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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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187 records · Page 11

Robust highly durable solid oxide fuel cell cathodes – Improved materials compatibility & self-regulating surface chemistry

Solid oxide fuel cells (SOFCs) are electrochemical conversion devices that directly transform hydrogen or hydrocarbon fuels to electricity, with energy efficiencies as high as 90%, coupled with reduced emissions. Several factors, however, remain to be addressed when considering scale-up of SOFC technology, including the need to overcome decreased performance due to sluggish rates of the oxygen reduction reaction (ORR) at the cathode under reduced temperatures and susceptibility to degradation in performance from surface poisoning e.g. from chromia, while limiting the use of critical raw materials (lanthanides and transition metals) present in high performing mixed ionic electronic conducting electrodes like (La,Sr)CoO 3 (LSC). In this project we explored the key descriptors for determining ORR activity in SOFC electrodes and tried to recover performance degradation by applying them to SOFC electrodes. In order to do this, we first selected a model mixed ionic electronic conducting (MIEC) oxide, Pr-doped CeO 2 (Pr 0.1 Ce 0.9 O 2-δ , PCO), which is a chemically stable fluorite and free of inherent poison sources (e.g. Sr segregation in LSC) that potentially react with external impurities such as Cr-species vaporized from the interconnect. The three approaches originally planned in this project are as follows: 1) evaluation of scavenger exsolution characteristics, 2) study of scavengers gettering efficacy following Cr and Si poisoning and 3) integration of new compositions into porous electrodes. Among them, exceptional progress has been made in 2) and 3), especially understanding the role of surface infiltrants in impacting electrode performance and degradation of PCO materials. We found that the Smith acidity scale for binary oxides serves as a powerful descriptor for tuning and predicting the oxygen exchange kinetics on MIEC PCO surfaces. As a result, with infiltration with binary oxides, ranging from strongly basic (Li 2 O) to strongly acidic (SiO 2 ) onto the surface of porous PCO, it was possible to systematically vary the chemical surface exchange coefficient (k chem ) by 6 orders of magnitude! L i2 O increased k chem by nearly 1,000 times over that of pristine PCO, while SiO 2 decreased k chem by nearly the same factor. Strikingly, although the pre-exponential of k chem scales linearly with the acidity of the infiltrated binary oxide, there is nearly no change in the activation energy. With this insight, we attributed the origin of these dramatic changes in k chem values to the systematic increase and decrease in the surface electron density induced by infiltrated binary oxides. More interestingly, although both Cr 2 O 3 and SiO 2 were determined to be acidic by Smith, suggesting that this feature could likely be the primary reason that these compounds serve to poison the ORR on SOFC cathodes, the effect of poisoning could be subsequently tuned by adding multiple infiltrants and controlling their relative surface acidities. We also systematically examined the effect of serial infiltration of basic and acidic oxides. It turned out that serial infiltration of Li not only recovers approximately 20-fold degraded k chem of PCO by acidic Cr 2 O 3 but its k chem is enhanced even beyond that of the non-infiltrated PCO by more than three orders of magnitude. This was further verified with a screen-printing PCO symmetric cell in terms of the electrode performance (area-specific resistance, ASR) related to approach 3). These observations point to acidity as a key descriptor not only in tuning and predicting the ORR activity of SOFC cathodes that largely determines the overall performance of SOFC, but in mitigating and reactivating poisoned electrode performance. This work provides novel guidelines for making the electrode performance much more active and robust in SOFCs, which can further be applied to all applications requiring oxygen exchange reaction, such as electrolyzers, permeation membranes and gas sensors.

30 DIRECT ENERGY CONVERSION↗

The Iodine Satellite (iSat) Propellant Feed System - Design and Demonstration

CUBESATS are relatively new spacecraft platforms that are typically deployed from a launch vehicle as a secondary payload, providing low-cost access to space for a wide range of end-users. These satellites are comprised of building blocks having dimensions of 10x10x10 cm3 and a mass of 1.33 kg (a 1-U size). While providing low-cost access to space, a major operational limitation is the lack of a propulsion system that can fit within a CubeSat and is capable of executing high Delta V maneuvers. This makes it difficult to use CubeSats on missions requiring certain types of maneuvers (i.e. formation flying, spacecraft rendezvous). Work has been performed investigating the use of iodine as a propellant for Hall-effect thrusters (HETs) that could subsequently be used to provide a high specific impulse path to CubeSat propulsion. One of the systems under development to support such a technology is the propellant feed system, which must be capable of storing solid iodine propellant, applying heat to sublime the stored solid into the vapor phase, and then control the flow of low-pressure gaseous iodine to both the thruster and cathode. In a test conducted in 2016, a first-generation iodine propellant feed system was integrated with a cathode and Hall thruster. While this test had to be terminated, the feed system in this first test was able to support both cathode and integrated cathode and thruster operation prior to the termination of the test. In the present paper, we describe work performed since that initial integrated test. The effort uses lessons learned from the previous integrated test, retiring risk associated with the iodine propellant feed system, answering open design-space questions, and demonstrating iodine flow control in an integrated system. The work is undertaken at both the component level and then at the integrated subsystem level to systematically improve the feed system design, improving the hardware fidelity so the appearance and operation of the system are as flight-like as possible. At the component level, the work focuses on the propellant tank, the feed system tubing, the valves used to control the flow to the cathode and thruster, and the heaters that maintain the temperature of the flowpaths and keep iodine from redepositing and clogging the system. Work on the propellant reservoir focuses on fabricating a tank that matches the geometry of the flight design, which allows for the identification of flight tank fabrication issues that may arise and permits thermal testing of a tank possessing the same size and thermal mass as the flight design, which can be used to anchor thermal modeling of the component. This is critical for finalizing the tank heater power requirements that feed into the heater design. All metallic materials in the feed system are hastelloy or Inconel, as these materials are resistant to chemical attack by the highly-reactive iodine vapor. The tubing in the iodine feed system must possess ports to permit a neutral gas purge of the system that clear impurities after iodine is loaded into the propellant tank. A procedure is discussed whereby these ports are crimped and sealed after the purge process is completed so as to not re-expose the iodine system to air. The valves are a critical component for control of the flow to the thruster and the cathode. Significant effort has gone into upgrading the materials of the valves to make them more resistant to chemical attack and into developing an understanding of the use of these valves during the startup and operation of the cathode and thruster. The heaters that line the entire feed system are designed to draw minimal power from the power processing unit (PPU) while still having the capacity to maintain all the feed system components at the temperatures required to discourage iodine deposition inside components downstream of the propellant tank exit. The heaters possess two separate resistive traces, giving the design redundancy should a failure occur in the primary heater circuit of one of the heater zones. The task of operating a feed system in conjunction with a thruster and cathode is undertaken in a series of sub-steps. The system is first assembled and operated on xenon gas, using the valves for cathode startup and thruster control based on measurement of the discharge current. After startup and control on xenon are demonstrated, the thruster will be transitioned to iodine operation, demonstrating thruster startup and feed system control while using a xenon-fed cathode. Finally, the last step is to integrate an iodine-compatible cathode with the system, demonstrate autonomous cathode start-up with open-loop control and thruster start-up with closed-loop control for multiple cycles.

Polzin, Kurt A.↗

Final Design for Thermal/Epithermal eXperiments (TEX) with Lithium Absorbers to Provide Validation Benchmarks for Y-12 Electrorefining Facility

One of the main goals of the Thermal/Epithermal eXperiments (TEX) project is to use existing Nuclear Criticality Safety Program (NCSP) assets to create critical experiment plutonium and uranium test beds for materials important to criticality safety that have insufficient benchmark evaluations. The plutonium test bed experiments were completed in 2018 and are published in the 2020 edition of the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Handbook. The uranium test bed assemblies were completed in 2023 and accepted in the 2024 edition of the ICSBEP Handbook. The Nuclear Criticality Safety (NCS) group at Y-12 National Security Complex has identified programmatic need for validation cases for uranium electrorefining operations at Y-12. The electrorefining operation credits lithium enriched in 6 Li in addition to 35 Cl as absorbers in the design criticality safety evaluation for precluding criticality under upset conditions in the large and geometrically unfavorable electro-refiner. There is, however, inadequate experimental validation for the 6 Li absorbers. As an extension of the TEX uranium test bed, TEX-Cl critical experiments were performed with sodium chloride salt to address the 35 Cl thermal absorption as well as other validation needs at Los Alamos National Laboratory (LANL). These experiments were completed in 2024 and accepted into the 2025 ICSBEP Handbook. To continue the methodology used in TEX-Cl, TEX-Li aims to accomplish the same. The overall design of both experiments was to use commercially available, high purity, salts with polyethylene moderator and HEU plates to configure a critical assembly. Three experiments are planned for TEX-Li using encapsulated lithium carbonate (Li 2 CO 3 ), with natural 6 Li abundance. For all experiments, the highly enriched uranium (HEU) Jemima plates will be used as fissile material. Multiple layers will be stacked together with encapsulated Li 2 CO 3 alternated with polyethylene in standard configurations. Standard stacking was found to be optimal in matching the different sensitivity profiles provided by the Y-12 models. Three configurations are proposed with varying polyethylene moderation and a constant 1/4” absorber thickness. The first uses 11 layers of 5/4” polyethylene, the second uses 9 layers of 3/4” polyethylene, and the third uses 10 layers of 1/2” polyethylene. Calculations showed that some alternative forms of lithium-based materials provided slightly less-optimal sensitivity profiles when compared to lithium carbonate but come with other drawbacks. These alternatives included lithium aluminate (LiAlO 2 ), Aluminum-2050 alloy, Aluminum-8090, Aluminum-2095, lithium hydride (LiH), and lithium fluoride (LiF). Lithium aluminate and aluminum-2050 provided comparable sensitivity profiles when compared to lithium carbonate and can be used instead if lithium carbonate cannot be readily procured. After a broad material study, lithium carbonate outperformed any alternative material with a balance in affordability and workability. The assessment of experimental uncertainties of the non-absorber and absorber components was predicted to be 0.00089 and 0.00093 Δk eff , respectively. The largest uncertainties may be reduced with precision dimensional inspection of the components. Many of the parts and equipment for IER 575 have already been fabricated or procured for previous projects and therefore do not contribute significantly to the overall cost of this experiment. This includes the Jemima plates and Comet critical assembly machine, which are existing NCSP assets, as well as the aluminum platen and polyethylene reflector rings, which were fabricated and authorized for the TEX experiment involving HEU with polyethylene. Lithium carbonate containers will be procured by LANL and will be filled by LLNL. The total material costs for TEX-Li experiments are estimated to be on the order of $\$$47,400. Precision inspection, including dimensional, mass, density, and impurity, is recommended for all components for an estimated cost of $\$$12,000.

35Cl↗

Czochralski growth and characterization of the multicomponent garnet (Lu 1/4 Yb 1/4 Y 1/4 Gd 1/4 ) 3 Al 5 O 12

This work demonstrates the potential for practical scalable growth of complex garnets and evaluates the implications of a multicomponent composition in the optical quality and elemental distribution of a Czochralski-grown crystal. Furthermore, our experimental approach was designed to elucidate the relation between a complex garnet composition ( Lu 1 / 4 Yb 1 / 4 Y 1 / 4 Gd 1 / 4 ) 3 Al 5 O 12 , crystal growth parameters, crystal structural, and elemental homogeneity. Our hypothesis is that combining multiple rare earths (REs) that will fractionally occupy the dodecahedral site in the aluminum garnet structure will result in a stable, single garnet compound that can be grown by the Czochralski method. Single-crystal and powder x-ray diffraction indicated a single garnet phase with an increasing unit cell volume from seed to tail. In addition, we propose that the pattern of elemental segregation will be based on the deviation of the ionic radius of each constituent RE from the average RE ionic radius of the multicomponent garnet. Electron probe microanalysis revealed that ions that are smaller than that average ( Lu 3 + and Yb 3 + ) are preferentially incorporated in the crystal, while elements that are larger than that average ( Gd 3 + ) are rejected. The ionic radius of Y 3 + is close to that average and yttrium segregation was minimal. The concentrations of the four REs are closer to stoichiometric on the tail end of the boule. Scanning electron microscopy and energy-dispersive x-ray spectroscopy analysis reveal Gd-rich inclusions with eutectic microstructures in the tail end of the boule.

36 MATERIALS SCIENCE↗

Multiple Sources of Riparian Wetland Suspended Solids during Episodic Rain Events: Influence on Uranium Transport

Suspended solids can be the primary vector for transporting contaminants in streams. The objective of this study was to determine whether changes in the properties of suspended solids during rain events impacted contaminant transport. Stream water was collected during five episodic events downstream from a U-contaminated wetland located in South Carolina, USA. The suspended particles were initially composed of Fe-flocs (particles formed in situ prior to the rain event) that had significantly greater Fe, Mn, organic-C, and U content than particles collected later during a sampling rain event. XANES and EXAFS revealed that U in the Fe-flocs was U(VI) and that it was not incorporated in a mineral structure but existed as inner- or outer-sphere adsorbed uranyl species associated with organic matter and Fe-oxides. The uranyl had an extraordinarily high affinity for the suspended solids, with solid to liquid U ratios of >72,000 (μg/kg)/(μg/L). After the initial flush of Fe-flocs, a greater fraction of the suspended solids had lower organic-C, Fe, Mn, and amorphous phases and were composed of more quartz, kaolinite, and gibbsite, resulting in lower U concentrations than those in the solids collected earlier in the rain event. This study highlights the importance of understanding suspended solids as transport vectors and their potential dynamic nature during rain events.

computer simulations↗

Boosting the Oxygen Evolution Reaction by Tuning the Interfacial Iron Adsorption on Layered Double Hydroxide

Understanding the interaction between ions in the electrolyte and electrode materials plays an important role in optimizing the water electrolysis performance for hydrogen production. Herein, the synergistic effect of iron (Fe) in the electrolyte and interlayer anions within the layered structure on the oxygen evolution reaction (OER) has been investigated by combining material synthesis with controlled structure, multiple characterization techniques, and first-principles calculations. Nickel aluminum layered double hydroxides (NiAl-LDHs) with different interlayer anions (CO 3 2– , Cl – , and Br – ) show similar oxygen evolution activity in the absence of Fe species in the electrolyte. The addition of Fe into the electrolyte results in improved performance for all of the NiAl-LDHs, following the rank LDH-Br > LDH-Cl > LDH-CO 3 , under all of the conditions with varied concentration of Fe. X-ray absorption spectroscopy and identical location electron microscopy analyses show that the LDH structure remains unchanged after the OER activity test, while in situ stationary probe rotating disk electrode inductively coupled plasma mass spectrometry (SPRDE-ICP-MS) measurements show partial dissolution of the intercalating halide ions during cycling, with less dissolution for Br-intercalated materials. Insights from theoretical calculations demonstrate the thermodynamic preference of Br – to remain intercalated in the presence of Fe, while the stronger adsorption of Fe(OH) 3 species on the LDH-Br sample promotes the OER activity. In conclusion, these results provide mechanistic insights into the rational design of active layered materials with an enhanced OER performance for efficient water electrolysis.

58 GEOSCIENCES↗

Final Design for Thermal/Epithermal eXperiments (TEX) with Chloride Absorbers to Provide Validation Benchmarks for Y-12 Electrorefining Facility

Uranium electrorefining operations at Y-12 require validation for chlorine absorption and reflection. Plutonium chloride solution operations at Los Alamos National Laboratory require chlorine absorption validation. The growing need for chlorine validation is evident to the wider criticality safety community, with multiple attendees at the recent TEX 2.0 meeting at Lawrence Livermore National Laboratory (May 2023) requesting validation for chlorine (Idaho National Laboratory (INL), Institute de radioprotection et de surete nucleaire (IRSN), Savannah River Nuclear Site (SRNS), LANL, and Y-12). Los Alamos National Laboratory has recently performed, and benchmarked, an experiment titled Chlorine Worth Study (CWS) for the internal operations at the lab, but due to the difficulties in precisely characterizing the material compositions of the chlorine absorbers it is advantageous to perform a complimentary study with a different chlorine-based absorber material. Furthermore, having a uranium-based vs plutonium-based experiment provides a separate and important validation basis for criticality safety and nuclear data evaluation. The original final design report for the study of chlorine absorption using the TEX-HEU experimental base was presented in 2022, but used the same chlorine-bearing materials that were found to be difficult to characterize in the LANL benchmark. A complete redesign of the experiment has been performed looking at alternative absorber materials in various forms to produce an experiment that is fully characterizable. This report presents five novel chlorine experiments using the TEX-HEU test bed which provides direct comparison to the Y-12 and INL/Terrapower application needs, utilizing sodium chloride (NaCl) absorber plates. The absorber plates will consist of granulated NaCl (≥99.5% pure), which will be fully encapsulated in aluminum tins, providing a simple but effective chlorine-based absorber material that can be completely characterized. Of the five configurations presented in this report, it is expected that two or three configurations will be down selected for the actual experiment, with the other configurations being alternates. Three of the configurations are in the standard configuration, where the absorber is placed directly on the HEU fuel plates, and two in the sandwich configuration, where the absorber is surrounded by polyethylene moderators to force additional neutron thermalization prior to reaching the absorber. There are two thicknesses of NaCl absorber plates: 3/16” and 1/4” active thicknesses (i.e. not including the encapsulation). Both variations of the absorbers have an active absorber radius of 6” and a total radius of 7.5” to match the diameter of the HEU plates, with the outer 1.5” being aluminum encapsulation. The high-density polyethylene (HDPE) moderators are of the thicknesses: 27/16”, 7/4”, 1/8”, 11/16”, and 3/4”. The final configurations have six (one sandwich and one standard configuration), eight (one sandwich and one standard configuration), and 18 total fuel layers (standard configuration). The standard and sandwich configurations were designed such that the differences in moderator thicknesses are 1” HDPE, which were already procured for the original CED-2. The proposed configurations were precisely tuned to closely match the sensitivity profiles and neutron spectra of the Y-12 upset cases and were also compared to the INL/Terrapower upset cases. The assessment of experimental uncertainties of the non-absorber components was predicted to be 0.00114 Δk eff . The assessment of uncertainties resulting from the absorbers was predicted to be 0.00029 Δk eff . This results in a total uncertainty of 0.00118 Δk eff . Many of the largest uncertainties, namely the moderator densities, may be reduced with precision dimensional inspection of the components. The 1” HDPE moderators as well as the HDPE reflectors from the original CED-2 were incorporated in the final designs presented here. Additional HDPE moderator plates must be fabricated to complete the configurations. NaCl absorber plates will by fabricated at LLNL. The total additional cost is expected to be $\$$54,250 for the remaining components. Precise inspection, including dimensional, mass, density, and impurity, is recommended for all components. LLNL estimates that these costs are around $\$$12,000. It is expected, based on previous TEX-HEU experiments, that three weeks of experimental facility time is needed to complete the experiments.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗