the energy per unit length may be a more appropriate parameter for quantifying the risk of ignition.

The International Energy Agency's Hydrogen Implementing Agreement (IEA HIA) was established in 1977 to pursue collaborative hydrogen research and development and information exchange among its member countries. Information and knowledge dissemination is a key aspect of the work within IEA HIA tasks and case studies technical reports and presentations/publications often result from the collaborative efforts. The work conducted in hydrogen safety under Task 31 and its predecessor Task 19 can positively impact the objectives of national programs even in cases for which a specific task report is not published. The interactions within Task 31 illustrate how technology information and knowledge exchange among participating hydrogen safety experts serve the objectives intended by the IEA HIA.

Hydrogen is being considered as a pathway to decarbonize large energy systems and for utility-scale energy storage. As these applications grow transportation infrastructure that can accommodate large quantities of hydrogen will be needed. Many millions of tons of hydrogen are already consumed annually some of which is transported in dedicated hydrogen pipelines. The materials and operation of these hydrogen pipeline systems however are managed with more constraints than a conventional natural gas pipeline. Transitional strategies for deep decarbonization of energy systems include blending hydrogen into existing natural gas systems where the materials and operations may not have the same controls. This study explores the hydrogen compatibility of existing pipeline steels and the suitability of these steels in hydrogen pipeline systems. Representative fracture and fatigue properties of pipeline grade steels in gaseous hydrogen are summarized from the literature. These properties are then considered in idealized design life calculations to inform materials performance for a typical gas pipeline.

Large-scale experiments examining spherical-flame acceleration in lean hydrogen-air mixtures were performed in a 64 m3 constant-pressure enclosure. Equivalence ratios ranging from 0.33 to 0.57 were examined using detailed front tracking for flame diameters up to 1.2 m through the use of a Background Oriented Schlieren (BOS) technique. From these measurements the critical radii for onset of instability for these mixtures on the order of 2–3 cm were obtained. In addition the laminar burning velocity and rate of flame acceleration as a function of radius were also measured.

Rational decision making in land use planning and licensing of H2 infrastructure surrounded by other industrial activities and population should take account of individual and societal risks. QRA produces a risk matrix of potential consequences versus event probabilities that is shrouded in ambiguity and lacking transparency. NIMBY and conflict are lurking. To counter these issues risk analysts should therefore also determine the utilities of decision alternatives which describe desirability of benefits on a single scale. Rationally weighing risks versus benefits results in more transparent and defendable decisions. Example risk analyses of two types of refuelling stations and three hydrogen supply transportation types applying Influence Diagram/BBNs are worked out. Keywords: risk assessment influence diagram decision making land use planning

HyRAM is a methodology and accompanying software toolkit which is being developed to provide a platform for integration of state-of-the-art validated science and engineering models and data relevant to hydrogen safety. As such the HyRAM software toolkit establishes a standard methodology for conducting quantitative risk assessment (QRA) and consequence analysis relevant to assessing the safety of hydrogen fueling and storage infrastructure. The HyRAM toolkit integrates fast-running deterministic and probabilistic models for quantifying risk of accident scenarios for predicting physical effects and for characterizing the impact of hydrogen hazards (thermal effects from jet fires thermal and pressure effects from deflagrations and detonations). HyRAM incorporates generic probabilities for equipment failures for nine types of hydrogen system components generic probabilities for hydrogen ignition and probabilistic models for the impact of heat flux and pressure on humans and structures. These are combined with fast-running computationally and experimentally validated models of hydrogen release and flame behaviour. HyRAM can be extended in scope via user contributed models and data. The QRA approach in HyRAM can be used for multiple types of analyses including codes and standards development code compliance safety basis development and facility safety planning. This manuscript discusses the current status and vision for HyRAM.

As hydrogen fuel cell vehicles become more widely adopted by consumers the demand for refuelling stations increases. Most vehicles require high-pressure (either 350 or 700 bar) hydrogen and therefore the refuelling infrastructure must support these pressures. Fast running reduced order physical models of releases from high-pressure sources are needed so that quantitative risk assessment can guide the safety certification of these stations. A release from a high pressure source is choked at the release point forming the complex shock structures of an under-expanded jet before achieving a characteristic Gaussian pro le for velocity density mass fraction etc. downstream. Rather than using significant computational resources to resolve the shock structure an equivalent source model can be used to quickly and accurately describe the ow in terms of velocity diameter and thermodynamic state after the shock structure. In this work we present correlations for the equivalent boundary conditions of a subsonic jet as a high-pressure jet downstream of the shock structure. Schlieren images of under-expanded jets are used to show that the geometrical structure of under-expanded jets scale with the square root of the static to ambient pressure ratio. Correlations for an equivalent source model are given and these parameters are also found to scale with square root of the pressure ratio. We present our model as well as planar laser Rayleigh scattering validation data for static pressures up to 60 bar.

As of 2014 the majority of the Codes and Standards required to initially deploy hydrogen technologies infrastructure in the US have been promulgated1. These codes and standards will be field tested through their application to actual hydrogen technologies projects. CCSI is process of identifying code issues that arise during project deployment and then develop codes solutions to these issues. These solutions would typically be proposed amendments to codes and standards. The process is continuous because of technology and the state of safety knowledge develops there will be a need for monitoring the application of codes and standards and improving them based on information gathered during their application. This paper will discuss code issues that have surfaced through hydrogen technologies infrastructure project deployment and potential code changes that would address these issues. The issues that this paper will address include:

• Setback distances for bulk hydrogen storage
• Code mandated hazard analyses
• Sensor placement and communication
• The use of approved equipment
• System monitoring and maintenance requirements

The United States has 11 distinct natural gas pipeline corridors: five originate in the Southwest four deliver natural gas from Canada and two extend from the Rocky Mountain region. This study assesses the potential to deliver hydrogen through the existing natural gas pipeline network as a hydrogen and natural gas mixture to defray the cost of building dedicated hydrogen pipelines.

Sandia National Laboratories has worked with stakeholders and original equipment manufacturers (OEMs) to develop scientific data that can be used to create risk-informed hydrogen codes and standards for the safe operation of indoor hydrogen fuel-cell forklifts. An important issue is the possibility of an accident inside a warehouse or other enclosed space where a release of hydrogen from the high-pressure gaseous storage tank could occur. For such scenarios computational fluid dynamics (CFD) simulations have been used to model the release and dispersion of gaseous hydrogen from the vehicle and to study the behavior of the ignitable hydrogen cloud inside the warehouse or enclosure. The overpressure arising as a result of ignition and subsequent deflagration of the hydrogen cloud within the warehouse has been studied for different ignition delay times and ignition locations. Both ventilated and unventilated warehouses have been considered in the analysis. Experiments have been performed in a scaled warehouse test facility and compared with simulations to validate the results of the computational analysis.

An experimental apparatus which was based on the ¼-scale garage previously used for studying helium release and dispersion in our laboratory was used to obtain effective diffusion coefficients of helium and hydrogen (released as forming gas for safety reasons) through gypsum panel. Two types of gypsum panel were used in the experiments. Helium or forming gas was released into the enclosure from a Fischer burner1 located near the enclosure floor for a fixed duration and then terminated. Eight thermal-conductivity sensors mounted at different vertical locations above the enclosure floor were used to monitor the temporal and spatial gas concentrations. An electric fan was used inside the enclosure to mix the released gas to ensure a spatially uniform gas concentration to minimize stratification. The temporal variations of the pressure difference between the enclosure interior and the ambience were also measured. An analytical model was developed to extract the effective diffusion coefficients from the experimental data.

The Department of Energy the Department of Defense's Defense Logistics Agency and the Department of Transportation's Federal Transit Administration have funded learning demonstrations and early market deployments to provide insight into applications of hydrogen technologies on the road in the warehouse and as stationary power. NREL's analyses validate the technology in real-world applications reveal the status of the technology and facilitate the development of hydrogen and fuel cell technologies manufacturing and operations. This paper presents the maintenance safety and operation data of fuel cells in multiple applications with the reported incidents near misses and frequencies. NREL has analyzed records of more than 225000 kilograms of hydrogen that have been dispensed through more than 108000 hydrogen fills with an excellent safety record.

Sandia National Laboratories is working with stakeholders to develop scientific data for use by standards development organizations to create hydrogen codes and standards for the safe use of liquid hydrogen. Knowledge of the concentration field and flammability envelope for high-pressure hydrogen leaks is an issue of importance for the safe use of liquid hydrogen. Sandia National Laboratories is engaged in an experimental and analytical program to characterize and predict the behaviour of liquid hydrogen releases. This paper presents a model for computing hydrogen dilution distances for cold hydrogen releases. Model validation is presented for leaks of room temperature and 80 K high-pressure hydrogen gas. The model accounts for a series of transitions that occurs from a stagnate location in the tank to a point in the leak jet where the concentration of hydrogen in air at the jet centerline has dropped to 4% by volume. The leaking hydrogen is assumed to be a simple compressible substance with thermodynamic equilibrium between hydrogen vapor hydrogen liquid and air. For the multi-phase portions of the jet near the leak location the REFPROP equation of state models developed by NIST are used to account for the thermodynamics. Further downstream the jet develops into an atmospheric gas jet where the thermodynamics are described as a mixture of ideal gases (hydrogen–air mixture). Simulations are presented for dilution distances in under-expanded high-pressure leaks from the saturated vapor and saturated liquid portions of a liquid hydrogen storage tank at 10.34 barg (150 PSIG).

The objective of this work was to enable the safe design of hydrogen pressure vessels by measuring the fatigue crack growth rates of ASME code-qualified steels in high-pressure hydrogen gas. While a design framework has recently been established for high-pressure hydrogen vessels a material property database does not exist to support the design calculations. This study addresses such voids in the database by measuring the fatigue crack growth rates of three different heats of ASME SA-372 Grade J steel in 100 MPa hydrogen gas. Results showed that the fatigue crack growth rates were similar for all three steel heats although the highest-strength steel appeared to exhibit the highest growth rates. Hydrogen accelerated the fatigue crack growth rates of the steels by as much as two orders of magnitude relative to anticipated crack growth rates in inert environments. Despite such dramatic effects of hydrogen on the fatigue crack growth rates measurement of these properties enables reliable definition of the design life of steel hydrogen containment vessels.

"This paper summarises the modelling and experimental programme in the EC FP6 project HYPER. A number of key results are presented and the relevance of these findings to installation permitting guidelines (IPG) for small stationary hydrogen and fuel cell systems is discussed. A key aim of the activities was to generate new scientific data and knowledge in the field of hydrogen safety and where possible use this data as a basis to support the recommendations in the IPG. The structure of the paper mirrors that of the work programme within HYPER in that the work is described in terms of a number of relevant scenarios as follows: 1. high pressure releases 2. small foreseeable releases 3. catastrophic releases and 4. the effects of walls and barriers. Within each scenario the key objectives activities and results are discussed.<br/>The work on high pressure releases sought to provide information for informing safety distances for high-pressure components and associated fuel storage activities on both ignited and unignited jets are reported. A study on small foreseeable releases which could potentially be controlled through forced or natural ventilation is described. The aim of the study was to determine the ventilation requirements in enclosures containing fuel cells such that in the event of a foreseeable leak the concentration of hydrogen in air for zone 2 ATEX is not exceeded. The hazard potential of a possibly catastrophic hydrogen leakage inside a fuel cell cabinet was investigated using a generic fuel cell enclosure model. The rupture of the hydrogen feed line inside the enclosure was considered and both dispersion and combustion of the resulting hydrogen air mixture were examined for a range of leak rates and blockage ratios. Key findings of this study are presented. Finally the scenario on walls and barriers is discussed; a mitigation strategy to potentially reduce the exposure to jet flames is to incorporate barriers around hydrogen storage equipment. Conclusions of experimental and modelling work which aim to provide guidance on configuration and placement of these walls to minimise overall hazards is presented. "

Solid state materials such as metal and chemical hydrides have been proposed and developed for high energy density automotive hydrogen storage applications. As these materials are implemented into hydrogen storage systems developers must understand their behavior during accident scenarios or contaminated refueling events. An ability to predict thermal and chemical processes during contamination allows for the design of safe and effective hydrogen storage systems along with the development of appropriate codes and standards. A model for the transport of gases within an arbitrary-geometry reactive metal hydride bed (alane -AlH3) is presented in this paper. We have coupled appropriate Knudsen-regime permeability models for flow through packed beds with the fundamental heat transfer and chemical kinetic processes occurring at the particle level. Using experimental measurement to determine and validate model parameters we have developed a robust numerical model that can be utilized to predict processes in arbitrary scaled-up geometries during scenarios such as breach-in-tank or contaminated refueling. Results are presented that indicate the progression of a reaction front through a compacted alane bed as a result of a leaky fitting. The rate of this progression can be limited by; 1) restricting the flow of reactants into the bed through densification and 2) maximizing the rate of heat removal from the bed.

We have modelled sudden hydrogen expansion from a cryogenic pressure vessel. This model considers real gas equations of state single and two-phase flow and the specific “vessel within vessel” geometry of cryogenic vessels. The model can solve sudden hydrogen expansion for initial pressures up to 1210 bar and for initial temperatures ranging from 27 to 400 K. For practical reasons our study focuses on hydrogen release from 345 bar with temperatures between 62 K and 300 K. The pressure vessel internal volume is 151 L. The results indicate that cryogenic pressure vessels may offer a safety advantage with respect to compressed hydrogen vessels because i) the vacuum jacket protects the pressure vessel from environmental damage ii) hydrogen when released discharges first into an intermediate chamber before reaching the outside environment and iii) working temperature is typically much lower and thus the hydrogen has less energy. Results indicate that key expansion parameters such as pressure rate of energy release and thrust are all considerably lower for a cryogenic vessel within vessel geometry as compared to ambient temperature compressed gas vessels. Future work will focus on taking advantage of these favourable conditions to attempt fail-safe cryogenic vessel designs that do not harm people or property even after catastrophic failure of the inner pressure vessel.

Hydrogen jet flames resulting from ignition of unintended releases can be extensive in length and pose significant radiation and impingement hazards. Depending on the leak diameter and source pressure the resulting consequence distances can be unacceptably large. One possible mitigation strategy to reduce exposure to jet flames is to incorporate barriers around hydrogen storage and delivery equipment. An experimental and modeling program has been performed at Sandia National Laboratories to better characterize the effectiveness of barrier walls to reduce hazards. This paper describes the experimental and modeling program and presents results obtained for various barrier configurations. The experimental measurements include flame deflection using standard and infrared video and high-speed movies (500 fps) to study initial flame propagation from the ignition source. Measurements of the ignition overpressure wall deflection radiative heat flux and wall and gas temperature were also made at strategic locations. The modeling effort includes three-dimensional calculations of jet flame deflection by the barriers computations of the thermal radiation field around barriers predicted overpressure from ignition and the computation of the concentration field from deflected unignited hydrogen releases. The various barrier designs are evaluated in terms of their mitigation effectiveness for the associated hazards present. The results show that barrier walls are effective at deflecting jet flames in a desired direction and can help attenuate the effects of ignition overpressure and flame radiative heat flux.

The properties of hydrogen compared to conventional fuels such as gasoline and diesel are substantially different requiring adaptations to the design and layout of test cells for hydrogen fuelled engines and vehicles. A comparison of hydrogen fuel properties versus conventional fuels in this paper provides identification of requirements that need to be adapted to design a safe test cell. Design examples of actual test cells are provided to showcase the differences in overall layout and ventilation safety features fuel supply and metering and emissions measurements. Details include requirements for ventilation patterns the necessity for engine fume hoods as well as hydrogen specific intake and exhaust design. The unique properties of hydrogen in particular the wide flammability limits and nonvisible flames also require additional safety features such as hydrogen sensors and flame cameras. A properly designed and implemented fuel supply system adds to the safety of the test cell by minimizing the amount of hydrogen that can be released. Apart from this the properties of hydrogen also require different fuel consumption measurement systems pressure levels of the fuel supply system additional ventilation lines strategically placed safety solenoids combined with appropriate operational procedures. The emissions measurement for hydrogen application has to be expanded to include the amount of unburned hydrogen in the exhaust as a measurement of completeness of combustion. This measurement can also be used as a safety feature to avoid creation of ignitable hydrogen-air mixtures in the engine exhaust. The considerations provided in this paper lead to the conclusion that hydrogen IC engines can be safely tested however properly designed test cell and safety features have to be included to mitigate the additional hazards related to the change in fuel characteristics.