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DOE OSTI2023

Technology Strategy Assessment: Findings from Storage Innovations 2030 Bidirectional Hydrogen Storage

Hydrogen is the most common element in the universe, comprising nearly 75% of all normal matter, and it has been used by scientists for centuries, but it was not fully recognized as an element until 1766, when it was isolated by Henry Cavendish. Early work focused on the generation of hydrogen through the oxidation of metals in water, which released hydrogen gas. Hydrogen’s lighter-than-air and flammable properties were immediately used in engines, zeppelins, and as feedstock for a wide variety of chemical reactions. Several approaches were developed for the production of hydrogen with the most common being associated with the production and conversion of hydrocarbon-based fuels. Coal gasification, steam methane reforming, and other reformation processes provide the majority of current hydrogen production due to the relatively low cost of hydrogen produced through these processes. More than 95% of hydrogen production is used for industrial processes rather than energy storage. To facilitate affordable decarbonization of these industrial processes and to advance the use of hydrogen as a fuel in transportation, DOE launched the Hydrogen Shot as part of the Energy Earthshots Initiative. The goal of the Hydrogen Shot is to reduce the cost of clean hydrogen by 80% to $1/kg of clean hydrogen production within one decade (known as the “1 1 1” goal). This is distinct from the Long-Duration Storage Shot, which is the primary focus of this report; however, it is intrinsically linked to bidirectional hydrogen storage. Several important chemical synthesis processes are dependent upon hydrogen, and the production and use of hydrogen is generally driven by its connection to one of these markets. For example, ammonia is one of the most highly produced chemicals in the world and it depends chiefly on hydrogen. Ammonia is primarily used for agricultural fertilizer and is considered to be largely responsible for a doubling of agricultural production per unit of land over the last century. Another one of hydrogen’s primary uses is as a catalyst in petroleum refining during the desulfurization process. Beyond chemical production, hydrogen is used as a reductant in the production of steel and has been demonstrated as a substitute for metallurgical coal in the production of raw iron. It is even used in the hydrogenation reaction for food products to create more shelf-stable semi-solid fats. However, while hydrogen is produced on the order of 100 million metric tons/year globally to feed these industries, more than 95% of hydrogen is produced from hydrocarbons that emit CO2 during the process. Conversely, electrolysis is a process by which electricity is used to separate hydrogen and oxygen in water molecules, usually across a membrane. Hydrogen production via electrolysis lowers the carbon intensity of produced hydrogen when coupled with low-carbon electricity. Currently, global electrolysis capacity is on the order of 1 GW, which equates to about 500 metric tons/day of hydrogen production. To support large-scale industrial decarbonization, capacity will likely need to increase by two to three orders of magnitude. Electrolysis technology is broadly separated into groups that are defined by the electrolyte used, with further subdivision based on the operating characteristics. The majority of commercial electrolyzer systems are based around three main technology groups: liquid alkaline, proton exchange membrane, and solid oxide. Liquid Alkaline (LA) electrolysis is the oldest, most mature, least expensive, and most common commercial technology, with 400 plants in operation by 1902. Its hydrogen output is low relative to the size of the system due to a low current density. LA electrolysis utilizes a liquid potassium hydroxide solution as the electrolyte. Proton exchange membrane (PEM) electrolysis (also known as polymer electrolyte membrane electrolysis), described in 1960, relies on an acid-impregnated polymer membrane as the electrolyte and typically offers three to six times higher hydrogen production per unit cell area than LA electrolysis. Solid oxide electrolysis, or high-temperature electrolysis, utilizes a ceramic cell as the electrolyte and operates on steam rather than liquid water, enabling electrical efficiencies of more than 90%, which is up from 60% with PEM. Two pre-commercial electrolyzer technologies to note are alkaline exchange membrane (AEM) and proton-conducting solid oxide electrolysis cell (SOEC). AEM potentially has the advantages of both LA and PEM technologies in that it is able to use low-cost materials like LA but with the ability to operate at higher output pressures with a smaller footprint like PEM. Proton-conducting SOEC is similar to commercial SOEC, which uses an oxide-conducting ceramic; however, it uses a proton-conducting ceramic that has the potential to operate at lower temperatures and has lower capital costs. Each of these technologies is experiencing a rapid improvement in performance and a reduction in installed cost, and each appears to be well suited to specific applications. Besides differences in the type of electrolyzer used, the main difference in the architecture of bidirectional hydrogen systems is how the hydrogen is stored. Currently, the most cost-effective way to store large amounts of hydrogen gas is underground, such as in large salt caverns that have been hollowed out. These salt caverns are geographically concentrated in small portions of the United States and are not generally near large metropolitan areas; however, other subsurface architectures are being investigated to expand this reach. A more widely deployable option is aboveground pressurized tanks. These systems are about 10 times as expensive because of the materials and safety margins required to hold hydrogen at high pressures. A third option is using materials-based storage, such as liquid organic hydrogen carriers. By reversibly attaching the produced hydrogen to other molecules, it can be stored at near atmospheric pressure and room temperature. This has the potential to reduce the material cost of storage but may result in a reduction in the efficiency of the process because there are both hydrogen uptake and release processes. While materials-based storage has not been used extensively for large-scale hydrogen storage in the past, there is currently significant activity regarding developing materials and processes for use in large-scale hydrogen storage applications. Electrolysis-produced hydrogen offers an unusual opportunity for energy storage applications. Unlike more conventional energy storage approaches, such as batteries, which operate entirely within electrical markets, hydrogen is a valuable product beyond the electric market and can be directed to the most lucrative use. Hydrogen also can be directly converted back to electricity using either a fuel cell or turbine, or it can be sold to other markets, such as chemical synthesis, steel production, or even export. In this way, excess electricity can be upgraded to the most valuable product. Finally, its use can be actively managed between multiple off-takers; for example, local hydrogen storage can provide a specific amount of stored electricity and any excess can be exported to ammonia production. This flexibility is amplified by the fact that hydrogen storage has fully decoupled power and energy components, which allows for affordable scaling options. Together, this allows a substantial amount of creativity to enable the economic utilization of variable power resources while supporting decarbonization of the industry.

08 HYDROGEN↗
DOE OSTI2024

A Managed Tokens Service for Securely Keeping and Distributing Grid Tokens

Fermilab is transitioning authentication and authorization for grid operations to using bearer tokens based on the WLCG Common JWT (JSON Web Token) Profile. One of the functionalities that Fermilab experimenters rely on is the ability to automate batch job submission, which in turn depends on the ability to securely refresh and distribute the necessary credentials to experiment job submit points. Thus, with the transition to using tokens for grid operations, we needed to create a service that would obtain, refresh, and distribute tokens for experimenters’ use. This service would avoid the need for experimenters to be experts in obtaining their own tokens and would better protect the most sensitive long-lived credentials. Further, the service needed to be widely scalable, as we are currently keeping credentials active for approximately 15 experiments, each with 1-3 different credentials, and distributing those credentials to 2-20 submit points per experiment, with those numbers steadily increasing. To address these issues, we created and deployed a Managed Tokens service. The service is written in Go, taking advantage of that language’s native concurrency primitives to easily be able to scale operations as we onboard experiments. The service uses as its first credentials a set of kerberos keytabs, stored on the same secure machine that the Managed Tokens service runs on. These kerberos credentials allow the service to use htgettoken via condor_vault_storer to store vault tokens in the HTCondor credential managers (credds) that run on the batch system scheduler machines (HTCondor schedds); as well as downloading a local, shorter-lived copy of the vault token. The kerberos credentials are then also used to distribute copies of the locally-stored vault tokens to experiment submit points. When experimenters schedule jobs to be submitted, these distributed vault tokens are used to access a Hashicorp Vault instance (run separately from the Managed Tokens service), and previously-stored refresh tokens there are used to obtain the bearer token that is submitted with the job. We will discuss here the design of the Managed Tokens service, including elaborating on certain choices we made with regards to concurrent operations, configuration, monitoring, and deployment.

Bhat, Shreyas↗
DOE OSTI2024

Identify and Assess Technical Challenges in Safeguards Measurements of Spent Advanced Reactor Fuels

Advanced reactor (AR) designs use various nuclear fuel types that can be significantly different than conventional light-water reactor (LWR) fuels, including differences in sizes, compositions, and chemical forms (e.g., oxide, carbide, metal). Nearly all the proposed AR fuels use high-assay low-enriched uranium (HALEU), which will have higher enrichments (5–20 wt% 235 U) than LWR fuels (currently limited to <5 wt% 235 U). In advance of the wide use of these new fuel types around the world, international safeguards organizations such as the International Atomic Energy Agency (IAEA]) are working with some of the AR vendors to formulate safeguards approaches for these AR fuel cycles. As part of the overall safeguards approach, it is important to identify the potential technical challenges in performing safeguards verification measurements of these AR fuels (both fresh and spent fuels) in advance of the widespread adoption of these new fuel types, because new safeguards technologies can take several years to develop, test, and approve for use. This report documents work performed in fiscal year 2024 based on modeling and simulation to assess the performance of the existing safeguards measurement technologies for irradiated or spent AR fuel elements or items. This work is a continuation of the work performed in fiscal year 2023 that focused on fresh AR fuels. Spent AR fuels have a distinct difference from their LWR counterparts: unlike the spent LWR fuels typically stored in a water-filled pool, some spent AR fuels—such as tristructural-isotropic (TRISO)-based fuels—will most likely be stored in air-filled hot cells. Because most safeguards measurements on spent fuel performed to date have been conducted under water, the air-filled hot cell environment could present unique challenges to safeguards measurements. Fork detector (FDET) and Cerenkov viewing device (CVD) systems have been the two primary instruments used by the IAEA for several decades to measure spent LWR fuel assemblies stored in pools for safeguards verification purposes. Because the lower refractive index of air causes Cerenkov light to be of lower intensity in air than in water, existing CVDs are likely unable to perform safeguards verification measurements for spent fuel stored in an air-filled hot cell, as is the case for the TRISO-based spent fuel elements (e.g., pebbles, graphite fuel blocks). Unlike FDET measurements, CVD measurements do not require fuel be moved, so they are a simpler and faster to take than FDET measurements. The inability to perform CVD measurements on the TRISO-based AR fuel types presents a major technical challenge in the effort to use existing technology to perform safeguards measurements on spent AR fuels. This study was mainly conducted through the modeling and simulation of an FDET or an FDET-like system on five spent AR fuel types, including one metallic fuel type and four TRISO-based fuel types in both pebble and graphite block forms in their respective storage configurations and environments. Because the various AR fuel types have significantly different dimensions, FDET systems must be adapted to accommodate them. Partial defect tests were also simulated in this study to assess the FDET’s ability to detect potential fuel diversions. The FDET measures the fuel’s total passive neutron and gamma emissions. The simulated FDET results from spent AR fuel items are compared against results from a typical spent pressurized water reactor (PWR) assembly. High-purity germanium (HPGe) gamma detector measurements were also simulated for the spent AR fuel types and the PWR assembly because the signature photopeaks have been used in LWR safeguards verifications, although HPGe is usually not used to detect diversions because of the fuel’s self-attenuation effects on those photopeaks. The results indicate that these detectors have significant challenges in performing safeguards measurements of the spent AR fuel items, including incompatibilities between AR fuel items and existing FDETs, lower neutron count rates, lower sensitivities to fuel diversions in certain AR fuel items, and significantly higher interference from a neighboring fuel item when the measurement is performed in air. These results suggest that an alternative technology or significant and timely technology development is needed to perform adequate safeguards measurements of some of these AR fuel items.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Data Summarization and Inference at Scale

This is the final report for the DOE ASCR grant SC-0022260, Data Summarization and Inference at Scale, PI: Alex Pothen, Purdue University. The goal of the project was to solve data-intensive and compute-intensive problems in the physical sciences, engineering, information science, data science, etc. by designing and implementing new algorithms that could work with a subset of the data. The four subgoals were: (a) The solution of problems where the data is too large to be stored in the memory of a computer. In this streaming model of computation, the data arrives as a stream of elements to the computer, each element is processed as it arrives, and a decision is made to discard the data or to store it; only a small subset of the data proportional to the size of the output solution is stored, and when all the data has been streamed, a solution to the problem is computed from the stored subset. (b) The use of machine learning methods to compute solutions to data-intensive problems. The use of GPUs is critical to obtain high performance on machine learning tasks, but their memory sizes are smaller relative to that of CPUs. For large-scale problems, the data is sampled many times, and small samples are used with repetition, for robustness, to compute solutions to inference tasks. This sampling reduces the memory required to solve the problem, but attention is needed to avoid slow convergence to the solutions, and reduced accuracy of inference. We propose submodular optimization, Large Language Models, and physics-informed neural networks to enable GPU computations here. (c) Modeling and visualization of high-dimensional data using interpretable features. Clinical proteomic data sets from immunology for the detection of cancer and other diseases are temporal and high-dimensional, and algorithms for visualizing these data sets using clinically interpretable features are lacking. We propose methods that compute distances based on the optimal transportation problem and graph edit distances to address this problem. We also propose the use of optimal transport-based distances, spatial statistics, and network structure to classify image data sets, We apply these algorithms to electron micrographs of the peripheral nervous system in the digestive tract. (d) The design of data-intensive algorithms on emerging architectures, specifically, noisy, intermediate-scale quantum (NISQ) devices. Quantum computers offer the possibility of exploring large solution spaces due to the principle of superposition, but current quantum computers are limited by few qubits, short coherence times due to noise, poor interconections among the qubits, etc. We propose the use of the divide and conquer paradigm to solve large-scale problems, wherein collections of small subproblems are solved on the quantum devices, and the solutions to the subproblems are integrated into a solution for the original problem on a classical computer.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2026

Pilot Development Progress to Demonstrate Electric Thermal Energy Storage (ETES) Using Low-Cost Particles

The rapid growth of future energy demand increases the need to economically store electrical energy over durations up to several days in long-duration energy storage (LDES) applications. LDES can reduce the grid stress for improving the resilience of the grid. The integration of renewable power and storage has several significant and positive impacts including expanding the renewable energy portion of electricity generation, meeting peak-load demand, and coordinating supply and demand. Several energy storage approaches including mechanical, chemical and electrochemical methods are currently deployed or under development. However, LDES requirements pose unique challenges for scalability, energy capacity, and cost. Thermal energy storage (TES) has the ability to store a large capacity of energy with improved site flexibility compared to incumbent LDES technologies (i.e., pumped hydro) and has attracted significant interest. Our development in TES technology using solid particles as the storage medium has shown feasibility and potential in serving LDES purposes. Particle TES has various advantages over commercialized molten nitrate salt TES and has emerged as a promising storage technology originating from Generation 3 concentrating solar power (CSP) development. Stable, inexpensive silica sand produced in the Midwestern U.S. was identified as a suitable storage medium and has been validated through lab heating and cycling tests. We have successfully developed particle TES for bidirectional electric energy storage to broaden the applications for TES beyond CSP technologies and into standalone electric-thermal energy storage (ETES) systems. Key component designs and performance were verified with prototype testing and model simulations. The ETES system uses high-temperature, low-cost particle thermal energy storage coupled with a unique pressurized fluidized bed heat exchanger that supports a high-efficiency, air-Brayton combined power cycle. At times of low energy demand or high renewable production, an electric particle heater heats large quantities of solid particles to high temperatures in excess of 1100 degrees C. The particles are stored in internally insulated silos. At times of high electricity demand, the hot particles are gravity-fed through the heat exchanger where stored thermal energy is transferred to the power cycle working fluid to drive the gas turbine power generation system, thereby converting the thermal energy back into electricity for the grid. The cold particles leaving the heat exchanger are returned to the storage silos by a well-insulated particle conveyor. This ETES technology using particle TES can be sited anywhere and is predicted to be economic and efficient. Moreover, this ETES technology could be co-located with a retired coal or gas plant to leverage existing power generation and grid infrastructure. Our work has focused on the development of each of the key components (e.g., the electric particle heater, particle storage silos, and the particle-to-gas pressurized fluidized bed heat exchanger) through conceptual designs, prototype testing, and computational modeling. These developments demonstrate technological feasibility and are an important step towards the next phase of development of this promising LDES technology. This presentation will show the progress in developing a pilot demonstration of the ETES system on a commercially relevant scale.

25 ENERGY STORAGE↗
DOE OSTI2024

Development and Implementation of a Bag Degradation Predictive Tool at Los Alamos National Laboratory

Nuclear material packaging involves many complex variables derived from the stored material's properties, the storage environment, and the synergistic interaction of said material and its environment on the containment boundary. In the Plutonium Facility (PF-4) at Los Alamos National Laboratory (LANL) the typical containment boundary found, starting from the stored material itself to the outermost containment layer, consists of the material contained within a stainless steel (typically 304) slip-lid (or other equivalent stainless steel packaging layer) wrapped in an sPVC bag-out bag contained within a facility approved outer container stored within the boundaries of an approved facility (i.e., a building designed and approved to store nuclear material). This packaging configuration, though occasionally deviated from in the past, represents the current procedurally enforced, expected containment structure for all interim nuclear material containment outside of an engineered control barrier (e.g., a glovebox). Over the life of containerization research at LANL, packaging engineers have become increasingly concerned with the degradation of the sPVC bag-out bag, which can cause corrosion to the outermost packaging layer as well as possible exposure to alpha contamination if the bag-out bag layer is degraded to the point of containment failure. A bag-out bag degradation predictive tool (BDT) is therefore needed to assess the current and future nuclear material inventory for possible bag degradation in order to continue to ensure safe operations for the facility and its workers to deliver on the vital national security mission of 30 PPY.

42 ENGINEERING↗
DOE OSTI2010

CONSOLIDATION OF K BASIN SLUDGE DATA AND EXPERIENCES ON AGGLOMERATE FORMATION

The formation of high sludge strength agglomerates is a key concern to the Sludge Treatment Project (STP) to ensure the sludge can be retrieved after planned storage for up to 10 years in Sludge Transport and Storage Containers (STSC) at T Plant. This report addresses observations of agglomerate formation, conditions that the data shows lead to agglomeration, the frequency of agglomerate formation and postulated physiochemical mechanisms that may lead to agglomeration. Although the exact underlying chemistry of K Basin sludge agglomerate formation is not known, the factors that lead to agglomeration formation, based on observations, are as follows: (1) High Total Uranium Content (i.e., sample homogeneity and influence from other constituents); (2) Distribution of Uranium Phases (i.e., extent of conversion from uraninite to uranium oxide hydroxide compounds); (3) Sample Dry-out (loss of cover water); (4) Elevated temperature; (5) Solubility ofU(IV) phases vs. U(VI) phases; and (6) Long storage times. Agglomerated sludge has occurred infrequently and has only been observed in four laboratory samples, five samples subjected to hydrothermal testing (performed for 7 to 10 hours at {approx}185 C and 225 psig), and indirectly during six sampling events in the KE Basin. In the four laboratory samples where agglomerates were observed, the agglomerates exhibited high shear strength and the sample container typically had to be broken to remove the solids. The total uranium content (dry basis) for the four samples (KE Pit, KC-2/3 SS, KC-2/3 M250 and 96-13) were {approx}8 wt%, {approx}59.0 wt%, 68.3 wt% and 82 wt%. The agglomerates that were present during the six sampling events were undoubtedly disturbed and easily broken apart during sample collection, thus no agglomerates were observed in subsequent laboratory analyses. The highest shear strengths measured for K Basin sludge samples were obtained after hydrothermal treatment (7 to 10 hr at 185 C) of high-uranium-content KE canister sludge. The unconfined compressive strength of samples from this testing, measured by a pocket penetrometer, infers that their shear strength may be between 120 kPa and 170 kPa (PNNL-16496). These short-duration hydrothermal tests were conducted at temperatures much greater than the temperature of the T Plant canyon cells (-7 C to 33 C); however, the strength results provide an initial bounding target for sludge stored for many years, and an upper range for simulants (042910-53451-TP02 Rev 1). Sampling and characterization activities conducted in 2009 have measured the total uranium content and speciation for sludge stored in Engineered Containers SCS-CON-220, -240, -250, and -260 (PNNL-19035). Based on on-going testing that has measured the shear strength of uranium samples containing varying uranium (IV) to uranium (VI) ratios and the characterization of the Engineered Containers SCS-CON-220, -240, -250, and -260, it is unlikely that agglomerates will form on a large scale in this sludge. The highest measured total uranium concentration in the Engineered Container SCS-CON-220 sludge is 35.2 wt% and only 4 wt% to 6 wt% (dry) in Engineered Containers SCS-CON -240, -250, and -260. The uranium concentrations in Engineered Containers SCS-CON-220, -240, -250, and -260 sludge are below the threshold for agglomerate formation. Settler sludge however is estimated to contain {approx} 80 wt% (dry) total uranium, which could lead to the formation of high strength agglomerates depending on the relative concentrations of U(IV) and U(VI) compounds. One of the chief concerns of the STP is sludge dry-out. Samples archived in PNNL hot cells have been known to dry out and form hard clods of material, which are then difficult to reconstitute (HNF-6705). In 1996, all but one of the samples archived at the 222-S Laboratory dried out. These samples were composed of sludge collected from the KE Basin floor and Weasel Pit. However, in the STP's current design plans for sludge stored in STSCs at T Plant, there are provisions for continual water level observation and periodic water replenishment when needed, which dramatically lowers the risk of a dryout event. Recent 2009 KE Engineered Container sludge and KW Engineered Container sludge physical characterization lead to opportunistic data on the behavior of dried sludge. As shown in section 5 of this report, sludge core samples taken from Engineered Container 220 that have inadvertently dried after characterization activities indicate that the sludge is mostly composed of very 'weak' and friable solids. Since Engineered Container SCS-CON-220 sludge has the highest total uranium (uranium metal and uranium oxide) concentration of the four Engineered Containers sampled to date, if a dry-out event should occur in the STSC while stored at T Plant there is qualitative evidence to suggest that the solids would be 'weak' and friable in nature and thus easily mobilized.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2010

Response to: “Long-term effectiveness and consequences of carbon dioxide sequestration” by Gary Shaffer, published in Nature Geosciences, 27 June 2010.

Shaffer’s (2010) article reports on the long term impact of less than perfect retention of anthropogenic CO2 stored in deep geologic reservoirs and in the ocean. The central thesis of this article is predicated on two deeply flawed assumptions. The first and most glaring is the implicit assumption that society has only one means of reducing greenhouse gas emissions, carbon dioxide capture and storage (CCS). Secondly, there is absolutely no geophysical nor geomechanical basis for assuming an exponential decay of CO2 stored in deep geologic formations as done by Schaffer. Shaffer’s analysis of the impact of leakage from anthropogenic CO2 stored in deep geologic reservoirs are based upon two fundamentally flawed assumptions and therefore the reported results as well as the public policy conclusions presented in the paper need to be read with this understanding in mind as far less CO2 stored below ground because society drew upon a broad portfolio of advanced energy technologies over the coming century coupled with a more technically accurate conceptualization of CO2 storage in the deep subsurface and the important role of secondary and tertiary trapping mechanisms would have yield a far less pessimistic view of the potential role that CCS can play in a broader portfolio of societal responses to the very serious threat posed by climate change.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2010

Final Report: Main Group Element Chemistry in Service of Hydrogen Storage and Activation

Replacing combustion of carbon-based fuels with alternative energy sources that have minimal environmental impact is one of the grand scientific and technological challenges of the early 21st century. Not only is it critical to capture energy from new, renewable sources, it is also necessary to store the captured energy efficiently and effectively for use at the point of service when and where it is needed, which may not be collocated with the collection site. There are many potential storage media but we focus on the storage of energy in chemical bonds. It is more efficient to store energy on a per weight basis in chemical bonds. This is because it is hard to pack electrons into small volumes with low weight without the use of chemical bonds. The focus of the project was the development of new chemistries to enable DOE to meet its technical objectives for hydrogen storage using chemical hydrogen storage systems. We provided computational chemistry support in terms of thermodynamics, kinetics, and properties prediction in support of the experimental efforts of the DOE Center of Excellence for Chemical Hydrogen Storage. The goal of the Center is to store energy in chemical bonds involving hydrogen atoms. Once the hydrogen is stored in a set of X-H/Y-H bonds, the hydrogen has to be easily released and the depleted fuel regenerated very efficiently. This differs substantially from our current use of fossil fuel energy sources where the reactant is converted to energy plus CO2 (coal) or CO2 and H2O (gasoline, natural gas), which are released into the atmosphere. In future energy storage scenarios, the spent fuel will be captured and the energy storage medium regenerated. This places substantial additional constraints on the chemistry. The goal of the computational chemistry work was to reduce the time to design new materials and develop materials that meet the 2010 and 2015 DOE objectives in terms of weight percent, volume, release time, and regeneration ability. This goal was met in terms of reducing the number of costly experiments and helping to focus the experimental effort on the potentially optimal targets. We have used computational chemistry approaches to predict the thermodynamic properties of a wide range of compounds containing boron, nitrogen, hydrogen, and other elements as appropriate including carbon. These calculations were done in most cases with high level molecular orbital theory methods that have small error bars on the order of ± 1 to 2 kcal/mol. The results were used to benchmark more approximate methods such as density functional theory for larger systems and for database development. We predicted reliable thermodynamics for thousands of compounds for release and regeneration schemes to aid/guide materials design and process design and simulation. These are the first reliable computed values for these compounds and for many represent the only available values. Overall, the computational results have provided us with new insights into the chemistry of main group and organic-base chemical hydrogen systems from the release of hydrogen to the regeneration of spent fuel. A number of experimental accomplishments were also made in this project. The experimental work on hydrogen storage materials centered on activated polarized σ- or π-bonded frameworks that hold the potential for ready dihydrogen activation, uptake, and eventually release. To this end, a large number of non-traditional valence systems including carbenes, cyanocarbons, and C-B and and B-N systems were synthesized and examined. During the course of these studies an important lead arose from the novel valency of a class of stable organic singlet bi-radical systems. A synthetic strategy to an “endless” hydrogen storage polymer has been developed based on our cyanocarbon chemistry. A key issue with the synthetic efforts was being able to link the kinetics of release with the size of the substituents as it was difficult to develop a low molecular weight molecule with the right kinetics. A novel hydrogen activation process has been developed which showed that Lewis acid-base pairs need not be “frustrated” in their reactivity towards activating H2. Reaction can occur at temperatures as low as -80 ºC. We established that the interaction of H2 with the electrophile is a key step in the activation process.

08 HYDROGEN↗
DOE OSTI2019

Overhead Protection Increases Fuel Quality and Natural Drying of Leaf-On Woody Biomass Storage Piles

Short-rotation woody crops (SRWC) have the potential to make substantial contributions to the supply of biomass feedstock for the production of biofuels and bioproducts. This study evaluated changes in the fuel quality (moisture, ash, and heating value) of stored spring harvested shrub willow (Salix spp.) and hybrid poplar (Populus spp.) chips with respect to pile protection treatments, location within the storage piles, and length of storage. Leaf-on willow and poplar were harvested in the spring, and wood chips and foliage with moisture content in the range of 42.1% to 49.9% (w.b.) were stored in piles for five months, from May to October 2016. Three protection treatments were randomly assigned to the piles. The control treatment had no cover (NC), so piles were exposed to direct solar radiation and rainfall. The second treatment had a canopy (C) installed above the piles to limit direct rainfall. The final treatment had a canopy plus a dome aeration system (CD) installed over the piles. Covering piles reduced and maintained the low moisture content in wood chip piles. Within 30 days of establishment, the moisture content in the core of the C pile decreased to less than 30%, and was maintained between 24%–26% until the end of the storage period. Conversely, the moisture content in the NC piles decreased in the first two months, but then increased to the original moisture content in the core (>45 cm deep) and up to 70% of the original moisture content in the shell (<45 cm deep). For all the treatments in the tested conditions, the core material dried faster than the shell material. The higher heating value (HHV) across all the treatments increased slightly from 18.31 ± 0.06 MJ/kg at harvest to 18.76 ± 0.21 MJ/kg at the end of the storage period. The lower heating value (LHV) increased by about 50% in the C and CD piles by the end of the storage period. However, in the NC piles, the LHV decreased by 3% in the core and 52% in the shell. Leaf-on SRWC biomass stored in piles created in late spring under climatic conditions in central and northern New York showed differing moisture contents when stored for over 60–90 days. Overhead protection could be used to preserve or improve the fuel quality in terms of the moisture content and heating value if more than two months of storage are required. However, the implementation of such management practice will depend on whether the end users are willing to pay a higher price for dryer biomass and biomass with a higher LHV.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Geologic Carbon Storage of Anthropogenic CO2 under the Colorado Plateau in Emery County, Utah

Geologic Carbon Storage (GCS) is a promising technology for storing large volumes of anthropogenic CO2 effectively and permanently. Numerical simulations are an integral part of site selection and characterization for any potential GCS site. As part of the DOE-funded CarbonSAFE Rocky Mountains Phase I project, a regional GCS analysis was undertaken to understand the efficacy of storing CO2 emissions from the power generation and heavy industry in central Utah’s favorable geology. In this study, the injection of CO2 for geologic storage was simulated in the Navajo Sandstone Formation in Emery County, Utah. Carbon dioxide was sourced from regional power generation stations and heavy industries throughout Utah, with an emphasis on emissions reduction at the Hunter Power Plant near Castle Dale, Utah. A simulation grid was extracted from the project’s geological model encompassing an area around Price, Huntington, and Castle Dale in central Utah. The Navajo Sandstone Member of the Glen Canyon Group was the target of CO2 injection with the overlying Carmel formation providing the primary seal. A suite of simulations was performed assessing the viability of this area for permanent CO2 storage. Results indicate that the area can not only store 46 million metric tons of anthropogenic CO2, meeting the project goals, but this area has the capacity to securely store at least 1.3 billion tons of CO2, suggesting the injection site and surrounding geology are suitable locations for commercial-scale GCS.

58 GEOSCIENCES↗
DOE OSTI2018

Effects of NOX Storage Component on Ammonia Formation in TWC for Passive SCR NOX Control in Lean Gasoline Engines

A prototype three-way catalyst (TWC) with NOX storage component was evaluated for ammonia (NH3) generation on a 2.0-liter BMW lean burn gasoline direct injection engine as a component in a passive ammonia selective catalytic reduction (SCR) system. The passive NH3 SCR system is a potential approach for controlling nitrogen oxides (NOX) emissions from lean burn gasoline engines. In this system, NH3 is generated over a close-coupled TWC during periodic slightly-rich engine operation and subsequently stored on an underfloor SCR catalyst. Upon switching to lean, NOX passes through the TWC and is reduced by the stored NH3 on the SCR catalyst. Adding a NOX storage component to a TWC provides two benefits in the context of a passive SCR system: (1) enabling longer lean operation by storing NOX upstream and preserving NH3 inventory on the downstream SCR catalyst; and (2) increasing the quantity and rate of NH3 production during rich operation. Since the fuel penalty associated with passive SCR NOX control depends on the fraction of time that the engine is running rich rather than lean, both benefits (longer lean times and shorter rich times achieved via improved NH3 production) will decrease the passive SCR fuel penalty. However, these benefits are primarily realized at low to moderate temperatures (300-500 °C), where the NOX storage component is able to store NOX, with little to no benefit at higher temperatures (>500 °C), where NOX storage is no longer effective. This study discusses engine parameters and control strategies affecting the NH3 generation over a TWC with NOX storage component.

Prikhodko, Vitaly↗
DOE OSTI2021

Methyl jasmonate effects on sugarbeet root responses to postharvest dehydration

Background: Sugarbeet (Beta vulgaris L.) roots are stored under conditions that cause roots to dehydrate, which increases postharvest losses. Although exogenous jasmonate applications can reduce drought stress in intact plants, their ability to alleviate the effects of dehydration in postharvest sugarbeet roots or other stored plant products is unknown. Research was conducted to determine whether jasmonate treatment could mitigate physiological responses to dehydration in postharvest sugarbeet roots. Methods: Freshly harvested sugarbeet roots were treated with 10 µM methyl jasmonate (MeJA) or water and stored under dehydrating and non-dehydrating storage conditions. Changes in fresh weight, respiration rate, wound healing, leaf regrowth, and proline metabolism of treated roots were investigated throughout eight weeks in storage. Results: Dehydrating storage conditions increased root weight loss, respiration rate, and proline accumulation and prevented leaf regrowth from the root crown. Under dehydrating conditions, MeJA treatment reduced root respiration rate, but only in severely dehydrated roots. MeJA treatment also hastened wound-healing, but only in the late stages of barrier formation. MeJA treatment did not impact root weight loss or proline accumulation under dehydrating conditions or leaf regrowth under non-dehydrating conditions. Both dehydration and MeJA treatment affected expression of genes involved in proline metabolism. In dehydrated roots, proline dehydrogenase expression declined 340-fold, suggesting that dehydration-induced proline accumulation was governed by reducing proline degradation. MeJA treatment altered proline biosynthetic and catabolic gene expression, with greatest effect in nondehydrated roots. Overall, MeJA treatment alleviated physiological manifestations of dehydration stress in stored roots, although the beneficial effects were small. Postharvest jasmonate applications, therefore, are unlikely to significantly reduce dehydrationrelated storage losses in sugarbeet roots.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1972

Microphysical, microchemical and adhesive properties of lunar material. 3: Gas interaction with lunar material

Knowledge of the reactivity of lunar material surfaces is important for understanding the effects of the lunar or space environment upon this material, particularly its nature, behavior and exposure history in comparison to terrestrial materials. Adsorptive properties are one of the important techniques for such studies. Gas adsorption measurements were made on an Apollo 12 ultrahigh vacuum-stored sample and Apollo 14 and 15 N2-stored samples. Surface area measurements were made on the latter two. Adsorbate gases used were N2, A, O2 and H2O. Krypton was used for the surface area determinations. Runs were made at room and liquid nitrogen temperature in volumetric and gravimetric systems. It was found that the adsorptive/desorptive behavior was in general significantly different from that of terrestrial materials of similar type and form. Specifically (1) the UHV-stored sample exhibited very high initial adsorption indicative of high surface reactivity, and (2) the N2-stored samples at room and liquid nitrogen temperatures showed that more gas was desorbed than introduced during adsorption, indicative of gas release from the samples. The high reactivity is a scribed cosmic ray track and solar wind damage.

Grossman, J. J.↗
NASA NTRS1973

Multifunction display system, volume 1

The design and construction of a multifunction display man/machine interface for use with a 4 pi IBM-360 System are described. The system is capable of displaying superimposed volatile alphanumeric and graphical data on a 512 x 512 element plasma panel, and holographically stored multicolor archival information. The volatile data may be entered from a keyboard or by means of an I/O interface to the 360 system. A 2-page memory local to the display is provided for storing the entered data. The archival data is stored as a phase hologram on a vinyl tape strip. This data is accessible by means of a rapid transport system which responds to inputs provided by the I/O channel on the keyboard. As many as 500 frames may be stored on a tape strip for access in under 6 seconds.

Source record↗
NASA NTRS1972

Cathodochromic cathode ray tube: An operations manual

A cathodochromic (CC) storage and display system capable of storing full TV resolution images has been built. The images are derived from standard TV signals: composite video, composite sync, composite blanking, horizontal drive, and vertical drive. Image storage takes place in the CC CRT; the fixed image is written for several TV frames for the contrast to be usable. Once stored on the CC CRT, the image can be read out in one of three modes: with the eye, a 35-mm camera, or a TV camera. Incoming information may also be stored in a storage tube similar to the CC CRT but with a phosphor layer behind the CC layer. By exciting the phosphor layer with a standard raster scan it is possible to read out an image stored in the CC layer in one of three modes: direct viewing, photography, or flying-spot readout using a photomultiplier.

Heyman, P. M.↗
NASA NTRS1980

Passive control of wing/store flutter

This paper presents results for a passive flutter suppression approach known as the decoupler pylon. The decoupler pylon dynamically isolates the wing from store pitch inertia effects by means of soft-spring/damper elements assisted by a low-frequency feedback-control system which minimizes static pitch deflections of the store due to maneuvers and changing flight conditions. Wind-tunnel tests and analyses show that this relatively simple pylon suspension system provides substantial increases in flutter speed and reduces the sensitivity of flutter to changes in store inertia and center-of-gravity location. Flutter characteristics of F-16 and YF-17 flutter models equipped with decoupler pylon-mount stores are presented and compared with results obtained on the same model configurations using active flutter suppression systems. These studies show both passive and active concepts to be effective in suppressing wing/store flutter. Also presented are data showing the influence of pylon stiffness nonlinearities on wing/store flutter.

Reed, W. H., III↗
NASA NTRS1980

Passive control of wing/store flutter

Results are presented for a passive flutter suppression approach known as the decoupler pylon. The decoupler pylon dynamically isolates the wing from store pitch inertia effects by means of soft spring/damper elements assisted by a low frequency feedback control system which minimizes static pitch deflections of the store because of maneuvers and changing flight conditions. Wind tunnel tests and analyses show that this relatively simple pylon suspension system provides substantial increases in flutter speed and reduces the sensitivity of flutter to changes in store inertia and center of gravity. Flutter characteristics of F-16 and YF-17 flutter models equipped with decoupler pylon mounted stores are presented and compared with results obtained on the same model configuration with active flutter suppression systems. These studies show both passive and active concepts to be effective in suppressing wing/store flutter. Also presented are data showing the influence of pylon stiffness nonlinearities on wing/store flutter.

Reed, W. H., III↗