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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 271 records · Page 15

Advancing Porous Carbons: Understanding the Importance of Surface Chemistry for the Energy–Environment Nexus

This review intends, in a critical way, the comprehensive view of the importance of porous carbons surface chemistry for their applications in an energy− environment nexus. Surface chemistry is presented as a combination of functional heteroatom-containing groups, dopants, and structural defects. First, we briefly address carbon surface chemical environment and the methods of its modification and characterization, indicating their practical limitations. Then, the effects of surface chemistry on separation, catalysis, energy storage, sensing and microwave absorption are introduced. Besides a critical analysis of published findings on these topics, we also include our views on the advancement in the processes which rely on porous carbons surface chemistry, and identify strategic areas and directions that should deserve further attention. We focus on new findings and important original contributions to the field. Since the community of carbon researchers grows following the strategic application of these materials, the role of functional groups, dopants and structural defects in various cutting-edge applications is emphasized, showing the progress in the field and the evolution of findings. A clear determination of the effects of carbon surface is often a challenge since carbons porosity and the locations of specific bonds/sites/ defects in the carbon texture provide nanoconfinement effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sustainable Shape Memory Elastomers with Reduced Melt Viscosity and Enhanced Stiffness

Melt reactive processing of lignin with nitrile rubber is a promising approach to synthesizing shape memory materials. The strong intramolecular interactions in lignin macromolecular structures, caused by π–π stacking in aromatic rings and hydrogen bonding, often result in large phase separation or low miscibility with rubbers. In this study, we investigated the chemical and molecular characteristics, as well as the stiffness and complex viscosity, of modified kraft lignin melt-reacted with an acrylonitrile/butadiene copolymer containing 41% acrylonitrile (NBR41). To enhance the macromolecular compatibility of kraft lignin with NBR41, kraft lignin was cross-linked with poly(propylene glycol) diglycidyl ether (PPDE) and trimethylolpropane triglycidyl ether (TTE), both rich in epoxy reactive groups capable of forming chemical bonds with hydroxyl and carboxyl groups. Here, our findings demonstrate that the modification of kraft lignin with PPDE and TTE resulted in significantly increased stiffness of the composites. The elastic modulus of NBR41-Kraft lignin-PPDE and NBR41-Kraft lignin-TTE increased by 82 and 162%, respectively. Both the yield strength and Young’s modulus of these two samples showed dramatic improvements. Specifically, the yield strength and Young’s modulus of NBR41-Kraft lignin-TTE increased nearly 4 and 3-fold, respectively, compared to the control sample. Interestingly, despite significant improvements in mechanical properties, the viscosity of NBR41-Kraft lignin-PPDE was substantially lower than that of the control sample. At 210 °C and an angular frequency of 1 rad/s, the complex viscosity of NBR41-Kraft lignin was approximately 100.25 ± 4.77 kPa·s, while that of NBR41-Kraft lignin-PPDE was significantly lower at 56 ± 0.93 kPa·s. These findings were validated through Fourier transform infrared spectroscopy, scanning electron microscopy, dynamic mechanical analysis, thermal characterization, rheological tests, and quasi-elastic neutron scattering techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modelling turbulent flame ignition and blowout

A statistical mixing model incorporating an overall rate equation to describe the fuel oxidation process was developed for studies of ignition and blowout in a combustor primary zone. This zone is treated as a partially stirred reactor whose composition is described by a statistical ensemble of equal mass fluid elements. This ensemble experiences mixing interactions, which represent the turbulent mixing process, at time intervals governed by an empirically determined mixing frequency. Each mixing interaction is computed by ramdomly selecting two different elements which are then allowed to mix completely so that they reach a mean composition depending on their thermodynamic states prior to mixing. The two elements then separate, and the chemical kinetics proceed depending on their new composition and temperature.

Radhakrishnan, K.↗

Design and development of a space station hazardous material system for assessing chemical compatibility

As the Space Station nears reality in funding support from Congress, NASA plans to perform over a hundred different missions in the coming decade. Incrementally deployed, the Space Station will evolve into modules linked to an integral structure. Each module will have characteristic functions, such as logistics, habitation, and materials processing. Because the Space Station is to be user friendly for experimenters, NASA is anticipating that a variety of different chemicals will be taken on-board. Accidental release of these potentially toxic chemicals and their chemical compatibility is the focus of this discourse. The Microgravity Manufacturing Processing Facility (MMPF) will contain the various facilities within the U.S. Laboratory (USL). Each facility will have a characteristic purpose, such as alloy solidification or vapor crystal growth. By examining the proposed experiments for each facility, identifying the chemical constituents, their physical state and/or changes, byproducts and effluents, those payloads can be identified which may contain toxic, explosive, or reactive compounds that require processing or containment in mission peculiar waste management systems. Synergistic reactions from mixed effluent streams is of major concern. Each experiment will have it own data file, complete with schematic, chemical listing, physical data, etc. Chemical compatibility information from various databases will provide assistance in the analysis of alternate disposal techniques (pretreatment, separate storage, etc.). Along with data from the Risk Analysis of the Proposed USL Waste Management System, accidental release of potentially toxic and catastrophic chemicals would be eliminated or reduced.

Congo, Richard T.↗

Method for using magnetic particles in droplet microfluidics

Methods of utilizing magnetic particles or beads (MBs) in droplet-based (or digital) microfluidics are disclosed. The methods may be used in enrichment or separation processes. A first method employs the droplet meniscus to assist in the magnetic collection and positioning of MBs during droplet microfluidic operations. The sweeping movement of the meniscus lifts the MBs off the solid surface and frees them from various surface forces acting on the MBs. A second method uses chemical additives to reduce the adhesion of MBs to surfaces. Both methods allow the MBs on a solid surface to be effectively moved by magnetic force. Droplets may be driven by various methods or techniques including, for example, electrowetting, electrostatic, electromechanical, electrophoretic, dielectrophoretic, electroosmotic, thermocapillary, surface acoustic, and pressure.

Shah, Gaurav Jitendra↗

Mars Aqueous Chemistry Experiment (MACE)

The concept of an aqueous-based chemical analyzer for Martian surface materials has been demonstrated to be feasible. During the processes of analysis, design, breadboarding, and most importantly, testing, it has become quite apparent that there are many challenges in implementing such a system. Nonetheless, excellent progress has been made and a number of problems which arose have been solved. The ability to conduct this work under a development environment which is separate and which precedes the project-level development has allowed us to find solutions to these implementation realities at low cost. If the instrument had been selected for a mission without this laboratory pre-project work, the costs of implementation would be much higher. In the four areas covered in Sections D, E, F, and G of this Final Report, outstanding progress has been made. There still remains the task of flight-qualifying certain of the components. This is traditionally done under the aegis of a Flight Project, but just as the concept development can be done at much lower cost when kept small and focused, so could the qualification program of critical parts benefit. We recommend, therefore, that NASA consider means of such qualifications and brass-boarding, in advance of final flight development. This is a generic recommendation, but hardware such as the Mars aqueous chemistry experiment (MACE) and other similarly-new concepts are particularly applicable. MACE now has wide versatility, in being able to reliably dispense both liquids and solids as chemical reagents to an entire suite of samples. The hardware and the experiment is much simpler than was developed for the Viking Biology instrument, yet can accomplish all the inorganic chemical measurements that the Viking desing was capable of. In addition, it is much more flexible and versatile to new experiment protocols (and reagents) than the Viking design ever could have been. MACE opens up the opportunity for many different scientific disciplines to design sub- experiments and to benefit from the investigations that can be conducted. In this sense, it will have the value of a facility, although our recommendation would be that it be under the stewardship of a single lead investigator to insure that conflicting requirements not compromise the straight-forward design that have been achieved. MACE is an excellent candidate for upcoming Mars missions, including the Mars Surveyor Program (MSP) lander missions in 2001 and 2003. In addition, it could be used for any mission to the surface of any other planet or planetary body (including small bodies). An important next step is to encourage various investigators to propose specific uses for this experiment that specifically address their major scientific objectives for upcoming missions.

Benton, Clark C.↗

Shake-Down Spectroscopy as State- and Site-Specific Probe of Ultrafast Chemical Dynamics

Tracking the multifarious ultrafast electronic and structural changes occurring in a molecule during a photochemical transformation is a challenging endeavor that benefits from recent experimental and computational progress in time-resolved techniques. Measurements of valence electronic states, which provide a global picture of the bonding structure of the molecule, and core electronic states, which provide insight into the local environment, traditionally require different approaches and are often studied separately. Here, we demonstrate that X-ray pulses from a seeded free-electron laser (FEL) enable the measurement of high-resolution, time-resolved X-ray photoelectron spectra (XPS) that capture weak satellite states resulting from shake-down processes in a valence-excited molecule. This approach effectively combines the advantages of both valence- and core-state investigations. We applied this method to investigate photoexcited CS2 molecules, where the role of internal conversion (IC) and intersystem crossing (ISC) in determining the predissociation dynamics is controversial. We present XPS spectra from photoexcited CS2, obtained at the FERMI FEL. High-resolution measurements, compared to the corresponding spectra obtained from accurate multireference quantum chemical calculations, reveal that shake-down satellite channels are highly sensitive to both valence electronic and geometric changes. Previous studies of the predissociation dynamics have led to uncertain assignments of the branching between singlet and triplet excited states. We derive a propensity rule that demonstrates the spin-selectivity of the shake-downs. This selectivity allows us to unequivocally assign contributions from the bright and dark singlet excited states, with populations tracked along the predissociation dynamic pathway.

Thompson, Henry J. [Univ. of Southampton (United K↗

ECUT (Energy Conversion and Utilization Technologies) program: Biocatalysis project

The Annual Report presents the fiscal year (FY) 1988 research activities and accomplishments, for the Biocatalysis Project of the U.S. Department of Energy, Energy Conversion and Utilization Technologies (ECUT) Division. The ECUT Biocatalysis Project is managed by the Jet Propulsion Laboratory, California Institute of Technology. The Biocatalysis Project is a mission-oriented, applied research and exploratory development activity directed toward resolution of the major generic technical barriers that impede the development of biologically catalyzed commercial chemical production. The approach toward achieving project objectives involves an integrated participation of universities, industrial companies and government research laboratories. The Project's technical activities were organized into three work elements: (1) The Molecular Modeling and Applied Genetics work element includes research on modeling of biological systems, developing rigorous methods for the prediction of three-dimensional (tertiary) protein structure from the amino acid sequence (primary structure) for designing new biocatalysis, defining kinetic models of biocatalyst reactivity, and developing genetically engineered solutions to the generic technical barriers that preclude widespread application of biocatalysis. (2) The Bioprocess Engineering work element supports efforts in novel bioreactor concepts that are likely to lead to substantially higher levels of reactor productivity, product yields and lower separation energetics. Results of work within this work element will be used to establish the technical feasibility of critical bioprocess monitoring and control subsystems. (3) The Bioprocess Design and Assessment work element attempts to develop procedures (via user-friendly computer software) for assessing the energy-economics of biocatalyzed chemical production processes, and initiation of technology transfer for advanced bioprocesses.

Baresi, Larry↗

Data Analytics for Catalysis Predictions: Are We Ready Yet?

Catalysis informatics has received tremendous attention in recent years as a tool to design catalysts and discover unique descriptors that capture the relationships between chemical properties and catalytic performance. One of the stop-gaps in understanding catalytic effects, which is often ignored and limits the deployment of data science tools, relates to the lack of uniform data. The catalytic cleavage of C–X (X= H, C, N, and O) bonds is relevant to many fundamental catalytic processes. In this Perspective, we performed data analytics on four groups of C–X cleavage reactions that are common in production, upcycling, or reactive separation: the C–C cleavage in cyclopropyl alcohol, the C–H cleavage in hydroacylation reactions, the C–O cleavage in β-O-4 linkages, and the C–N cleavage in amides, using experimental data collected from the literature to understand their underlying correlations. Experimental variables of high impact are identified for each reaction by dimensionality reduction methods. We highlight the urgent need for experimental data sets that include full details on the reaction conditions, such as reagent concentration, reaction temperature, or time in machine-readable forms. We discuss the potential improvement of the data of these reactions and promising approaches such as autonomous experiments to fill the gaps in unbiased experimental data. Finally, we also address the early stage consideration of separation aspects in the experimental design of efficient catalytic systems for these fundamental examples of chemical reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CMPO-Functionalized Silica Sorbents for pH-Tunable Separation and Enrichment of Rare-Earth Elements from Environmental Matrices

Rare-earth elements (REEs) are crucial in many applications, yet mutual separation is challenging due to their similar chemical behavior. Octylphenyl- N,N-diisobutyl carbamoyl methyl phosphine oxide (CMPO) is an organophosphorus ligand originally developed for extracting actinides and lanthanides from spent nuclear fuel. Here, we report a pH-tunable CMPOfunctionalized silica sorbent for selective REE separation from complex aqueous matrices. A CMPO-associated silica gel sorbent was synthesized and characterized by Brunauer−Emmett−Teller (BET) surface area, scanning electron microscopy, and X-ray photoelectron spectroscopy to confirm the surface functionalization and binding behavior. Sorbent performance was evaluated by using a synthetic 46- element solution and a real phosphate rock fertilizer leachate. Notably, REEs were successfully eluted with ultrapure water, demonstrating reversible desorption controlled by pH adjustment. Packed-bed column studies increased the REE mass fraction from 3.6% to 64% (20-fold enrichment), with up to 30-fold enrichment of neodymium. The adsorption process follows the Langmuir isotherm behavior and follows pseudo-second-order kinetics. The uptake capacity of 1 μmol of REEs per 4.2 μmol of CMPO supports the formation of a predominantly 4:1 ligand:rare earth element(III) pseudocomplex. These results demonstrate CMPO-functionalized silica as a selective, water-elutable, and low-chemical-input platform for sustainable REE recovery from environmental and industrial sources.

chelating ligands↗

Treatment Prevents Corrosion in Steel and Concrete Structures

In the mid-1990s, to protect rebar from corrosion, NASA developed an electromigration technique that sends corrosion-inhibiting ions into rebar to prevent rust, corrosion, and separation from the surrounding concrete. Kennedy Space Center worked with Surtreat Holding LLC, of Pittsburgh, Pennsylvania, a company that had developed a chemical option to fight structural corrosion, combining Surtreat's TPS-II anti-corrosive solution and electromigration. Kennedy's materials scientists reviewed the applicability of the chemical treatment to the electromigration process and determined that it was an effective and environmentally friendly match. Ten years later, NASA is still using this approach to fight concrete corrosion, and it has also developed a new technology that will further advance these efforts-a liquid galvanic coating applied to the outer surface of reinforced concrete to protect the embedded rebar from corrosion. Surtreat licensed this new coating technology and put it to use at the U.S. Army Naha Port, in Okinawa, Japan. The new coating prevents corrosion of steel in concrete in several applications, including highway and bridge infrastructures, piers and docks, concrete balconies and ceilings, parking garages, cooling towers, and pipelines. A natural compliment to the new coating, Surtreat's Total Performance System provides diagnostic testing and site analysis to identify the scope of problems for each project, manufactures and prescribes site-specific solutions, controls material application, and verifies performance through follow-up testing and analysis.

Source record↗

Isotope harvesting from a NSCL beam blocker: Isolation of 173,174 lu

A decommissioned beam blocker from the National Superconducting Cyclotron Laboratory was processed for recovery of long-lived Lu radioisotopes at Lawrence Livermore National Laboratory. The beam blocker was a W alloy that had built up considerable levels of activation from high energy particle irradiation over the course of 20 years. The isolation of 173,174 Lu from the bulk material required a complex chemical separation scheme due to the large mass and the wide variety of elements present. The final yield of 173,174 Lu was 76.7 ± 4.8% with an extremely high radiopurity and chemical purity. The reduction in W mass from the initial material to the final sample was 8 × 10 10 . In conclusion, the results show great promise for extracting large quantities of Lu radioisotopes from these types of W beam blockers at the Facility for Rare Isotope Beams, which will be irradiated at levels significantly higher than the beam blocker investigated here.

and nuclear chemistry↗

Bubble Mass Transport Measurement in the Large-Scale Test Loops at Oak Ridge National Laboratory

Molten salts are complex fluids that incorporate multi-phase behavior depending on the chemistry and the physical properties of the entrained components. These components include the carrier salt, the actinide fuel, and fission, activation, and corrosion products, the concentrations of which depends on the burnup history of the salt. Radionuclide transport from the salt into the cover gas / off-gas system depends on volatility as predicted by thermochemistry, but data from the Molten Salt Reactor Experiment (MSRE) conducted in the late 1960s suggest that bubble formation and transport are also important. Anomalously high fractions of noble metals were found in the off-gas system and were attributed to transportation with parent salt aerosols and their association with rising noble gas bubbles. The prediction of such phenomena requires coupled neutronic, thermal hydraulic, and chemical equilibrium calculations, the framework of which is being developed within the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program supported by the US Department of Energy (DOE) Office of Nuclear Energy (NE). However, separate effects tests and models of experiments using tools such as SAM and Thermochimica can guide model developers through important processes. Conversely, model development guides the choice of experiments and systems to provide data that are relevant for validation. This report describes several experiments that tracked gas transport in molten salts, ranging from small-scale systems to large-scale loops. Gas transportation in a molten salt, LiCl-KCl, has been studied using the shadowgraph technique. Sensors such as residual gas analysis, Raman spectroscopy, and laser-induced breakdown spectroscopy have been tested for off-gas measurements. These data were used to interpret how the gases move through the upstream salt / cover gas and the interface between them. Differential pressure measurements were able to detect individual gas bubbles as they popped at the liquid–gas interface. Salt aerosols were collected on a cascade impactor. Their formation was also observed directly via the shadowgraph method, and most of these aerosols were launched ballistically into the cover gas. Fine mists could also be observed. Convection currents through the salt were visualized and can be used to calculate the thermophysical properties of the salt itself. The apparatuses described in this report and in a previous work (McFarlane et al. 2023) have been commissioned and are available for use in making further measurements of salt/surrogate fission product behavior. Novel approaches using neutron imaging are planned for the study of fluoride salts, which cannot be contained in quartz, so shadowgraph visualization is not available. Bubble transport in convective flow and in a slow-moving salt column are planned. The mobile laser-induced breakdown spectroscopy (LIBS) system is available for several applications, including iodine capture in a molten hydroxide scrubber, H2 transport though molten salts to complement Raman analysis, and online tracking of salt aerosol generation, transport, and deposition. This report summarizes the findings from FY24 and the plans for FY25. The work completes milestone M2AT-24OR0702013 of the DOE-NE Advanced Reactor Technology, Molten Salt Reactor Campaign, DOE-NE-5.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Advanced air revitalization for optimized crew and plant environments

The Hybrid Air Revitalization System (HARS) closed ecosystem concept presented encompasses electrochemical CO2 and O2 separators, in conjunction with a mechanical condenser/separator for maintaining CO2, O2, and humidity levels in crew and plant habitats at optimal conditions. HARS requires no expendables, and allows flexible process control on the bases of electrochemical cell current, temperature, and airflow rate variations. HARS capacity can be easily increased through the incorporation of additional chemical cells. Detailed system flowcharts are provided.

Lee, M. G.↗

Toward Rapid Actinium-225 Purification via Membrane Adsorbers with Covalently Tethered Diglycolamide Ligands

Extractive diglycolamide (DGA) resins are used in several state-of-the-art techniques for purifying 225 Ac, a promising radiometal for targeted alpha therapy. Unfortunately, separation processes that rely on resins are often limited to slow flow rates, high elution volumes, and long processing times. Membrane adsorbers functionalized with DGA ligands are an alternative separation material that may overcome these challenges. This work presents (1) the synthesis of an aminated tetrahexyldiglycolamide ligand, (2) the covalent tethering of the ligand to electrospun poly(vinylbenzyl chloride) fiber mats, and (3) the adsorption and desorption of La(III) and 225 Ac. Chemical and physical characterization supports the covalent tethering of the ligand to the fiber mat, as well as the preservation of the fiber surface area and porosity after functionalization. Equilibrium adsorption experiments were performed with stable La(III) and radioactive 225 Ac. Trends in affinity are consistent between commercial resins and the synthesized membrane adsorbers; however, the Langmuir constants and the maximum binding capacity of the membrane adsorbers were generally lower than the resins. Despite these differences, the modeled selectivity for an equimolar solution of La(III)/ 225 Ac in 10 M nitric acid is 57. Furthermore, 225 Ac is rapidly desorbed from the fibers in 10 M nitric acid (<20 min). The La(III)/ 225 Ac selectivity and rapid 225 Ac desorption indicate this class of materials is promising for rapid radioanalytical separations.

07 ISOTOPE AND RADIATION SOURCES↗

Assessment of critical-fluid extractions in the process industries

The potential for critical-fluid extraction as a separation process for improving the productive use of energy in the process industries is assessed. Critical-fluid extraction involves the use of fluids, normally gaseous at ambient conditions, as extraction solvents at temperatures and pressures around the critical point. Equilibrium and kinetic properties in this regime are very favorable for solvent applications, and generally allow major reductions in the energy requirements for separating and purifying chemical component of a mixture.

Source record↗

Unravelling the radiation-induced redox chemistry of plutonium ions in aqueous solution

Plutonium plays a critical role in nuclear fuel cycle technologies, but our understanding of its fundamental radiation-induced redox chemistry is limited. Changes in oxidation states affect the speciation and transport of plutonium ions in solution. For example, solvent extraction techniques used to separate and recover plutonium from used nuclear fuel rely on the selective formation, maintenance, and complexation of specific plutonium oxidation states. However, radiolytically generated radicals, ions, and molecules can drive the oxidation state distribution of plutonium ions far from equilibrium, ultimately changing the physical and chemical properties of the bulk system. These radiation-induced processes are inevitable due to the ionizing radiation fields generated by the radioactive decay of plutonium and its daughter nuclides. Therefore, mechanistically understanding how plutonium's various oxidation states respond to ionizing radiation is essential for predicting its behavior in solution. Here, we present significant advances in our understanding of radiation-induced plutonium redox chemistry by using time-resolved (electron pulse) and dose accumulation (alpha and gamma) irradiation techniques, along with quantitative multiscale modeling methods.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Plasma Chemical Conversion and Resource Generation Beyond Low-Earth Orbit

As humanity gears up for its return to the moon after more than half a century, collaborative efforts between NASA, Artemis Accords Partners, and private industry are underway to establish the necessary infrastructure and technologies for lunar habitation and eventual Mars exploration. However, the traditional ISS resupply and waste management model is impractical and economically infeasible for prolonged missions to the Moon and Mars. Advanced chemical conversion technologies are needed to generate vital consumable products from local planetary resources (ISRU) and recycled gasses and waste within semi-closed loop life-support systems. Low-temperature plasma reactors are emerging power-to-gas technologies with the potential to facilitate various chemical synthesis processes with hardware commonality and redundancy. In plasma-based systems, electrical power is used to ionize a feedstock gas, creating a highly reactive environment that leverages electron excitation chemistry to break stable molecular bonds and form value added products. Unlike thermal chemical processes, plasma reactors operate at non-equilibrium conditions, allowing for lower-temperature operation and instantaneous start-up, making them adaptable to intermittent power availability. Moreover, their scalability permits deployment in both portable astronaut systems and large-scale industrial setups for colonies. One promising application of plasmas is for CO 2 conversion. Carbon dioxide comprises 96% of the Martian atmosphere and is a byproduct of human respiration, which typically must be scrubbed and vented from space habitats. A plasma source integrated with membrane separation technology could generate a stream of oxygen for life support and rocket propellant. CO 2 splitting may also be beneficial as a precursor to manufacture carbon-based products and fuels in situ, like methane, methanol, and polyethylene. Plasma-assisted CO 2 conversion is a simpler case to study without the concern of selectivity and is the first step toward complex chemical synthesis. This work presents preliminary experimental case study from a plasma reactor for CO 2 conversion and casts a vision for the potential of plasma technologies in a sub-architecture for resource production to enable the next generation of human spaceflight activities.

Plasma↗