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Program Overview Laboratory Directed Research and Development FY2020 (Annual Report)

Throughout this year’s report, we highlight how the LDRD program invests in ideas that make the world a safer place. We review key accomplishments and performance indicators, and we share snapshots of some of our talented staff. I also encourage you to visit our LDRD website and learn more about the 244 projects that we supported during fiscal year 2020. Looking to the future, I am confident that LDRD investments will continue to help LLNL remain at the forefront of innovative research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Techno-economic Analysis and Optimization of Point Source Solvent-Based Carbon Capture Systems at High CO2 Capture Levels for NGCC Power Plants

This poster was presented at the 2024 FECM / NETL Carbon Management Research Project Review Meeting held during Aug 5-9, 2024. It summarizes the research done as a part of CCSI2 for determining the optimal design and operating conditions of an MEA solvent-based carbon capture system connected to a commercial scale NGCC plant, operating at CO2 capture levels beyond 90%. The techno-economic optimization approach is outlined, along with the trends of key cost and performance indicators across high capture levels.

Deshpande, Anuja↗

User's design handbook for a Standardized Control Module (SCM) for DC to DC Converters, volume 2

A unified design procedure is presented for selecting the key SCM control parameters for an arbitrarily given power stage configuration and parameter values, such that all regulator performance specifications can be met and optimized concurrently in a single design attempt. All key results and performance indices, for buck, boost, and buck/boost switching regulators which are relevant to SCM design considerations are included to facilitate frequent references.

Lee, F. C.↗

Vehicle performance impact on space shuttle design and concept evaluation

The continuing examination of widely varied space shuttle concepts makes an understanding of concept interaction with vehicle performance imperative. The estimation of vehicle performance is highly appurtenant to all aspects of shuttle design and hence performance has classically been a key indicator of overall concept desirability and potential. Vehicle performance assumes the added role of defining interactions between specific design characteristics, the sum total of which define a specific concept. Special attention is given to external tank effects.

Craig, M. K.↗

Electrolyte Immersion Increases Photoconductivity in a Model Polymer Photocathode

Immersing polymer solar cells in aqueous electrolyte for photoelectrochemical (PEC) hydrogen production is likely to cause photophysical changes that could present both challenges and opportunities for engineering functional and durable devices. Herein we study the bulk heterojunction blend poly(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)-alt-(2-(((2-ethylhexyl)oxy)carbonyl)-3-fluorothieno[3,4-b]thiophene-4,6-diyl):poly(N,N'-di(2-octyldodecyl)naphthalene-1,8:4,5-bis(dicarboximide)-2,6-diyl)-alt-(2,2-bithiophene-5,5'-diyl) (PTB7-Th:N2200) excited-state dynamics in electrolyte from femtosecond to millisecond time scales using pump-probe microwave conductivity and absorption spectroscopy. While the blend swells very little, electrolyte exposure increases the microwave-frequency mobility and possibly the yield of photogenerated charges while also decreasing crystallinity. These results indicate an enhancement in key performance metrics, implying that any limitations on the performance of PEC test devices do not arise from active layer-electrolyte interactions. For the PTB7-Th:N2200 blend or similar photocathode systems, our results indicate that improving the interfacial kinetics and/or the carrier lifetime should be prioritized, not protecting the active layer from the electrolyte. Since this observation may not be universal to all polymer systems, future research should focus on identifying their limiting photophysical processes. electrolyte.

14 SOLAR ENERGY↗

Bootstrap estimation of the effect of instrument response function uncertainty on the reconstruction of fusion neutron sources

Neutron imagers are important diagnostics for the inertial confinement fusion implosions at the National Ignition Facility. They provide two- and three-dimensional reconstructions of the neutron source shape that are key indicators of the overall performance. To interpret the shape results properly, it is critical to estimate the uncertainty in those reconstructions. There are two main sources of uncertainties: limited neutron statistics, leading to random errors in the reconstructed images, and incomplete knowledge of the instrument response function (the pinhole-dependent point spread function). While the statistical errors dominate the uncertainty for lower yield deuterium-tritium (DT) shots, errors due to the instrument response function dominate the uncertainty for DT yields on the order of 10 16 neutrons or higher. In this work, a bootstrapping method estimates the uncertainty in a reconstructed image due to the incomplete knowledge of the instrument response function. The main reconstruction is created from the fixed collection of pinhole images that are best aligned with the neutron source. Additional reconstructions are then built using subsets of that collection of images. Variations in the shapes of these additional reconstructions originate solely from uncertainties in the instrument response function, allowing us to use them to provide an additional systematic uncertainty estimate.

47 OTHER INSTRUMENTATION↗

Risk of Performance Decrement and Crew Illness Due to an Inadequate Food System

NASA is preparing for long duration manned missions beyond low-Earth orbit that will be challenged in several ways, including long-term exposure to the space environment, impacts to crew physiological and psychological health, limited resources, and no resupply. The food system is one of the most significant daily factors that can be altered to improve human health, and performance during space exploration. Therefore, the paramount importance of determining the methods, technologies, and requirements to provide a safe, nutritious, and acceptable food system that promotes crew health and performance cannot be underestimated. The processed and prepackaged food system is the main source of nutrition to the crew, therefore significant losses in nutrition, either through degradation of nutrients during processing and storage or inadequate food intake due to low acceptability, variety, or usability, may significantly compromise the crew's health and performance. Shelf life studies indicate that key nutrients and quality factors in many space foods degrade to concerning levels within three years, suggesting that food system will not meet the nutrition and acceptability requirements of a long duration mission beyond low-Earth orbit. Likewise, mass and volume evaluations indicate that the current food system is a significant resource burden. Alternative provisioning strategies, such as inclusion of bioregenerative foods, are challenged with resource requirements, and food safety and scarcity concerns. Ensuring provisioning of an adequate food system relies not only upon determining technologies, and requirements for nutrition, quality, and safety, but upon establishing a food system that will support nutritional adequacy, even with individual crew preference and self-selection. In short, the space food system is challenged to maintain safety, nutrition, and acceptability for all phases of an exploration mission within resource constraints. This document presents the evidence for the Risk of Performance Decrement and Crew Illness Due to an Inadequate Food System and the gaps in relation to exploration, as identified by the NASA Human Research Program (HRP). The research reviewed here indicates strategies to establish methods, technologies, and requirements that increase food stability, support adequate nutrition, quality, and variety, enable supplementation with grow-pick-and-eat salad crops, ensure safety, and reduce resource use. Obtaining the evidence to establish an adequate food system is essential, as the resources allocated to the food system may be defined based on the data relating nutritional stability and food quality requirements to crew performance and health.

Douglas, Grace L.↗

Closed-loop pressure retarded osmosis draw solutions and their regeneration processes: A review

Pressure-Retarded Osmosis (PRO) is an osmotic process that has been used to harvest energy from salinity gradients using a semi permeable membrane. A comparison between open-loop PRO (OLPRO) and closed-loop PRO (CLPRO) was made regarding their performance and costs. In CLPRO, where the diluted draw solution is re-concentrated in the regeneration system to be reutilized in the process, has recently received an intensive focus as the most viable configuration for a standalone power plant. The choice of the PRO draw solution in CLPRO is crucial to garner a high osmotic pressure as the key for the feasibility of the process. Here, in this review, the draw solutions are critically evaluated in the literature in terms of energy output as well as the method of regeneration used to recirculate them. A set of practical criteria has been suggested to appraise the adequacy of the solution for CLPRO application. It was concluded that NH 3 – CO 2 theoretically can produce 170 W/m 2 of power density. Inorganic draw solutes such as NaCl can generate high power density up to 87 W/m 2 . Organic draw solutes with their remarkably low reverse salt flux (RSF) have promising potential for future application in PRO. Similarly, the regeneration systems of the diluted draw solutions have also been reviewed and discussed. How the energy consumption of the regeneration process affects the feasibility of CLPRO is explained. For the specific case of osmotic heat engines (OHEs), when the energy of the regeneration process is supplied by heat waste, the range of applicability of the heat waste in CLPRO in terms of efficiency is defined and compared to Organic Rankine Cycle (ORC). The results showed that CLPRO has better efficiency than ORC for temperatures T < 80 °C, which makes it a promising process or low-grade heat energy recovery. In addition, a PRO-RO hybrid system coupled with solar power can reduce the net specific energy consumption (SEC) to 0.39 kWh/m 3 . The conditions that regeneration processes should operate under to make PRO viable are discussed in the last section. Overall, the study indicates the key factors for optimizing the performance of CLPRO process.

42 ENGINEERING↗

Primary display latency criteria based on flying qualities and performance data

With a pilots' increasing use of visual cue augmentation, much requiring extensive pre-processing, there is a need to establish criteria for new avionics/display design. The timeliness and synchronization of the augmented cues is vital to ensure the performance quality required for precision mission task elements (MTEs) where augmented cues are the primary source of information to the pilot. Processing delays incurred while transforming sensor-supplied flight information into visual cues are unavoidable. Relationships between maximum control system delays and associated flying qualities levels are documented in MIL-F-83300 and MIL-F-8785. While cues representing aircraft status may be just as vital to the pilot as prompt control response for operations in instrument meteorological conditions, presently, there are no specification requirements on avionics system latency. To produce data relating avionics system latency to degradations in flying qualities, the Navy conducted two simulation investigations. During the investigations, flying qualities and performance data were recorded as simulated avionics system latency was varied. Correlated results of the investigation indicates that there is a detrimental impact of latency on flying qualities. Analysis of these results and consideration of key factors influencing their application indicate that: (1) Task performance degrades and pilot workload increases as latency is increased. Inconsistency in task performance increases as latency increases. (2) Latency reduces the probability of achieving Level 1 handling qualities with avionics system latency as low as 70 ms. (3) The data suggest that the achievement of desired performance will be ensured only at display latency values below 120 ms. (4) These data also suggest that avoidance of inadequate performance will be ensured only at display latency values below 150 ms.

Funk, John D., Jr.↗

Nano-engineering the material structure of preferentially oriented nano-graphitic carbon for making high-performance electrochemical micro-sensors

Direct synthesis of thin-film carbon nanomaterials on oxide-coated silicon substrates provides a viable pathway for building a dense array of miniaturized (micron-scale) electrochemical sensors with high performance. However, material synthesis generally involves many parameters, making material engineering based on trial and error highly inefficient. Here, we report a two-pronged strategy for producing engineered thin-film carbon nanomaterials that have a nano-graphitic structure. First, we introduce a variant of the metal-induced graphitization technique that generates micron-scale islands of nano-graphitic carbon materials directly on oxide-coated silicon substrates. A novel feature of our material synthesis is that, through substrate engineering, the orientation of graphitic planes within the film aligns preferentially with the silicon substrate. This feature allows us to use the Raman spectroscopy for quantifying structural properties of the sensor surface, where the electrochemical processes occur. Second, we find phenomenological models for predicting the amplitudes of the redox current and the sensor capacitance from the material structure, quantified by Raman. Our results indicate that the key to achieving high-performance micro-sensors from nano-graphitic carbon is to increase both the density of point defects and the size of the graphitic crystallites. Our study offers a viable strategy for building planar electrochemical micro-sensors with high-performance.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Improving Student Achievement in Math and Science

As the new millennium approaches, a long anticipated reckoning for the education system of the United States is forthcoming, Years of school reform initiatives have not yielded the anticipated results. A particularly perplexing problem involves the lack of significant improvement of student achievement in math and science. Three "Partnership" projects represent collaborative efforts between Xavier University (XU) of Louisiana, Southern University of New Orleans (SUNO), Mississippi Valley State University (MVSU), and the National Aeronautics and Space Administration (NASA), Stennis Space Center (SSC), to enhance student achievement in math and science. These "Partnerships" are focused on students and teachers in federally designated rural and urban empowerment zones and enterprise communities. The major goals of the "Partnerships" include: (1) The identification and dissemination of key indices of success that account for high performance in math and science; (2) The education of pre-service and in-service secondary teachers in knowledge, skills, and competencies that enhance the instruction of high school math and science; (3) The development of faculty to enhance the quality of math and science courses in institutions of higher education; and (4) The incorporation of technology-based instruction in institutions of higher education. These goals will be achieved by the accomplishment of the following objectives: (1) Delineate significant ?best practices? that are responsible for enhancing student outcomes in math and science; (2) Recruit and retain pre-service teachers with undergraduate degrees in Biology, Math, Chemistry, or Physics in a graduate program, culminating with a Master of Arts in Curriculum and Instruction; (3) Provide faculty workshops and opportunities for travel to professional meetings for dissemination of NASA resources information; (4) Implement methodologies and assessment procedures utilizing performance-based applications of higher order thinking via the incorporation of Global Learning Observations To Benefit the Environment (GLOBE), Mission to Planet Earth and the use of Geographic Imaging Systems into the K-12th grade curriculum.

Sullivan, Nancy G.↗

Fundamental Interactions of Bimetallic Cu x Pd y ( x + y = 4) Clusters Supported on the α-WC(0001) Surface and Their Performance for CO 2 Adsorption and Dissociation

The tungsten carbide α-WC(0001) surface, an active system for the activation of H 2 and important hydrogenation processes involving unsaturated hydrocarbons, can serve as a support of bimetallic clusters to produce materials with unique catalytic properties, opening routes for a wide range of technical applications. In particular, Cu x Pd y clusters are of particular interest because they combine metals with different properties. A stochastic method was applied to obtain the geometry of Cu x Pd y (x + y = 4) bare clusters, evaluating thousands of possibilities to obtain stable structures, yielding one isomer for Cu 4 , Cu 2 Pd 2 , Cu 1 Pd 3 , and Pd 4 and two isomers for Cu 3 Pd 1 . These clusters were supported on C and W terminations of the tungsten carbide (0001) surface, exploring all of the binding possibilities. The adsorption energies on the C and W terminations are in the ranges from −2.51 to −3.02 eV and from −2.26 to −3.30 eV, respectively. The strongest and weakest binding was seen for monometallic Cu 4 and Pd 4 clusters on both C and W terminations, while the Cu-Pd bimetallics have intermediate adsorption energies but lack a clear trend in terms of composition. The location of Cu x Pd y clusters over the (0001) surface induces a decrease in the work function relative to the pristine surface, while the cluster-surface Bader charge transfer and variations in the partial density of states point to changes in the electronic structure of the carbide atoms upon binding of the metallic clusters. The d-band center of the Cu x Pd y deposited on WC(0001) indicates an intermediate reactivity among Cu(111) and Pd(111) surfaces, modulating the reactivity with small numbers of Cu and Pd atoms, i.e., atom economy in catalyst design. The likelihood of existence of the most stable Cu x Pd y (x + y = 4) clusters in the temperature range of 298-400 K is 100%. The composite Cu x Pd y /α-WC(0001) (x + y = 4), is a nontrivial system since 22 isomers are needed to completely describe its structural properties. Among the isomers, seven structures are necessary to represent Cu 3 Pd 1 /α-WC(0001), five for Pd 4 /α-WC(0001), two for Cu 4 /α-WC(0001), and four for Cu 2 Pd 2 /α-WC(0001) and Cu 1 Pd 3 /α-WC(0001). The large number of cluster isomers supported on the tungsten carbide surface opens the door for several applications in the heterogeneous catalysis of the Cu x Pd y /α-WC(0001) composite, with the possibility of modulating the geometric, electronic, and chemical properties according to a desired application. Test studies for the adsorption of CO 2 indicate that the Cu x Pd y /α-WC(0001) composites are highly active for the adsorption and decomposition of the molecule, with bimetallic and admetal-carbide interactions playing a key role in the binding performance. In conclusion, this high activity indicates that these systems should be useful as catalysts for the conversion of CO 2 to oxygenates or light alkanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Efficiency Evaporated CdSeTe/CdTe Solar Cells With and Without MgZnO Buffer Layer

High efficiencies of ~19% CdTe solar cell devices were made using a thermal evaporation technique to deposit absorber layers of CdSe and CdTe. The absorber films were very high quality for a device fabrication, and with demonstrated high efficiency, it is a viable option to employ thermal evaporation in research and manufacturing. We also investigated four different interfaces scenarios of with and without MZO and CdSe in the device near front interface. The results clearly indicate that Se plays a key role in improving device performance, but the MZO is not necessarily required unless experiment goals demanded. Removing the MZO layer from the device structure and being able to use thermal evaporator for CdTe deposition will help with cost reduction in manufacturing.

41 EE - Solar Energy Technologies Office (EE-4S)↗

Performance Data Report: Space Medicine Division, Human Research Program, Behavioural Health and Performance Research Element

This report is the result of a collaborative effort between NASA?s Behavioral Health & Performance (BHP) Research and Operations Group to investigate and determine the availability of data pertaining to behavioral performance (and other pertinent variables) that have been collected by the laboratories at NASA?s Johnson Space Center. BHP?s Operations and Research groups collaborated to systematically identify what types of performance data are needed in relevant BHP performance domains and also to conduct structured interviews with NASA personnel to identify which data do or do not exist currently (and for instances where such data exist, to evaluate the type, quality, accessibility, and confidentiality of those data). The authors defined outcome categories of performance that encapsulate BHP performance domains, mapped BHP Research Risks and Gaps onto those performance outcome categories, and identified and prioritized indicators for each outcome category. The team identified key points of contact (subject matter experts [SMEs]) as potential interviewees, created a template for structured interview questions about sources and accessibility of performance data, and coordinated and conducted structured interviews with the SMEs. The methodology, results, and implications of this effort, as well as forward work needed, are discussed in this report.

Shea, Camille↗

Origin of rate limitations in solid-state polymer batteries from constrained segmental dynamics within the cathode

Currently, one of the key challenges preventing the wide commercialization of polymer-based solid-state batteries is achieving high-rate capabilities. This work unravels chain structure and segmental dynamics in a polymer-based composite cathode consisting of LiFePO 4 (LFP), carbon, and poly(ethylene oxide) (PEO) with lithium bis(trifluoromethanesulfonyl)imide. Small-angle neutron scattering (SANS) data reveal that PEO chains are adsorbed on the surface of LFP particles during slurry processing to make the composite electrode. The strong interaction between LFP and PEO chains leads to greatly reduced segmental dynamics of PEO, as discovered by quasi-elastic neutron scattering (QENS). The reduced segmental dynamics results in 70% decreased Li + mobility of the polymer electrolyte in the composite cathode. The combined SANS and QENS study indicates that one of the key bottlenecks that limits the rate performance of PEO-based polymer batteries originates from molecular interactions within the cathode.

25 ENERGY STORAGE↗

Kinetics of Direct Olefin Synthesis from Syngas over Mixed Beds of Zn–Zr Oxides and SAPO-34

A packed bed containing a physical mixture of both Zn–Zr mixed oxide catalyst and SAPO-34 converts syngas directly into a mixture of C 2 –C 5 olefins and paraffins. Specifically, the mixed oxide catalyst is responsible for intermediate oxygenate synthesis from syngas while the molecular sieve catalyzes olefin synthesis from the oxygenate intermediates. Kinetic measurements with cofed propylene over each catalyst independently confirm olefin hydrogenation activity over both components of the composite bed. The addition of either water or CO to the feed drops the activity of propylene hydrogenation over the Zn–Zr oxide. In sum, under reaction conditions of syngas feed and produced water, olefin hydrogenation predominantly occurs over the SAPO-34 catalyst, rather than over the catalyst responsible for hydrogenating CO into oxygenate intermediates. Here, a developed kinetic model consistent with this conclusion describes measurements at differing feed compositions, temperatures, space velocities, and bed catalyst mixing ratios. Technoeconomic analysis of the process indicates that the olefin-to-paraffin ratio is a key performance metric for commercial scale syngas conversion and highlights the importance of considering olefin hydrogenation rates over the molecular sieve component.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An industrial perspective on catalysts for low-temperature CO 2 electrolysis

Electrochemical conversion of CO 2 to useful products at temperatures below 100 °C are nearing the commercial scale. Pilot units for CO 2 conversion to CO are already in testing. Units to convert CO 2 to formic acid are projected to reach pilot scale in the next year. Further, several investigators are starting to observe industrially relevant rates of the electrochemical conversion of CO 2 conversion to ethanol and ethylene with the needed hydrogen coming from water. In each case, Faradaic efficiencies of 80% or more and currents above 200 mA/cm –2 can be reproducibly achieved. In this study we describe the key advances in nano catalysts that lead to the impressive performance, indicate where additional work is needed and provide benchmarks that others can use to compare their results.

10 SYNTHETIC FUELS↗

Mission analysis for earth atmospheric measurements using a Shuttle-Spacelab lidar system

Orbital characteristics and launch conditions of a spaceborne lidar system proposed for a Shuttle Spacelab mission are analyzed. Mission design tradeoffs between instrument fields of view, resolutions, orbit groundtrack repetition parameters (Q), and orbital altitudes are shown. In the multi-experiment application of the Spacelab-lidar system, where scene illumination is the key mission parameter for the performance of the lidar instrument, results indicate that selected daytime or nighttime coverage can be programmed into Spacelab lidar missions by a judicious selection of Shuttle launch time. In addition to controlling the location of nighttime measurements, results indicate that, by the proper selection of Shuttle launch time, the magnitude and variability of solar lighting angles can be optimized to fit the requirements of the Spacelab lidar experiments.

Lawrence, G. F.↗