The Sandia HyMARC team continued its development of new synthetic, modeling, and diagnostic tools that are providing new insights into all major classes of storage materials, ranging from relatively simple systems such as PdHx and MgH2, to exceptionally complex ones, such as the metal borohydrides, as well as materials thought to be very well-understood, such as Ti-doped NaAlH4. This unprecedented suite of capabilities, capable of probing all relevant length scales within storage materials, is already having a significant impact, as they are now being used by both Seedling projects and collaborators at other laboratories within HyMARC. We expect this impact to grow as new Seedling projects begin and through collaborations with other scientists outside HyMARC. In the coming year, Sandia efforts will focus on the highest impact problems, in coordination with the other HyMARC National Laboratory partners, to provide the foundational science necessary to accelerate the discovery of new hydrogen storage materials.
A theoretical comparison is made of the “well to waves” (WTW) greenhouse gas (GHG) and criteria pollutant emissions from the SF-BREEZE high-speed hydrogen PEM fuel cell ferry and the VALLEJO ferry powered by traditional diesel engine technology but constrained to Tier 4 emissions standards. The emissions were calculated for a common maritime mission, the current ferry route between Vallejo CA and San Francisco CA. Calculations are made of the energy required for the SF-BREEZE and VALLEJO to perform the mission route profile. The SF-BREEZE requires 10.1% more fuel energy than the VALLEJO, primarily due to the SF-BREEZE being heavier. Estimates are made for the SF-BREEZE GHG emissions associated with five LH2 fuel production pathways including renewable and non-renewable (fossil-fuel based) methods. Estimates are also made for GHG emissions associated with fossil-diesel production and delivery as well as those for biodiesel, which can be considered a renewable “drop-in” fuel replacement for conventional diesel fuel. We find that the GHG emissions for the SF-BREEZE using non-renewable LH2 are significantly higher than for the Tier 4 diesel-fueled VALLEJO on a per passenger basis. However, using renewable LH2, the GHG emissions for the SF-BREEZE ferry are reduced 75.8% compared to the diesel-fueled VALLEJO operating at Tier 4 emissions standards. We also compare the criteria pollutant emissions (NOx, HC, PM10) for the SF-BREEZE to that of the VALLEJO held to Tier 4 emissions standards fueled by diesel fuel or biodiesel. Hydrogen PEM fuel cell technology dramatically reduces NOx and HC emissions below the most advanced Tier 4 criteria pollutant emissions requirements regardless of whether the LH2 is made by NG reforming or via water electrolysis using 70% renewable energy. Renewable LH2 made with greater than 84% renewable process energy is needed to also drop the SF-BREEZE PM10 emissions below that of Tier 4 for high-speed fuel cell ferry transportation. Overall, the results show that operating a hydrogen fuel cell ferry on nearly 100% renewable hydrogen provides the dramatic reduction in GHG and criteria pollutant emissions commensurate with the problems of global climate change and maritime air pollution worldwide.
We review liquid hydrogen (LH2) as a maritime vessel fuel, from descriptions of its fundamental properties to its practical application and safety aspects, in the context of the San Francisco Bay Renewable Energy Electric Vessel with Zero Emissions (SF-BREEZE) high-speed fuel-cell ferry. Since marine regulations have been formulated to cover liquid natural gas (LNG) as a primary propulsion fuel, we frame our examination of LH2as a comparison to LNG, for both maritime use in general, and the SF-BREEZE in particular. Due to weaker attractions between molecules, LH2is colder than LNG, and evaporates more easily. We describe the consequences of these physical differences for the size and duration of spills of the two cryogenic fuels. The classical flammability ranges are reviewed, with a focus on how fuel buoyancy modifies these combustion limits. We examine the conditions for direct fuel explosion (detonation) and contrast them with initiation of normal (laminar) combustion. Direct fuel detonation is not a credible accident scenario for the SF-BREEZE. For both fuels, we review experiments and theory elucidating the deflagration to detonation transition (DDT). LH2fires have a shorter duration than energy-equivalent LNG fires, and produce significantly less thermal radiation. The thermal (infrared) radiation from hydrogen fires is also strongly absorbed by humidity in the air. Hydrogen permeability is not a leak issue for practical hydrogen plumbing. We describe the chemistry of hydrogen and methane at iron surfaces, clarifying their impact on steel-based hydrogen storage and transport materials. These physical, chemical and combustion properties are pulled together in a comparison of how a LH2or LNG pool fire on the Top Deck of the SF-BREEZE might influence the structural integrity of the aluminum deck. Neither pool fire scenario leads to net heating of the aluminum decking. Overall, LH2and LNG are very similar in their physical and combustion properties, thereby posing similar safety risks. For ships utilizing LH2or LNG, precautions are needed to avoid fuel leaks, minimize ignition sources, minimize confined spaces, provide ample ventilation for required confined spaces, and to monitor the enclosed spaces to ensure any fuel accumulation is detected far below the fuel/air mix threshold for any type of combustion.
The structure-dependent vibrational properties of different Mg(BH4)2 polymorphs (α, β, γ, and δ phases) were investigated with a combination of neutron vibrational spectroscopy (NVS) measurements and density functional theory (DFT) calculations, with emphasis placed on the effects of the local structure and orientation of the BH4- anions. DFT simulations closely match the neutron vibrational spectra. The main bands in the low-energy region (20-80 meV) are associated with the BH4- librational modes. The features in the intermediate energy region (80-120 meV) are attributed to overtones and combination bands arising from the lower-energy modes. The features in the high-energy region (120-200 meV) correspond to the BH4- symmetric and asymmetric bending vibrations, of which four peaks located at 140, 142, 160, and 172 meV are especially intense. There are noticeable intensity distribution variations in the vibrational bands for different polymorphs. This is explained by the differences in the spatial distribution of BH4- anions within various structures. An example of the possible identification of products after the hydrogenation of MgB2, using NVS measurements, is presented. These results provide fundamental insights of benefit to researchers currently studying these promising hydrogen-storage materials.
An analysis is presented of a method to protect the reticle (mask) in an extreme ultraviolet (EUV) mask inspection tool using a showerhead plenum to provide a continuous flow of clean gas over the surface of a reticle. The reticle is suspended in an inverted fashion (face down) within a stage/holder that moves back and forth over the showerhead plenum as the reticle is inspected. It is essential that no particles of 10-nm diameter or larger be deposited on the reticle during inspection. Particles can originate from multiple sources in the system, and mask protection from each source is explicitly analyzed. The showerhead plate has an internal plenum with a solid conical wall isolating the aperture. The upper and lower surfaces of the plate are thin flat sheets of porous-metal material. These porous sheets form the top and bottom showerheads that supply the region between the showerhead plate and the reticle and the region between the conical aperture and the Optics Zone box with continuous flows of clean gas. The model studies show that the top showerhead provides robust reticle protection from particles of 10-nm diameter or larger originating from the Reticle Zone and from plenum surfaces contaminated by exposure to the Reticle Zone. Protection is achieved with negligible effect on EUV transmission. The bottom showerhead efficiently protects the reticle from nanoscale particles originating from the Optics Zone. With similar mass flow rates from the two showerheads, this system provides efficient protection even when a significant overpressure exists between the Optics Zone and the Reticle Zone. Performance is insensitive to the fraction of incident particles that sticks to walls, the accommodation coefficient, the aperture geometry, and the gas pressure. The showerheads also protect the aperture (and therefore the Optics Zone) during mask loading and unloading. Commercially available porous-metal media have properties suitable for these showerheads at the required flow rates. The benefits of the approach compared to a conceptual EUV pellicle are described.