United States

Recent advances in optical sensors show promise for the development of new wide area monitoring and distributed optical network hydrogen detection systems. Optical hydrogen sensing technologies reviewed here are: 1) open path Raman scattering systems 2) back scattering from chemically treated solid polymer matrix optical fiber sensor cladding; and 3) schlieren and shearing interferometry imaging. Ultrasonic sensors for hydrogen release detection are also reviewed. The development status of these technologies and their demonstrated results in sensor path length low hydrogen concentration detection ability and response times are described and compared to the corresponding status of hydrogen spot sensor network technologies.

Polymers for O-rings valve seats gaskets and other sealing applications in the hydrogen infrastructure face extreme conditions of high-pressure H2 (0.1 to 100 MPa) during normal operation. To fill current knowledge gaps and to establish standard test methods for polymers in H2 environments these materials can be tested in laboratory scale H2 manifolds mimicking end use pressure and temperature conditions. Beyond the influence of high pressure H2 the selection of gases used for leak detection in the H2 test manifold their pressures and times of exposure gas types relative diffusion and permeation rates are all important influences on the polymers being tested. These effects can be studied ex-situ with post-exposure characterization. In a previous study four polymers (Viton A Buna N High Density Polyethylene (HDPE) and Polytetrafluoroethylene (PTFE)) commonly used in the H2 infrastructure were exposed to high-pressure H2 (100 MPa). The observed effects of H2 were consistent with typical polymer property-structure relationships; in particular H2 affected elastomers more than thermoplastics. However since high pressure He was used for purging and leak detection prior to filling with H2 a study of the influence of the purge gas on these polymers was considered necessary to isolate the effects of H2 from those of the purge gas. Therefore in this study Viton A Buna N and PTFE were exposed to the He purge procedure without the subsequent H2 exposure. Additionally six polymers Viton A Buna N PTFE Polyoxymethylene (POM) Polyamide 11 (Nylon) and Ethylenepropylenediene monomer rubber (EPDM) were subjected to high pressure Ar (100 MPa) followed by high pressure H2 (100 MPa) under the same static isothermal conditions to identify the effect of a purge gas with a significantly larger molecular size than He. Viton A and Buna N elastomers are more prone to irreversible changes as a result of H2 exposure from both Ar and He leak tests as indicated by influences on storage modulus extent of swelling and increased compression set. EPDM even though it is an elastomer is not as prone to high-pressure gas influences. The thermoplastics are generally less influenced by high pressure regardless of the gas type. Conclusions from these experiments will provide insight into the influence of purging processes and purge gases on the subsequent testing in high pressure gaseous H2. Control for the influence of purging on testing results is essential for the development of robust test methods for evaluating the effects of H2 and other high-pressure gases on the properties of polymers.

To examine the effect of initial turbulence on vented explosions experiments were performed for lean hydrogen–air mixtures with hydrogen concentrations ranging from 12 to 15% vol. at elevated initial turbulence. As expected it was found that an increase in initial turbulence increased the overall flame propagation speed and this increased flame propagation speed translated into higher peak overpressures during the external explosion. The peak pressures generated by flame–acoustic interactions however did not vary significantly with initial turbulence. When flame speeds measurements were examined it was found that the burning velocity increased with flame radius as a power function of radius with a relatively constant exponent over the range of weak initial turbulence studied and did not vary systematically with initial turbulence. Instead the elevated initial turbulence increased the initial flame propagation velocities of the various mixtures. The initial turbulence thus appears to act primarily by generating higher initial flame wrinkling while having a minimal effect on the growth rate of the wrinkles. For practical purposes of modelling flame propagation and pressure generation in vented explosions the increase in burning velocity due to turbulence is suggested to be approximated by a single constant factor that increases the effective burning velocity of the mixture. When this approach is applied to a previously developed vent sizing correlation the correlation performs well for almost all of the peaks. It was found however that in certain situations this approach significantly under predicts the flame–acoustic peak. This suggests that further research may be necessary to better understand the influence of initial turbulence on the development of flame–acoustic peaks in vented explosions.

Experimental data from vented explosion tests using lean hydrogen–air mixtures with concentrations from 12 to 19% vol. are presented. A 63.7-m3 chamber was used for the tests with a vent size of either 2.7 or 5.4 m2. The tests were focused on the effect of hydrogen concentration ignition location vent size and obstacles on the pressure development of a propagating flame in a vented enclosure. The dependence of the maximum pressure generated on the experimental parameters was analyzed. It was confirmed that the pressure maxima are caused by pressure transients controlled by the interplay of the maximum flame area the burning velocity and the overpressure generated outside of the chamber by an external explosion. A model proposed earlier to estimate the maximum pressure for each of the main pressure transients was evaluated for the various hydrogen concentrations. The effect of the Lewis number on the vented explosion overpressure is discussed.

An increase in the number of hydrogen-fuelled applications in the marketplace will require a better understanding of the potential for fires and explosion associated with the unintended release of hydrogen within a structure. Predicting the temporally evolving hydrogen concentration in a structure with unknown release rates leak sizes and leak locations is a challenging task. A simple analytical model was developed to predict the natural and forced mixing and dispersion of a buoyant gas released in a partially enclosed compartment with vents at multiple levels. The model is based on determining the instantaneous compartment over-pressure that drives the flow through the vents and assumes that the helium released under the automobile mixes fully with the surrounding air. Model predictions were compared with data from a series of experiments conducted to measure the volume fraction of a buoyant gas (at 8 different locations) released under an automobile placed in the center of a full-scale garage (6.8 m × 5.4 m × 2.4 m). Helium was used as a surrogate gas for safety concerns. The rate of helium released under an automobile was scaled to represent 5 kg of hydrogen released over 4 h. CFD simulations were also performed to confirm the observed physical phenomena. Analytical model predictions for helium volume fraction compared favourably with measured experimental data for natural and forced ventilation. Parametric studies are presented to understand the effect of release rates vent size and location on the predicted volume fraction in the garage. Results demonstrate the applicability of the model to effectively and rapidly reduce the flammable concentration of hydrogen in a compartment through forced ventilation.

The Hydrogen Incident Reporting and Lessons Learned website (www.h2incidents.org) was launched in 2006 as a database-driven resource for sharing lessons learned from hydrogen-related safety events to raise safety awareness and encourage knowledge-sharing. The development of this database its first uses and subsequent enhancements have been described at the Second and Third International Conferences on Hydrogen Safety [1] [2]. Since 2009 continuing work has not only highlighted the value of safety lessons learned but enhanced how the database provides access to another safety knowledge tool Hydrogen Safety Best Practices (http://h2bestpractices.org). Collaborations with the International Energy Agency (IEA) Hydrogen Implementing Agreement (HIA) Task 19 – Hydrogen Safety and others have enabled the database to capture safety event learning’s from around the world. This paper updates recent progress highlights the new “Lessons Learned Corner” as one means for knowledge-sharing and examines the broader potential for collecting analyzing and using safety event information.

Hydrogen sensors are recognized as a critical element in the safety design for any hydrogen system. In this role sensors can perform several important functions including indication of unintended hydrogen releases activation of mitigation strategies to preclude the development of dangerous situations activation of alarm systems and communication to first responders and to initiate system shutdown. The functionality of hydrogen sensors in this capacity is decoupled from the system being monitored thereby providing an independent safety component that is not affected by the system itself. The importance of hydrogen sensors has been recognized by DOE and by the Fuel Cell Technologies Office’s Safety and Codes Standards (SCS) program in particular which has for several years supported hydrogen safety sensor research and development. The SCS hydrogen sensor programs are currently led by the National Renewable Energy Laboratory Los Alamos National Laboratory and Lawrence Livermore National Laboratory. The current SCS sensor program encompasses the full range of issues related to safety sensors including development of advance sensor platforms with exemplary performance development of sensor-related code and standards outreach to stakeholders on the role sensors play in facilitating deployment technology evaluation and support on the proper selection and use of sensors.

RCS for hydrogen technologies were first developed approximately sixty years ago when hydrogen was being sold as an industrial commodity. The advent of new hydrogen technologies such as Fuel Cell Electric Vehicles (FCEVs) created a need for new RCS. These RCS have been developed with extensive support from the US DOE. These new hydrogen technologies are approaching commercial deployment and this process will produce information on RCS field performance that will create more robust RCS.

Unintentional leaks at hydrogen fuelling stations have the potential to form hydrogen jet flames which pose a risk to people and infrastructure. The heat flux from these jet flames are often used to develop separation distances between hydrogen components and buildings lot-lines etc. The heat flux and visible flame length is well understood for releases from round nozzles but real unintended releases would be expected to be be higher aspect-ratio cracks. In this work we measured the visible flame length and heat-flux characteristics of cryogenic hydrogen flames from high-aspect ratio nozzles. We compare this data to flames of both cryogenic and compressed hydrogen from round nozzles. The aspect ratio of the release does not affect the flame length or heat flux significantly for a given mass flow under the range of conditions studied. The engineering correlations presented in this work that enable the prediction of flame length and heat flux can be used to assess risk at hydrogen fuelling stations with liquid hydrogen and develop science-based separation distances for these stations.

The capabilities in the Hydrogen Effects on Materials Laboratory (HEML) at Sandia National Laboratories and the related materials testing activities that support standards development and technology deployment are reviewed. The specialized systems in the HEML allow testing of structural materials under in-service conditions such as hydrogen gas pressures up to 138 MPa temperatures from ambient to 203 K and cyclic mechanical loading. Examples of materials testing under hydrogen gas exposure featured in the HEML include stainless steels for fuel cell vehicle balance of plant components and Cr-Mo steels for stationary seamless pressure vessels.