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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 1,279 records · Page 71

Dual Tunability for Uncatalyzed N‐Alkylation of Primary Amines Enabled by Plasma‐Microdroplet Fusion

Abstract The fusion of non‐thermal plasma with charged microdroplets facilitates catalyst‐free N‐alkylation for a variety of primary amines, without halide salt biproduct generation. Significant reaction enhancement (up to >200×) is observed over microdroplet reactions generated from electrospray. This enhancement for the plasma‐microdroplet system is attributed to the combined effects of energetic collisions and the presence of reactive oxygen species (ROS). The ROS (e.g., O 2 ⋅ − ) act as a proton sink to increase abundance of free neutral amines in the charged microdroplet environment. The effect of ROS on N‐alkylation is confirmed through three unique experiments: (i) utilization of radical scavenging reagent, (ii) characterization of internal energy distribution, and (iii) controls performed without plasma, which lacked reaction acceleration. Establishing plasma discharge in the wake of charged microdroplets as a green synthetic methodology overcomes two major challenges within conventional gas‐phase plasma chemistry, including the lack of selectivity and product scale‐up. Both limitations are overcome here, where dual tunability is achieved by controlling reagent concentration and residence time in the microdroplet environment, affording single or double N‐alkylated products. Products are readily collected yielding milligram quantities in eight hours. These results showcase a novel synthetic strategy that represents a straightforward and sustainable C−N bond‐forming process.

Chemistry↗

Nanoscale Perspectives of Metal Degradation via In Situ Atom Probe Tomography

Abstract We report a unique in situ instrument development effort dedicated to studying gas/solid interactions relevant to heterogeneous catalysis and early stages of oxidation of materials via atom probe tomography and microscopy (APM). An in situ reactor cell, similar in concept to other reports, has been developed to expose nanoscale volumes of material to reactive gas environments, in which temperature, pressure, and gas chemistry are well controlled. We demonstrate that the combination of this reactor cell with APM techniques can aid in building a better mechanistic understanding of resultant composition and surface and subsurface structure changes accompanying gas/surface reactions in metal and metal alloy systems through a series of case studies: O 2 /Rh, O 2 /Co, and O 2 /Zircaloy-4. In addition, the basis of a novel operando mode of analysis within an atom probe instrument is also reported. The work presented here supports the implementation of APM techniques dedicated to atomic to near-atomically resolved gas/surface interaction studies of materials broadly relevant to heterogeneous catalysis and oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Fulvic Acid on Uranium(VI) Sorption Kinetics

Many studies by Dr. James A. Davis and others have demonstrated the influence of natural organic matter (NOM) on metal sorption and transport behavior in subsurface environments. Overall, NOM effects on metal sorption have been ascribed to: (1) different sorption affinities of metal-ligand solution complexes compared to ‘free’ metals in solution, and (2) NOM sorption onto minerals leading to competitive sorption behavior and/or changes in mineral surface characteristics. All of these processes have the potential to decrease metal sorption onto mineral surfaces, and alter the pH-dependence of metal sorption characteristics. Maybe even more importantly, a change in metal sorption mechanisms in the presence of NOM may lead to differences in metal surface speciation and affect the potential for later metal desorption and remobilization. Furthermore, it is well-known that overall reaction rates change if the series of elemental reactions comprising a reaction pathway has been altered. In the presence of NOM, metal-ligand dissociation reactions occurring prior to the sorption of ‘free’ metal ions may slow down overall metal sorption kinetics. In addition, a competition between metals and organic ligands binding to the same reactive surface sites may potentially decrease metal sorption rates based on mass action principles. Last, the sorption kinetics of metal-ligand solution complexes may be controlled by the rates of NOM surface reactions, which could be either faster or slower than ‘free’ metal sorption depending on ligand sorption mechanisms. In this presentation, we will use a uranium(VI)-fulvic acid-silica sand system to demonstrate how kinetic sorption experiments – combined with modeling strategies – can provide a powerful tool to study changes in metal sorption mechanisms as a function of organic ligand concentrations. Based on our kinetic sorption data and modeling-based data interpretation, U(VI) sorption onto silica sand can be either faster or slower in the presence of fulvic acid compared to a ligand-free system, depending on the relative concentrations of metals, organic ligands and mineral surface sites. Supporting simulations of U(VI) solution speciation and mineral surface characterization data further allowed us to conclude that a shift occurred from competitive sorption behavior to strong influences of uranium(VI)-fulvic acid complexes with increasing ligand concentrations in this system.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Feedback regulation of crystal growth by buffering monomer concentration

Abstract Crystallization is a ubiquitous means of self-assembly that can organize matter over length scales orders of magnitude larger than those of the monomer units. Yet crystallization is notoriously difficult to control because it is exquisitely sensitive to monomer concentration, which changes as monomers are depleted during growth. Living cells control crystallization using chemical reaction networks that offset depletion by synthesizing or activating monomers to regulate monomer concentration, stabilizing growth conditions even as depletion rates change, and thus reliably yielding desired products. Using DNA nanotubes as a model system, here we show that coupling a generic reversible bimolecular monomer buffering reaction to a crystallization process leads to reliable growth of large, uniformly sized crystals even when crystal growth rates change over time. Buffering could be applied broadly as a simple means to regulate and sustain batch crystallization and could facilitate the self-assembly of complex, hierarchical synthetic structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Redox-controlled reorganization and flavin strain within the ribonucleotide reductase R2b–NrdI complex monitored by serial femtosecond crystallography

Redox reactions are central to biochemistry and are both controlled by and induce protein structural changes. Here, we describe structural rearrangements and crosstalk within the Bacillus cereus ribonucleotide reductase R2b–NrdI complex, a di-metal carboxylate-flavoprotein system, as part of the mechanism generating the essential catalytic free radical of the enzyme. Femtosecond crystallography at an X-ray free electron laser was utilized to obtain structures at room temperature in defined redox states without suffering photoreduction. Together with density functional theory calculations, we show that the flavin is under steric strain in the R2b–NrdI protein complex, likely tuning its redox properties to promote superoxide generation. Moreover, a binding site in close vicinity to the expected flavin O 2 interaction site is observed to be controlled by the redox state of the flavin and linked to the channel proposed to funnel the produced superoxide species from NrdI to the di-manganese site in protein R2b. These specific features are coupled to further structural changes around the R2b–NrdI interaction surface. The mechanistic implications for the control of reactive oxygen species and radical generation in protein R2b are discussed

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Diffusion in mixed solvents - On the viscosity question

Linear plots of reaction rate vs reciprocal of solvent viscosity are generally used as the classifying criteria for diffusion controlled reactions in fluid solutions and to determine reaction mechanisms in mixed hydroxylic solvents like glycerol and water. This paper presents data which shows that the above-mentioned criteria are insufficient in many cases where nonideal mixed solvent systems are used to increase solvent viscosity. Data correlations suggest that the excess functions determine the variation in reaction rate constants. Kinetic parameters are presented for sucrose-water and methanol-water solvent systems for a reaction involving Fe(CN)6 and zinc uroporphyrin.

Carapellucci, P. A.↗

Attitude control of large solar power satellites

Satellite power systems are a promising future source of electrical energy. However, the very large size solar power satellites (relative to contemporary spacecraft) requires investigation of the resulting attitude control problems and of appropriate control techniques. The principal effects of the large size are a great increase in sensitivity to gravity-gradient torques and a great reduction in structural bending frequencies with the attendant likelihood of undesirable control system interaction. A wide variety of control techniques are investigated to define approaches that minimize implementation penalties. These techniques include space-constructed momentum wheels, gravity-gradient stabilization, quasi-inertial free-drift modes, and various reaction control thruster types, some of which reduce the implementation penalties to a few percent of the spacecraft mass. The control system/structural dynamic interaction problem is found to have a tractable solution. Some of the results can be applied to other large space structure spacecraft.

Oglevie, R. E.↗

LQC control for the Mini-Mast experiment

The Mini-Mast system is briefly reviewed, and results of a simulation study of the LQG control for the Mini-Mast experiment are reported. In particular, attention is given to problems and limitations related to the testing of control laws using reaction mass actuators, such as accounting for force and stroke limits of these devices. The local controller used in the study and the algorithm for converting the force commands of the LQG algorithm to position commands for the reaction mass device are described. It is shown that the LQG generated damping is reduced when a local controller is used and the position command is not saturated; it drops still further when the position command is saturated.

Montgomery, R. C.↗

Electron-impact ionization and electron attachment cross sections of radicals important in transient gaseous discharges

Electron-impact ionization and electron attachment cross sections of radicals and excited molecules were measured using an apparatus that consists of an electron beam, a molecular beam and a laser beam. The information obtained is needed for the pulse power applications in the areas of high power gaseous discharge switches, high energy lasers, particle beam experiments, and electromagnetic pulse systems. The basic data needed for the development of optically-controlled discharge switches were also investigated. Transient current pulses induced by laser irradiation of discharge media were observed and applied for the study of electron-molecule reaction kinetics in gaseous discharges.

Lee, Long C.↗

Calcium-Magnesium-Alumino-Silicates (CMAS) Reaction Mechanisms and Resistance of Advanced Turbine Environmental Barrier Coatings for SiC/SiC Ceramic Matrix Composites

Environmental barrier coatings (EBCs) and SiC/SiC ceramic matrix composites (CMCs) systems will play a crucial role in future turbine engines for hot-section component applications because of their ability to significantly increase engine operating temperatures, reduce engine weight and cooling requirements. The development of prime-reliant environmental barrier coatings is an essential requirement to enable the applications of the 2700-3000 F EBC - CMC systems. This presentation primarily focuses on the reaction mechanisms of advanced NASA environmental barrier coating systems, when in contact with Calcium-Magnesium Alumino-Silicates (CMAS) at high temperatures. Advanced oxide-silicate defect cluster environmental barrier coatings are being designed for ultimate balanced controls of the EBC temperature capability and CMAS reactivity, thus improving the CMAS resistance. Further CMAS mitigation strategies are also discussed.

Environmental barrier coatings (EBCs)↗

Coupling subsurface and above-surface models for optimizing the design of borefields and district heating and cooling systems in the presence of varying water-table depth. In: Proceedings, 46th Workshop on Geothermal Reservoir Engineering

Dynamic energy simulation is important for the design and sizing of district heating and cooling systems with geothermal heat exchange. Current modeling approaches in building and district energy simulation tools typically consider heat conduction through the ground between boreholes, without flow of groundwater. On the other hand, detailed simulation tools for subsurface heat and mass transfer exist, but these fall short in simulating above-surface energy systems. To support the design and operation of such systems, we have developed a coupled model including a software package for building and district energy simulation, and software for detailed heat and mass transfer in the ground. For the first, we use the open-source Modelica Buildings Library, which includes dynamic simulation models for building and district energy and control systems. For the heat and mass transfer in the soil, we use the TOUGH simulator. TOUGH can model heat and multi-phase, multi-component mass transport for a variety of fluid systems, as well as chemical reactions, in fractured porous media. In previous work, we described the coupling of these software packages, including how time-dependent boundary conditions for the borehole walls are synchronized for use in Modelica and TOUGH. We verified that the coupled Modelica/TOUGH code produced consistent results with the original Modelica code for an idealized problem in which heat transfer was purely by conduction in a uniform geologic medium. Here, we examine less idealized problems for which TOUGH’s advanced capabilities for modeling fluid flow are required. The first problem has a shallow vadose zone, and the second problem has a thicker vadose zone with a water-table depth that varies in time, which requires a fine vertical grid discretization for the TOUGH model.

Doughtry, Christine↗

Lunar Reconnaissance Orbiter (LRO) Sun Safe Mode

The Lunar Reconnaissance Orbiter (LRO), a spacecraft designed and built at the National Aeronautics and Space Administration s (NASA) Goddard Space Flight Center (GSFC) in Greenbelt, MD, was launched on June 18, 2009 from Cape Canaveral. It is currently in orbit about the Moon taking detailed science measurements and providing a highly accurate mapping of the suface in preparation for the future return of astronauts to a permanent moon base. Onboard the spacecraft is a complex set of algorithms designed by the attitude control engineers at GSFC to control the pointig for all operational events, including anomalies that require the spacecraft to be put into a well known attitude configuration for a sufficiently long duration to allow for the investigation and correction of the anomaly. GSFC level requirements state that each spacecraft s control system design must include a configuration for this pointing and lso be able to maintain a thermally safe and power positive attitude. This stable control algorithm for anomalous events is commonly referred to as the safe mode and consists of control logic thatwill put the spacecraft in this safe configuration defined by the spacecraft s hardware, power and environment capabilities and limitations. The LRO Sun Safe mode consists of a coarse sun-pointing set of algorithms that puts the spacecraft into this thermally safe and power positive attitude and can be achieved wihin a required amount of time from any initial attitude, provided that the system momentum is within the momentum capability of the reaction wheels. On LRO the Sun Safe mode makes use of coarse sun sensors (CSS), an inertial reference unit (IRU) and reaction wheels (RW) to slew the spacecraft to a solar inertial pointing. The CSS and reaction wheels have some level of redundancy because of their numbers. However, the IRU is a single-point-failure piece of hardware. Without the rate information provided by the IRU, the Sun Safe control algorithms could not maintain the required pointing, so a sub-mode of the Sun Safe mode that does not use the IRU was designed. This submode, referred to as the Sun Safe Gyroless control mode, consists of an algorithm that estimates rate information from the CSS and the RW measurements. RW momentum information is used to estimate the body rate parallel to the target sunline, which CSS alone would not be able to observe. Sun Safe can be autonomously, or via ground command, entered from any other control mode and in the event the IRU is not providing rate information, the control mode is switched to the gyroless submode. This paper looks at the design of the Sun Safe modes and discusses the constraints placed on the algorithm and how the mode wored around these constraints. Items of particular interest include CSS placement on the Solar Array (SA) and its implications to design, estimation of body rate information for the Sun Safe Gyroless control mode, and the effect of solar eclipse on each of the Sun Safe modes. Placing CSS on the SA was necessary for the means to put the Sun along the targeted sun-line, nominally normal to the SA panels, for all operational considerations. This had design implications for determining a sun vector during normal SA operations, if one or both gimbals become inoperable and when the SA is in a stowed configuration. The ability of body rate estimation in Sun Safe Gyroless not only uses CSS sun vector data but requires RW momentum measuremens to estimate rates parallel to the sun-line. LRO encounters solar eclipses of some length for most of its orbits about the Moon. With the lack of CSS measurement data a design was implemented in both Sun Safe and Sun Safe Gyroless, they differ because of having or not having IRU measurement data, to carry the spacecraft through these eclipse periods. This paper also includes some discussion of sun avoidance and how it affected design decisions during nominal and eclipse perids for each of the Sun Safe modes.

Garrick, Joseph↗

Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst, prepared at The University of Tulsa, at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

Abraham, Martin↗

Chemically controlled shape-morphing of elastic sheets

Two-dimensional responsive materials that change shape into complex three-dimensional structures are valuable for creating systems ranging from wearable electronics to soft robotics. Typically, the final 3D structure is unique and predetermined through the materials’ processing. Here, we use theory and simulation to devise a distinctive approach for driving shape changes of 2D elastic sheets in fluid-filled microchambers. The sheets are coated with catalyst to generate controllable fluid flows, which transform the sheets into complex 3D shapes. A given shape can be achieved by patterning the arrangement of the catalytic domains on the sheet and introducing the appropriate reactant to initiate a specific catalytic reaction. Moreover, a single sheet that encompasses multiple catalytic domains can be transformed into a variety of 3D shapes through the addition of one or more reactants. Materials systems that morph on-demand into a variety of distinct structures can simplify manufacturing processes and broaden the utility of soft materials.

36 MATERIALS SCIENCE↗

Design of an Excavation Robot: Regolith Advanced Surface Systems Operations Robot (RASSOR) 2.0

To continue on a sustainable and flexible path, NASA needs to address the challenge of collecting and moving large amounts of regolith at the destination. Acquiring the water resources on Mars will require mining significant quantities of regolith and this is not possible with the state-of-the-art low mass excavation systems. Low gravity environments (Mars = 3/8 G) and launch mass restrictions limit the traction and the resulting reaction force of the vehicle, making current terrestrial techniques impractical. This project addressed this challenge by developing a completely new technology that can mine large quantities of regolith on Mars. Recent measurements by the “Curiosity” rover on Mars have found that the regolith contains ~ 2% water by weight globally, ~4% in Jezero Crater (Human Architecture Team’s reference landing site), and much more at the poles(Leshin et al, 2013). RASSOR 2.0 is a planetary excavator, which has a mass of 66 kg, with a 0.38 kg vehicle mass per kilogram, per hour of excavation rate and power usage of 4 W per kg of regolith excavation rate. A single RASSOR 2.0 can excavate a minimum of 2.7 metric tons of regolith per day.This is accomplished by using counteracting excavation forces on two opposing digging implements called bucket drums and an autonomous mining control system. This work has addressed several major research areas outlined in the NASA Technology Area (TA) 04 Robotics & Autonomous Systems and TA 07 Human Destination Systems roadmaps. This project started at Technology Readiness Level (TRL) 4 as a low fidelity “proof of concept” prototype which has successfully demonstrated basic regolith simulant excavation functionality in a lab-scale gravity off load test. The foundational technology described here was awarded US patent number: US 9027265 for a “Zero horizontal reaction force excavator” on May 12, 2015.

RASSOR↗

Impact of different catalysis supported by oyster shells on the pyrolysis of tyre wastes in a single and a double fixed bed reactor

Highlights: • An innovative way in the disposal of tyre wastes with energy recovery by pyrolysis is proposed. • Performance of catalysts is improved by spreading them over layers of oyster shells. • One or two levels of supported catalytic beds may favor the quantity and/or the calorific value of the pyrolysis by-products. - Abstract: The treatment and disposal of tyres from vehicles has long been of considerable environmental importance. Studies have been undertaken to reduce their environmental impact. In this study, an alternative gas was produced from automobile tyre wastes by the means of a controlled pyrolysis. To do so, a novel catalytic system was designed with the aim of increasing the rate of conversion and improving the quality of the pyrolysis products. This work aimed also to reduce the severity of the overall reactions, by using powder catalysts (MgO, Al{sub 2}O{sub 3}, CaCO{sub 3}, and zeolite ZSM-5) uniformly distributed on two layers of oyster shells (OS) particles. The catalyst/tyres mass ratio was kept for all the tests at 1/30. The pyrolysis reactor was maintained at 500 °C and the influence of each catalyst and of the number of shell beds (0, 1 or 2), on the yield and composition of the derived products, was examined. The gas yields could contribute by 1.2% of total consumption in Tunisia. Furthermore, some combinations could upgrade the derived gas and made it possible to use it as such or with the minimum of post-treatment. It was found that, with the use of supported catalyst, the gas produced is 45% greater compared to classical thermal pyrolysis. The Heating value of the produced gas was also improved by the use of supported catalysts; it was found 16% greater with the use of Al{sub 2}O{sub 3}/OS compared to non-catalytic pyrolysis. When compared to the gas obtained from only one catalytic supported bed, the sulfur content was reduced by 80% with the use of CaCO{sub 3}/OS on two catalytic beds.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments

Uranyl peroxide capsules are a fascinating class of polyoxometalates (POMs), discovered only in the 21st century. Understanding the reactivity between peroxide, alkali cations, and uranyl in alkaline solutions is important in nuclear science disciplines including mineralogy, nuclear energy, and legacy nuclear wastes. In this work, we have developed a general procedure to isolate different fragments of the uranyl-peroxide POM capsules, using organic solvents to partially remove K + salts from crude solids of the monomer building block UO 2 (O 2 ) 3 4– (K–U 1 ), leading to stabilization of these reactive fragments. Higher polarity organic solvents remove more K + salts from the crude solid, owed to higher solubility, resulting in more extensive linking of uranyl peroxide building units. By this strategy we have isolated and structurally characterized a dimer K 6 [(UO 2 ) 2 (O 2 ) 4 (OH) 2 ]·7H 2 O (K–U 2 ) and a hexamer face frequently observed in the capsules, K 12 [(UO 2 ) 6 (O 2 ) 9 (OH) 6 ]$·x$H 2 O(K–U 6 ). Comparing experimental and computed Raman spectra shows that these intermediates crystallize by a solid-to-solid transformation, via polymerization of the monomer building block. By small-angle X-ray scattering (SAXS), we track the conversion of the fragments to POM capsules; the reaction rate increases from K–U 1 (days) < K–U 2 (hours) < K–U 6 (instantaneous). This study provides a general synthetic procedure to isolate metastable uranyl peroxide oligomers and control the oligomerization, which will be later applied to systems with the heavier alkalis that are even less stable.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Achieving the hydrogen shot: Interrogating ionomer interfaces

The aim of this study is to enable the hydrogen economy and decarbonize various sectors in our environment that requires less expensive and more durable water electrolyzers, which can meet the Hydrogen-Shot target. The key is to improve the ionomer interfaces in low-temperature water electrolyzers as rapidly as possible, but to do so, it requires a systematic and holistic campaign combining both experiments and theory. In this perspective, we discuss the issues of electrolyzers and needs for translational science. We then present the approach that the Energy EarthShot Research Center: Center for Ionomer-based Water Electrolysis is taking in hopes of inspiring the community with this approach that can be leveraged to multiple problems and technologies.Graphical abstractHighlightsOne way to achieve the Hydrogen-Shot goal of low-cost, clean hydrogen, is advancing research and development on the interfaces of water electrolyzers for both performance and lifetime. The Center for Ionomer-based Water Electrolysis is exploring new techniques and strategies to not only interrogate interfacial phenomena in water electrolyzers to increase efficiency and durability, but also a new paradigm related to synergistic, cojoined experimental and theoretical research.DiscussionCatalyst\ionomer interfaces are complex and not fully understood, but through investigating different interfaces and utilizing digital and physical twins, we can elucidate key mechanisms and understanding.Understanding the dynamic double layer in electrochemical systems that use solid electrolytes is crucial to identifying and mitigating the controlling phenomena to enable increased performance and durability at the technology level.Studying the time and length scales of interfacial changes can be a powerful tool to understand reaction mechanisms and changes in the electrolyzer performance and durability.

Fornaciari, Julie C↗