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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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At least 577 records · Page 32

Ultrastructure of Critical-Gel-like Polyzwitterion–Polyoxometalate Complex Coacervates: Effects of Temperature, Salt Concentration, and Shear

The structure of unconventional complex coacervates, such as polymer-nonpolymer complex coacervates, remains less investigated than that of the conventional coacervates formed between oppositely charged polyelectrolytes with symmetric charge species. Yet, their microscopic structural organization is important to further elucidate the mechanism of liquid-liquid-phase separation processes upon complexation. In this work, we characterize the microstructural organization of complex coacervates formed between inorganic polyoxometalate (POM) and polyzwitterion by small-angle X-ray scattering (SAXS) with in situ temperature and shear control. Furthermore, despite the apparent transparent and homogeneous morphology of dense coacervates as observed by optical microscopy, our previous results (Macromolecules 2018, 51, 22, 9405-9411) suggest that dense polyzwitterion-POM coacervates exhibit critical-gel-like networks containing both complex-poor region (mesh pore) and complex-rich region (connective network). SAXS results as reported in this work support that the complex-rich region is actually in the form of loosely packed POM aggregates linked by polyzwitterion, designated as complex particles. The structure of aggregating complex particles is further examined against varied composition and salt concentrations, temperature, and shear, thanks to the high X-ray scattering contrast of POMs from that of other components in the coacervates. The complex particles in the dense coacervates appear to grow with more tightly packed POM aggregates with increasing POM-to-polyzwitterion concentration ratio, in contrast to more loosely packed POM aggregates with decreasing salt concentration. Conversely, increasing temperature could result in smaller complex particles containing more loosely packed POM aggregates, consistent with temperature-dependent viscoelasticity of dense coacervates. Furthermore, such POM-based hybrid dense coacervates exhibit intriguing strain-hardening behavior, resulting from shear-enhanced POM packing inside the complex particles. Distinct from the shear-thinning behavior of most conventional crosslinked polymeric networks, the strain-hardening property combined with thermal- and salt-responsive characteristics of polyzwitterion-POM coacervates could broaden the applications of hybrid organic-inorganic macroion coacervates as smart functional materials working under extreme environmental conditions.

36 MATERIALS SCIENCE↗

Probing the meta-stability of oxide core/shell nanoparticle systems at atomic resolution

Hybrid nanoparticles allow exploiting the interplay of confinement, proximity between different materials and interfacial effects. However, to harness their properties an in-depth understanding of their (meta)stability and interfacial characteristics is crucial. This is especially the case of nanosystems based on functional oxides working under reducing conditions, which may severely impact their properties. Here, the in-situ electron-induced selective reduction of Mn 3 O 4 to MnO is studied in magnetic Fe 3 O 4 /Mn 3 O 4 and Mn 3 O 4 /Fe 3 O 4 core/shell nanoparticles by means of high-resolution scanning transmission electron microscopy combined with electron energy-loss spectroscopy. Such in-situ transformation allows mimicking the actual processes in operando environments. A multi-stage image analysis using geometric phase analysis combined with particle image velocity enables direct monitoring of the relationship between structure, chemical composition and strain relaxation during the Mn 3 O 4 reduction. In the case of Fe 3 O 4 /Mn 3 O 4 core/shell the transformation occurs smoothly without the formation of defects. However, for the inverse Mn 3 O 4 /Fe 3 O 4 core/shell configuration the electron beam-induced transformation occurs in different stages that include redox reactions and void formation followed by strain field relaxation via formation of defects. This study highlights the relevance of understanding the local dynamics responsible for changes in the particle composition in order to control stability and, ultimately, macroscopic functionality.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advancements in Development and Testing of Thermal Power Dispatch Simulators

Flexible plant operations and generation (FPOG) offer nuclear power plants (NPPs) the chance to leverage alternative, non-electric revenue streams while ensuring their continued role as reliable, clean, and constant sources of baseload electrical power. The excess thermal energy generated from NPPs during periods of low electricity demand can be channeled as raw materials to numerous industrial processes via a thermal power dispatch (TPD) system. Hydrogen production via high-temperature steam electrolysis (HTSE) is an optimal use case based on technical and economic feasibility. Researchers at Idaho National Laboratory (INL) have conducted previous works that developed and implemented TPD system models within the GSE Solutions Generic Pressurized Water Reactor (GPWR) simulator to support human-in-the-loop (HITL) scenario-based evaluations. The first part of this report documents modifications made to the GPWR TPD model and HMI from the previous iteration in line with a new Sargent and Lundy (S&L) TPD design with an automatic control system. The was done in collaboration with Westinghouse using their three-loop pressurizer water reactor (W3LPWR) simulator which contains an industrial grade automatic control system for the TPD. This was installed in the Human Systems Simulation Laboratory (HSSL) at INL. The second part of the report documents findings from an all-hands-on-deck integration and verification workshop that was conducted in the HSSL over several days. The research team comprised INL human factors and TPD experts, a nuclear engineer from GSE Solutions who implemented the revised TPD model for GPWR, the human-machine interface (HMI) prototyping and human factors team from the University of Idaho, and personnel with operations experience with pressurized water reactors. The workshop provided time and expertise to conduct the final activities to bring the operations, HMI, and simulator into a functional state. The goals of the integration and verification workshop were: 1. to install the revised GPWR TPD model into the HSSL 2. verify the TPD HMI prototype was functional 3. integrate the HTSE Simulink model to GPWR. 3. Issues were identified for resolution, but overall the workshop accomplished its goal to integrated and verify the majority of the intended functional. Future work will resolve the identified issues and use the integrated simulation to support an evaluation and demonstration in the next fiscal year.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Down-Selection of Four Common Habitat Variants

The Common Habitat is a large habitat developed as an alternative architecture study, not part of the current NASA baseline, that uses the SLS core stage liquid oxygen tank as its primary structure. It has a gravity-independent internal architecture, such that identical units can be used on the lunar surface, Mars surface, and in microgravity. In developing the habitat, two key architectural questions emerged. Should the internal layout use a vertical or horizontal orientation of the tank? Should the crew size be four or eight? This led to the design of four variants: a four-crew horizontal, four-crew vertical, eight-crew horizontal, and eight-crew vertical. The four-crew variants use a shortened version of the tank while the eight-crew variants use the entire tank. The primary consideration applied for down-selection is the crew experience living and working in the habitat, inclusive of crew productivity, well-being, and survivability. Based on this consideration, a series of seven assessments were performed to compare the variants. This analysis was performed as an unfunded, volunteer activity leveraging civil servants across multiple field centers, most with expertise working in various Artemis teams. Additionally, the evaluation was limited to the use of CAD models, images, and spreadsheet data, with no resources available for mockups or Virtual Reality. A logistics analysis developed a standard logistics module and then estimated how much stowage could be carried onboard each Common Habitat and how many logistics modules are required by each variant for a given mission duration. It also considered the amounts of water to be stored in each variant. A functional analysis identified and compared the living and working functions across the habitats, ranking them relative to each other. A crew time assessment first estimated the total crew time, building a weekly crew timeline for both four and eight-person crews. It then allocated time to activities linked to living and working functions, comparing how much time was available for each function in each variant. A science productivity assessment developed a relative metric using crew time, science stowage, and assumed rates of experiment consumables use to analytically compare the four variants. It also comparatively ranked the habitats with respect to a number of subjective parameters and a workstation acceptability rating. A maintenance capacity assessment identified and compared eleven generic maintenance capabilities across the variants and also ranked them for their predicted ability to complete twelve fabrication, maintenance, and repair scenarios. A contingency responsiveness analysis examined twelve serious in-flight contingencies. For each scenario, the number of crew needed to respond were predicted and acceptability of various aspects of contingency response were evaluated, comparing the variants against each other. Finally, in a habitability assessment, 120 habitability characteristics reflecting 13 major categories were evaluated for each habitat. These results were compared to identify the most acceptable habitat in each category. Ultimately, the data favored the horizontal orientation over the vertical and an eight-person crew over four. Implications of selecting this variant are discussed, including specific architectural challenges that result from the use of the full tank.

Habitability↗

Down-Selection of Four Common Habitat Variants

The Common Habitat is a large habitat that uses the Space Launch System core stage liquid oxygen tank as its primary structure. It has a gravity-independent internal architecture, such that identical units can be used on the lunar surface, Mars surface, and in microgravity. In developing the habitat, two key architectural questions emerged. Should the internal layout use a vertical or horizontal orientation of the tank? Should the crew size be four or eight? This led to the design of four variants: a four-crew horizontal, four-crew vertical, eight-crew horizontal, and eight-crew vertical. The primary consideration applied for down-selection was the crew experience living and working in the habitat, inclusive of crew productivity, well-being, and survivability. Based on this consideration, a series of seven assessments was performed to compare the four variants. A stowage assessment developed a standard logistics module and then considered the amounts of water to be stored in each variant. It then estimated how much stowage could be carried onboard each Common Habitat and how many logistics modules are required by each variant for a given mission duration. A functional analysis identified and compared the living and working functions across the four habitat, ranking them relative to each other. A crew time assessment first estimated the total crew time, building a weekly crew timeline for both four and eight-person crews. It then allocated time to activities linked to living and working functions, comparing how much time was available for each function in each variant. A science productivity assessment developed a relative metric using crew time, science stowage, and assumed rates of experiment consumables use to analytically compare the four variants. It also comparatively ranked the habitats with respect to a number of subjective parameters and a workstation acceptability rating. A maintenance capacity assessment identified and compared eleven generic maintenance capabilities across the four variants and also ranked the variants for their predicted ability to complete twelve fabrication, maintenance, and repair scenarios. A contingency responsiveness analysis examined twelve serious in-flight contingencies. For each scenario, the number of crew needed to respond was predicted and acceptability of various aspects of contingency response was evaluated, comparing the four variants against each other. Finally, in a habitability assessment, 120 habitability characteristics reflecting 13 major categories were evaluated for each habitat. These results were compared to identify the most acceptable habitat in each category. Ultimately, the data was shown to favor the horizontal orientation over the vertical and an eight-person crew over four. Implications of selecting this variant are discussed, including specific architectural challenges that result from the use of the full SLS liquid oxygen tank.

Habitability↗

Effect of Fluorination on Lithium Transport and Short-Range Order in Disordered-Rocksalt-Type Lithium-Ion Battery Cathodes

Fluorine substitution is a critical enabler for improving the cycle life and energy density of disordered rocksalt (DRX) Li-ion battery cathode materials which offer prospects for high energy density cathodes, without the reliance on limited mineral resources. Due to the strong Li–F interaction, fluorine also is expected to modify the short-range cation order in these materials which is critical for Li-ion transport. In this work, density functional theory and Monte Carlo simulations are combined to investigate the impact of Li–F short-range ordering on the formation of Li percolation and diffusion in DRX materials. Additionally, the modeling reveals that F substitution is always beneficial at sufficiently high concentrations and can, surprisingly, even facilitate percolation in compounds without Li excess, giving them the ability to incorporate more transition metal redox capacity and thereby higher energy density. It is found that for F levels below 15%, its effect can be beneficial or disadvantageous depending on the intrinsic short-range order in the unfluorinated oxide, while for high fluorination levels the effects are always beneficial. Using extensive simulations, a map is also presented showing the trade-off between transition-metal capacity, Li-transport, and synthetic accessibility, and two of the more extreme predictions are experimentally confirmed.

25 ENERGY STORAGE↗

Leveraging Curvature on N–Doped Carbon Materials for Hydrogen Storage

Carbon sorbent materials have shown great promise for solid-state hydrogen (H 2 ) storage. Modification of these materials with nitrogen (N) dopants has been undertaken to develop materials that can store H 2 at ambient temperatures. In this work density functional theory (DFT) calculations are used to systematically probe the influence of curvature on the stability and activity of undoped and N-doped carbon materials toward H binding. Specifically, four models of carbon materials are used: graphene, [5,5] carbon nanotube, [5,5] D 5d -C 120 , and C 60 , to extract and correlate the thermodynamic properties of active sites with varying degrees of sp 2 hybridization (curvature). From the calculations and analysis, it is found that graphitic N-doping is thermodynamically favored on more pyramidal sites with increased curvature. In contrast, it is found that the hydrogen binding energy is weakly affected by curvature and is dominated by electronic effects induced by N-doping. These findings highlight the importance of modulating the heteroatom doping configuration and the lattice topology when developing materials for H 2 storage.

08 HYDROGEN↗

Quantifying biofilm propagation on chemically modified surfaces

Conditions affecting biofilm formation differ among bacterial species and this presents a challenge to studying biofilms in the lab. This work leverages functionalized silanes to control surface chemistry in the study of early biofilm propagation, quantified with a semi-automated image processing algorithm. These methods support the study of Pantoea sp. YR343, a gram-negative bacterium isolated from the poplar rhizosphere. We found that Pantoea sp. YR343 does not readily attach to hydrophilic surfaces but will form biofilms with a “honeycomb” morphology on hydrophobic surfaces. Our image processing algorithm described here quantified the evolution of the honeycomb morphology over time, and found the propagation to display a logarithmic behavior. This methodology was repeated with a flagella-deficient fliR mutant of Pantoea sp. YR343 which resulted in reduced surface attachment. Quantifiable differences between Pantoea WT and ΔfliR biofilm morphologies were captured by the image processing algorithm, further demonstrating the insight gained from these methods.

59 BASIC BIOLOGICAL SCIENCES↗

Functional plasticity of HCO 3 – uptake and CO 2 fixation in Cupriavidus necator H16

Despite its prominence, the ability to engineer Cupriavidus necator H16 for inorganic carbon uptake and fixation is underexplored. We tested the roles of endogenous and heterologous genes on C. necator inorganic carbon metabolism. Deletion of β-carbonic anhydrase can had the most deleterious effect on C. necator autotrophic growth. Replacement of this native uptake system with several classes of dissolved inorganic carbon (DIC) transporters from Cyanobacteria and chemolithoautotrophic bacteria recovered autotrophic growth and supported higher cell densities compared to wild-type (WT) C. necator in batch culture. Strains expressing Halothiobacillus neopolitanus DAB2 (hnDAB2) and diverse rubisco homologs grew in CO 2 similarly to the wild-type strain. Our experiments suggest that the primary role of carbonic anhydrase during autotrophic growth is to support anaplerotic metabolism, and an array of DIC transporters can complement this function. This work demonstrates flexibility in HCO 3 - uptake and CO 2 fixation in C. necator, providing new pathways for CO 2 -based biomanufacturing.

59 BASIC BIOLOGICAL SCIENCES↗

Using electron channeling contrast imaging to inform and improve the growth of high-efficiency GaAs solar cells on nanopatterned GaAs substrates

Patterned substrates provide opportunities for reducing the cost of high-efficiency III-V devices by incorporating mechanically weak layers beneficial for substrate reuse (e.g. by spalling). In this work, the functionality of electron channeling contrast imaging (ECCI) as a tool to efficiently understand and mitigate defect formation is exemplified by developing a process in which high-quality III-V material can be grown on nanopatterned GaAs substrates. Reactive ion etching used in the patterning process was found to damage the GaAs substrate surface, leading to the formation of stacking faults in the epitaxial material as observed by ECCI. Etching the patterned substrates in a 1 NH4OH: 1 H2O2: 50 DI H2O solution for 10 s prior to growth removed the substrate surface damage and stacking faults were no longer present. Growth of solar cell device structures initially produced samples with many macroscale flaws creating shunts in the devices, which complicated the assessment of material quality by device measurements. However, ECCI revealed that the epitaxial material surrounding macroscale flaws was free from any crystallographic defects such as stacking faults and threading dislocations. With this knowledge, we focused on refining the patterning process to eliminate the macroscale flaws. Solar cells were then grown on the improved nanopatterned substrates and exhibited device structures with defect densities less than 5 x 105 cm -2 and average conversion efficiency of 24.8%, nearly identical to devices grown on unpatterned epi-ready substrates (25.0%).

14 SOLAR ENERGY↗

Time-interval distributions in a digital gamma multi-channel analyzer at extreme input rates

Here, this study explores the relationship between experimentally observed inter-event time-interval distributions (TIDs) and measured dead times for pulses generated by a HPGe gamma detector and processed by a digital spectrometer. The system utilizes a fast and slow channel, pile-up rejector, trapezoid filtering, and flash analog-to-digital converter. The experimentally derived TIDs were compared with theory for validation. The results demonstrate that the theoretical model reliably describes measured TIDs up to 40% dead time. However, significant distortion effects become increasingly pronounced at higher input rates. It appears that the deviation between the measured and calculated time-interval distributions take the shape of higher-order convolutions of the TID, which represent the time difference between counts for more than two successive events. In this work, theoretical functions for the TID are expanded to reproduce measurements up to 90%. This refinement in the interpretation and treatment of the measured TIDs provides improved accuracy and precision in the prediction of the true event rate and measured dead time in the counter. Even though it reflects occasional count loss that is specific to the set-up, it is expected that a similar adjustment may be applicable to other detection systems as well.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Standardized nomenclature for photovoltaic connectors

Photovoltaic (PV) systems rely on discrete connectors for the efficient and safe flow of power from module to module and from strings to combiner boxes and inverters. Despite their functional importance, no common nomenclature for PV connectors currently exists, resulting in confusion and miscommunication. Misunderstood terms like "MC4 compatible", "cross-mating", "intermating", "female", and "male" can lead to installation and maintenance errors and compromise system reliability. We believe a standardized terminology will reduce confusion, help support installation best practices, aid in maintenance and repair, inform next-generation designs, and provide a technical basis for improved codes and standards. To that end, we are proposing a standardized glossary for 4 mm PV connectors (the most common type of connector used in PV applications) based on, and validated by, a Sandia National Laboratories' investigation that included the following sources: 1) a comprehensive review of official documents from 20 connector manufacturers, including schematics, datasheets, installation manuals, and catalogs, as well as relevant patents; 2) two rounds of surveys distributed to stakeholders, including connector manufacturers, engineers, asset owners, test labs, and researchers; and 3) visual examination of 25 different models of 4 mm single-pole DC PV connectors to document variations in design and functionality. This work provides a foundation for establishing a clear and consistent terminology for PV connectors that will in turn enable progress toward greater reliability and collaboration across the industry.

14 SOLAR ENERGY↗

Graphite Lithiation under Fast Charging Conditions: Atomistic Modeling Insights

The charging of lithium ion batteries in a fast and safe manner is critical for promoting the mass adoption of electric vehicles. Li intercalation in graphite electrodes is known to be one of the bottlenecks during the fast charging process. The mechanism of Li diffusion in highly polarized graphite anode at high current rates remains, however, not well understood. In this work, Density Functional Theory (DFT) calculations are used to gain insights into the Li diffusion process in graphite when it is far from equilibrium under fast charging conditions. The effect of uncompensated charges on Li mobility is determined in the highly polarized regions of the anode close to the interfaces. The extra charge was found to increase the interlayer spacing in the diffusion layer and adjacent channels, increasing the diffusivity and promoting the formation of Li clusters. A concerted diffusion mechanism at the edge of high-concentration Li domains is proposed to enhance the diffusion of Li.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Latent Representation Learning for Structural Characterization of Catalysts

Supervised machine learning-enabled mapping of the X-ray absorption near edge structure (XANES) spectra to local structural descriptors offers new methods for understanding the structure and function of working nanocatalysts. We briefly summarize a status of XANES analysis approaches by supervised machine learning methods. We present an example of an autoencoder-based, unsupervised machine learning approach for latent representation learning of XANES spectra. This new approach produces a lower-dimensional latent representation, which retains a spectrum–structure relationship that can be eventually mapped to physicochemical properties. Furthermore, the latent space of the autoencoder also provides a pathway to interpret the information content “hidden” in the X-ray absorption coefficient. Our approach (that we named latent space analysis of spectra, or LSAS) is demonstrated for the supported Pd nanoparticle catalyst studied during the formation of Pd hydride. By employing the low-dimensional representation of Pd K-edge XANES, the LSAS method was able to isolate the key factors responsible for the observed spectral changes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Powerful Organic Molecular Oxidants and Reductants Enable Ambipolar Injection in a Large-Gap Organic Homojunction Diode

Doping has proven to be a critical tool for enhancing the performance of organic semiconductors in devices like organic light-emitting diodes. However, the challenge in working with high-ionization-energy (IE) organic semiconductors is to find p-dopants with correspondingly high electron affinity (EA) that will improve the conductivity and charge carrier transport in a film. Here, we use an oxidant that has been recently recognized to be a very strong p-type dopant, hexacyano-1,2,3-trimethylene-cyclopropane (CN6-CP). The EA of CN6-CP has been previously estimated via cyclic voltammetry to be 5.87 eV, almost 300 meV higher than other known high-EA organic molecular oxidants. We measure the frontier orbitals of CN6-CP using ultraviolet and inverse photoemission spectroscopy techniques and confirm a high EA value of 5.88 eV in the condensed phase. The introduction of CN6-CP in a film of large-band-gap, large-IE phenyldi(pyren-1-yl)phosphine oxide (POPy 2 ) leads to a significant shift of the Fermi level toward the highest occupied molecular orbital and a 2 orders of magnitude increase in conductivity. Using CN6-CP and n-dopant (pentamethylcyclopentadienyl)(1,3,5-trimethylbenzene)ruthenium (RuCp*Mes)2, we fabricate a POPy 2 -based rectifying p–i–n homojunction diode with a 2.9 V built-in potential. Blue light emission is achieved under forward bias. Furthermore, this effect demonstrates the dopant-enabled hole injection from the CN6-CP-doped layer and electron injection from the (RuCp*Mes) 2 -doped layer in the diode.

36 MATERIALS SCIENCE↗

Boosting Thermoelectric Performance in Nanocrystalline Ternary Skutterudite Thin Films through Metallic CoTe 2 Integration

Metal–semiconductor nanocomposites have emerged as a viable strategy for concurrently tailoring both thermal and electronic transport properties of established thermoelectric materials, ultimately achieving synergistic performance. In this investigation, a series of nanocomposite thin films were synthesized, embedding metallic cobalt telluride (CoTe 2 ) nanophase within the nanocrystalline ternary skutterudite (Co(Ge 1.22 Sb 0.22 )Te 1.58 or CGST) matrix. Our approach harnessed composition fluctuation-induced phase separation and in situ growth during thermal annealing to seamlessly integrate the metallic phase. The distinctive band structures of both materials have developed an ohmic-type contact characteristic at the interface, which raised carrier density considerably yet negligibly affected the mobility counterpart, leading to a substantial improvement in electrical conductivity. The intricate balance in transport properties is further influenced by the metallic CoTe 2 phase’s role in diminishing lattice thermal conductivity. The presence of the metallic phase instigates enhanced phonon scattering at the interface boundaries. Consequently, a 2-fold enhancement in the thermoelectric figure of merit (zT ~ 1.30) is attained with CGST-7 wt. % CoTe 2 nanocomposite film at 655 K compared to that of pristine CGST.

36 MATERIALS SCIENCE↗

Spatially Resolved Potential and Li-Ion Distributions Reveal Performance-Limiting Regions in Solid-State Batteries

The performance of solid-state electrochemical systems is intimately tied to the potential and lithium distributions across electrolyte–electrode junctions that give rise to interface impedance. Here, we combine two operando methods, Kelvin probe force microscopy (KPFM) and neutron depth profiling (NDP), to identify the rate-limiting interface in operating Si-LiPON-LiCoO 2 solid-state batteries by mapping the contact potential difference (CPD) and the corresponding Li distributions. The contributions from ions, electrons, and interfaces are deconvolved by correlating the CPD profiles with Li-concentration profiles and by comparisons with first-principles-informed modeling. Furthermore, we find that the largest potential drop and variation in the Li concentration occur at the anode–electrolyte interface, with a smaller drop at the cathode–electrolyte interface and a shallow gradient within the bulk electrolyte. Correlating these results with electrochemical impedance spectroscopy following battery cycling at low and high rates confirms a long-standing conjecture linking large potential drops with a rate-limiting interfacial process.

25 ENERGY STORAGE↗