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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Microscopic Investigation of H 2 Reduced CuO x /Cu(111) and ZnO/CuO x /Cu(111) Inverse Catalysts: STM, AP-XPS, and DFT Studies

Understanding the reduction mechanism of ZnO/CuO x interfaces by hydrogen is of great importance for advancing the performance of industrial catalysts for CO 2 hydrogenation to methanol. Here, the reduction of pristine and ZnO-modified CuO x /Cu(111) by H 2 was investigated using ambient pressure scanning tunnelling microscopy (AP-STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory (DFT). The morphological changes and reaction rates seen for the reduction of CuO x /Cu(111) and ZnO/CuO x /Cu(111) are very different. On CuO x /Cu(111), perfect "44" and "29" structures displayed a very low reactivity towards H 2 at room temperature. A long induction period associated with an autocatalytic process was observed to enable the reduction by the removal of chemisorbed non-lattice oxygen initially and lattice oxygen sequentially at the CuO x -Cu interface, which led to formation of oxygen deficient "5-7" hex and honeycomb structures. In the final stages of the reduction process, regions of residual oxygen species and metallic Cu were seen. The addition of ZnO particles to CuO x /Cu(111) opened new reaction channels. On the ZnO sites, the dissociation of H 2 was fast and H adatoms easily migrated to adjacent regions of copper oxide. This hydrogen spillover substantially enhanced the rate of oxygen removal, resulting in the rapid reduction of the copper oxide located in the periphery of the zinc oxide islands with no signs for the reduction of ZnO. The deposited ZnO completely modified the dynamics for H 2 dissociation and hydrogen migration, providing an excellent source for CO 2 hydrogenation processes on the inverse oxide/metal system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Electronic origin of reorganization energy in interfacial electron transfer

Electron transfer (ET) reactions underpin energy conversion and chemical transformations in both biological and a biological systems. The efficiency of any ET process relies on achieving a desired ET rate within an optimal driving force range. Marcus theory provides a microscopic framework for understanding the activation free energy—and therefore the rate—of ET in terms of a key parameter: the reorganization energy. For electrified solid–liquid interfaces, it has long been conventionally understood that only factors in the electrolyte phase are responsible for determining the reorganization energy and that the electronic density of states (DOS) of the electrode only serves to dictate the number of thermally accessible channels for ET. Here we show instead that the electrode DOS plays a central role in governing the reorganization energy, far outweighing its conventionally assumed role. Using atomically layered heterostructures, we tune the DOS of graphene and measure outer-sphere ET kinetics. We find the ensuing variation in ET rate arises from strong modulation in a reorganization energy associated with image potential localization in the electrode. Here we redefine the traditional paradigm of heterogeneous ET kinetics, revealing a deeper role of the electrode electronic structure in interfacial reactivity.

Electrochemistry↗
DOE OSTI2020

Multi-modal surface analysis of porous films under operando conditions

Practical catalysts with a porous framework, such as zeolites, host catalytic reactions at active sites engrained in the pores and channels of the scaffold. The mechanism of interaction at these active sites, defining catalyst performance, remains elusive, in large part, due to the lack of surface characterization methods available for thick films or powders. Here, we present thin film analogs of practical catalysts that allow for the implementation of surface characterization tools, including advanced microscopy and operando spectroscopy methodologies. Specifically, we investigated bilayer silica, MFI nanosheets, and UiO-66 thin films using a multi-modal approach addressing film growth, characterization, and gas adsorption aimed at understanding catalytic activity, reactivity, and selectivity properties, as defined by molecular-level changes in the reaction mechanism.

36 MATERIALS SCIENCE↗
NASA NTRS1997

O2 Herzberg State Reaction with N2: A Possible Source of Stratospheric N2O

The goal of this one-year investigation was to determine whether N2O is formed in atmospherically significant quantities by the reaction of vibrationally excited levels of the O2((A3 Sigma(sub u)(sup +)) state with nitrogen. O2(A3 Sigma(sub u)(sup +)) is made throughout the upper stratosphere in considerable amounts by solar photoabsorption, and only a very small reactive yield is necessary for this mechanism to be a major N2O source. By long-term 245-252 nm irradiation of O2/N2 mixtures on- and off-resonance with absorption lines in the O2(A3 Sigma(sub u)(sup +) - X3 Sigma(sub g)(sup -)) transition, followed by N2O analysis by frequency-modulated diode laser absorption spectroscopy, we determined an upper limit for the N2O yield of the candidate reaction. This limit, 3 x 10(exp -5), eliminates O2(A3 Sigma(sub u)(sup +)) + N2 as a significant channel for the generation of stratospheric N2O. In further measurements, we established that N2O is stable under our photolysis conditions, showing that the small amounts of ozone generated from the reaction of O2(A) and O2 do not indirectly lead to destruction of N2O.

Slanger, Tom G.↗
DOE OSTI2020

Direct time-resolved detection and quantification of key reactive intermediates in diethyl ether oxidation at T = 450–600 K

High-pressure multiplexed photoionization mass spectrometry (MPIMS) with tunable vacuum ultraviolet (VUV) ionization radiation from the Lawrence Berkeley Labs Advanced Light Source is used to investigate the oxidation of diethyl ether (DEE). Kinetics and photoionization (PI) spectra are simultaneously measured for the species formed. Several stable products from DEE oxidation are identified and quantified using reference PI cross-sections. In addition, we directly detect and quantify three key chemical intermediates: peroxy (ROO˙), hydroperoxyalkyl peroxy (˙OOQOOH), and ketohydroperoxide (HOOP[double bond, length as m-dash]O, KHP). These intermediates undergo dissociative ionization (DI) into smaller fragments, making their identification by mass spectrometry challenging. Furthermore, with the aid of quantum chemical calculations, we identify the DI channels of these key chemical species and quantify their time-resolved concentrations from the overall carbon atom balance at T = 450 K and P = 7500 torr. This allows the determination of the absolute PI cross-sections of ROO˙, ˙OOQOOH, and KHP into each DI channel directly from experiment. The PI cross-sections in turn enable the quantification of ROO˙, ˙OOQOOH, and KHP from DEE oxidation over a range of experimental conditions that reveal the effects of pressure, O 2 concentration, and temperature on the competition among radical decomposition and second O 2 addition pathways.

42 ENGINEERING↗
DOE OSTI2020

Comparison of Hafnium Dioxide and Zirconium Dioxide Grown by Plasma-Enhanced Atomic Layer Deposition for the Application of Electronic Materials

We report the growth of nanoscale hafnium dioxide (HfO 2 ) and zirconium dioxide (ZrO 2 ) thin films using remote plasma-enhanced atomic layer deposition (PE-ALD), and the fabrication of complementary metal-oxide semiconductor (CMOS) integrated circuits using the HfO 2 and ZrO 2 thin films as the gate oxide. Tetrakis (dimethylamino) hafnium (Hf[N(CH 3 ) 2 ] 4 ) and tetrakis (dimethylamino) zirconium (IV) (Zr[N(CH 3 ) 2 ] 4 ) were used as the precursors, while O 2 gas was used as the reactive gas. The PE-ALD-grown HfO 2 and ZrO 2 thin films were analyzed using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HRTEM). The XPS measurements show that the ZrO 2 film has the atomic concentrations of 34% Zr, 2% C, and 64% O while the HfO 2 film has the atomic concentrations of 29% Hf, 11% C, and 60% O. The HRTEM and XRD measurements show both HfO 2 and ZrO 2 films have polycrystalline structures. n-channel and p-channel metal-oxide semiconductor field-effect transistors (nFETs and pFETs), CMOS inverters, and CMOS ring oscillators were fabricated to test the quality of the HfO 2 and ZrO 2 thin films as the gate oxide. Current-voltage (IV) curves, transfer characteristics, and oscillation waveforms were measured from the fabricated transistors, inverters, and oscillators, respectively. The experimental results measured from the HfO 2 and ZrO 2 thin films were compared.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS1992

Spectral identification of chemisorbed CO2 and application to Mars analog materials

The goal of this work is to identify the spectral signature of chemisorbed CO2, to test the efficacy of carbonate formation on Mars-analog materials via CO2 chemisorption, and to identify the surface-chemical characteristics of good chemisorbents, with the intent of assessing the possible geochemical importance of CO2 chemisorption as a quasipermanent CO2 sink in the Martian environment. Our approach is to search for infrared spectral bands that result from chemisorption of CO2 molecules onto chemical reagents and Mars-analog materials, and to identify the salient differences in adsorbents that favor strong, permanent CO2 chemisorption. The total amount of CO2 in the early Martian atmosphere, and consequent surface temperatures, are unknown. A CO2 greenhouse may not have been an adequate mechanism under any circumstances; however, it if were, then most of that CO2 must still be in the near-surface environment; no escape mechanism that could remove it after the decline of channeling has been identified. The only plausible reservoir is carbonate, and there are various remote sensing techniques that can be used to search for it. We are investigating CO2 chemisorption as a permanent CO2 sink, and to aid in interpretation of remotely sensed IR spectra of Mars. A common effect reported in CO2 adsorption studies is the formation of a layer of carbonate or bicarbonate anions on adsorbents that have OH- groups available on their surfaces. Inorganic hydroxyls occur on phyllosilicates, amorphous silicates, metal oxides and hydroxides; it is the most abundant and reactive surface functional group on the surfaces of terrestrial silicates. The process responsible for the reaction is chemisorption. Chemisorption is distinguished from physical adsorption in that there is a transfer of electrons between species, and the formation of a chemical bond. The heat of chemisorption is typically of the same order as heats of chemical reaction (i.e., a few hundred to a few thousand kJ/mole), as opposed to heats of physical adsorption (a few kJ per mole). Chemisorption is an activated process that is promoted by an increase in temperature - quite the opposite of physical adsorption. Chemisorption is not reversible in the sense that physical adsorption is.

Zent, A. P.↗
DOE OSTI2022

Updates and Validation for the n+ 63,65 Cu Cross Sections [Abstract]

The neutron induced total, elastic, and capture cross sections of 63,65 Cu isotopes were selected for evaluation in the resolved and unresolved resonance energy ranges by the National Criticality Safety Program to resolve discrepancies related to benchmark performance. This is especially evident for the series of ZEUS benchmarks in which copper is used as a reflector. Because copper is also used as structural material in both fission and fusion reactors, the need to address benchmark discrepancies linked to nuclear data deficiencies is a task of primary importance. The aim of this work is to describe the steps of evaluation work towards a consistent improvement of the benchmark performance. The R-matrix analysis with the SAMMY code focused on the 63 Cu(n,γ) reaction channel between 100-300 keV coupled to unresolved resonance region parameters up to 650 keV to fit average cross section data from a recent experiment. Due to the high sensitivity of many benchmarks to elastic scattering angular distribution data, especially for the 65 Cu isotope, the impact of these data was tested by generating Legendre coefficients from both resonance parameters and the Hauser-Feshbach model. Guided by the findings of Shaw et al., the performance of the current evaluation for 65 Cu was compared to that of ENDF/B-VII.1 and ENDF/B-VIII.0 by testing the reactivity coefficients corresponding to the validation suite of experimental criticality benchmarks for thermal, intermediate, and fast systems taken from the International Criticality Safety Benchmark Experiments Project Handbook. The benchmark performance is especially sensitive to 63 Cu(n,γ) and 65 Cu elastic scattering for neutron energies in the 100–500 keV region, whereas 100 keV is the upper limit of the resolved resonance region in the ENDF/B-VIII.0 evaluations for 63,65 Cu. The results highlight the need to handle the transition from the resolved resonance region to the high energy region carefully.

07 ISOTOPE AND RADIATION SOURCES↗
NASA NTRS1996

Chlorine Deactivation in the Lower Stratospheric Polar Regions during late Winter: Results from UARS

Recovery from enhanced chlorine conditions in the lower stratospheric polar regions of both hemispheres is investigated using data from the Upper Atmosphere Research Satellite (UARS). Microwave Limb Sounder (MLS) measurements of ClO within the polar vortices are used to infer ClO(sub x) (ClO + 2Cl202) abundances that are then correlated with simultaneous Cryogenic Limb Array Etalon Spectrometer (CLAES) measurements of ClON02 and Halogen Occultation Experiment (HALOE) measurements of HCl obtained starting within 5 days of the end of the MLS and CLAES high-latitude observing periods in each hemisphere. Time series of vortex-averaged mixing ratios are calculated on two potential temperature surfaces (585 K and 465 K) in the lower stratosphere for approximately month-long intervals during late winter: August 17 - September 17, 1992, in the southern hemisphere and February 12 - March 16, 1993, in the northern hemisphere. The observed mixing ratios are adjusted for the effects of vertical transport using diabatic vertical velocities estimated from CLAES tracer data. In the northern hemisphere, the decrease in ClO, is balanced on both surfaces by an increase in ClON02- In the southern hemisphere, continuing polar stratospheric cloud activity prevents ClO from undergoing sustained decline until about September 3. In contrast to the northern hemisphere, there is no significant chemical change in vortex-averaged ClON02 at 465 K, and there is an apparent decrease in ClON02 at 585 K, even after the enhanced ClO abundances have started to recede. Results from the SLIMCAT chemical transport model initialized with UARS data and run with OH + ClO yields HCl + 02 as an 8% channel suggest that the primary recovery product in the south during this time period is not ClON02, but HCl. HALOE HCl mixing ratios are extrapolated back to the time of the MLS and CLAES data. At 585 K, the chlorine budget can be made to balance by extrapolating HCl back to a value of 0.6 parts per billion by volume (ppbv) at the beginning of the study period; at 465 K, the contribution from extrapolated HCl is not sufficient to offset the loss in ClOx, and there is a slight imbalance between the decrease in reactive chlorine and the change in chlorine reservoirs. The difficulty in closing the chlorine budget in the southern hemisphere may arise from complications caused by ongoing activation, incomplete photochemical assumptions, and/or inadequate data quality.

Santee, M. L.↗
NASA NTRSDate not supplied

Advancing Autonomy in Distributed Space Systems: Insights From on-Orbit Testing with the Starling 1.0 Mission

Autonomous decision-making is crucial for enhancing mission effectiveness in Distributed Space Systems (DSS), particularly in multi-spacecraft operations where communication constraints and mission complexity pose challenges. The Distributed Spacecraft Autonomy (DSA) team at NASA’s Ames Research Center is advancing autonomy in DSS through five key technical areas: distributed resource and task management, reactive operations, system modeling and simulation, human-swarm interaction, and ad hoc network communications. The DSA experiment onboard the Starling 1.0 Mission showcases collaborative resource allocation for multi-point science data collection with four small spacecraft. Autonomy in decision-making is highlighted as a crucial factor for multi-spacecraft missions, enabling spacecraft to operate independently, reducing reliance on ground control. This capability is particularly significant for future deep-space missions, where communication delays and limited data transmission capacity make traditional command and control approaches impractical. This demonstration focuses on a GPS Channel Selection Experiment, leveraging emergent capabilities like "shared sampling" and "simultaneous sampling" to optimize channel selection across the spacecraft swarm. The experiment aims to capture ionospheric phenomena such as the Equatorial Ionization Anomaly and Polar Patches. The DSA system's autonomous reconfiguration ability is showcased, emphasizing its adaptability to natural phenomena without significant integration efforts. The GPS Channel Selection Experiment utilizes a dual-band GPS receiver to estimate plasma density in the ionosphere. Explorative and exploitative channel selections are employed based on the nature of observed phenomena. The performance of DSA algorithms is evaluated in terms of optimal channel allocations and responsiveness to changes in observed features. The DSA Flight Software utilizes the Core Flight System (cFS) framework, ensuring compatibility with the Starling 1.0 flight mission software. DSA showcases results from RTI’s Connext DDS Micro communication middleware, enabling message routing over the Ad-Hoc Network of Starling 1.0. This paper provides a comprehensive overview of the DSA experiment's initial results, emphasizing the advancements in autonomy for Distributed Space Systems and the successful collaboration with the Starling 1.0 mission.

Caleb Ashmore Adams↗
NASA NTRS1981

Metal-semiconductor interfacial reactions - Ni/Si system

X-ray photoelectron spectroscopy and channeling measurements with MeV He-4(+) ions have been used to probe the structure of the interface in the Ni/Si system. It is found that reactions occur where Ni is deposited on Si at 10 to the -10th torr: Si atoms are displaced from lattice sites, the Ni atoms are in an Si-rich environment, and the Ni/Si interface is graded in composition. Composition gradients are present at both interfaces in the Si/Ni2/Si/Ni system. For the Ni-Si system, cooling the substrate to 100 K slows down the reaction rate. The temperature dependence of the interfacial reactivity indicates the kinetic nature of metal-semiconductor interfaces.

Cheung, N. W.↗
DOE OSTI2020

Influence of ozone addition on the low-temperature oxidation of dimethyl ether in a jet-stirred reactor

The influence of ozone addition on the low-temperature oxidation of dimethyl ether (DME) was investigated experimentally in an atmospheric-pressure jet-stirred reactor, over the temperature range of 400–800 K. Detailed speciation information was obtained by employing synchrotron vacuum ultraviolet photoionization mass spectrometry. Experimental results revealed that the ozone addition had a positive influence on the production of the highly reactive intermediates. Moreover, the low-temperature reactivity of DME was significantly enhanced, which resulted in the broadening of the temperature window of fuel consumption and intermediates formation at lower temperatures. Therefore, novel experimental data of the low temperature regime (400–500 K) could be obtained. The data set of this special temperature regime yielded insights into the DME low-temperature kinetics, which were further supported with modeling analysis based on two existing DME models (Metcalfe et al., 2013; Wang et al., 2015) combined with an ozone sub-mechanism (Zhao et al., 2016). The analysis showed that temperature-sensitive reactions such as the second oxygen channel could be nearly “frozen” at this low temperature (T < 440 K). Furthermore, the production of some intermediates was found to be strongly governed by reaction pairs, such as CH 3 OCH 2 + O 2 = CH 3 OCH 2 O 2 and CH 3 OCH 2 + O 2 = 2 CH 2 O + OH for the CH 2 O formation. This finding could be useful for examining branching ratios in both models, and the analysis suggested the further modification of the branching ratios for the oxygen addition to CH 3 OCH 2 O 2 pathways and the CH 3 OCH 2 O 2 self-reactions were required. Finally, the influences of the O 3 addition in the sensitive reactions of the fuel initial low-temperature oxidation were investigated in this work. It was interesting to note that O 3 addition could change the dominating reactions in the initial low-temperature oxidation, by the addition of some O 3 -related pathways with relatively high sensitivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Fluid inertia controls mineral precipitation and clogging in pore to network-scale flows

Mineral precipitation caused by fluid mixing presents complex control and predictability challenges in a variety of natural and engineering processes, including carbon mineralization, geothermal energy, and microfluidics. Precipitation dynamics, particularly under the influence of fluid flow, remain poorly understood. Combining microfluidic experiments and three-dimensional reactive transport simulations, we demonstrate that fluid inertia controls mineral precipitation and clogging at flow intersections, even in laminar flows. We observe distinct precipitation regimes as a function of Reynolds number (Re). At low Reynolds numbers (Re < 10), precipitates form a thin, dense layer along the mixing interface, which shuts precipitation off, while at high Reynolds numbers (Re > 50), strong three-dimensional flows significantly enhance precipitation over the entire intersection, resulting in rapid clogging. When injection rates from two inlets are uneven, flow symmetry-breaking leads to unexpected flow bifurcation phenomena, which result in enhanced concurrent precipitation in both downstream channels. Finally, we extend our findings to rough channel networks and demonstrate that the identified inertial effects on precipitation at the intersection scale are also present and even more dramatic at the network scale. This study sheds light on the fundamental mechanisms underlying mixing-induced mineral precipitation and provides a framework for designing and optimizing processes involving mineral precipitation.

Science & Technology - Other Topics↗
DOE OSTI2022

Comparison of basin-scale in situ and meteoric 10 Be erosion and denudation rates in felsic lithologies across an elevation gradient at the George River, northeast Tasmania, Australia

Long-term erosion rates in Tasmania, at the south ern end of Australia’s Great Dividing Range, are poorly known; yet, this knowledge is critical for making informed land-use decisions and improving the ecological health of coastal ecosystems. Here, we present quantitative, geologically relevant estimates of erosion rates for the George River basin, in northeast Tasmania, based on in situ-produced 10 Be ( 10 Be i ) measured from stream sand at two trunk channel sites and seven tributaries (mean: 24.1 ± 1.4 Mg km -2 yr -1 ; 1σ). These new 10 Bei-based erosion rates are strongly related to elevation, which appears to control mean annual precipitation and temperature, suggesting that elevation-dependent surface processes influence rates of erosion in northeast Tas mania. Erosion rates are not correlated with slope in contrast to erosion rates along the mainland portions of Australia’s Great Dividing Range. We also extracted and measured meteoric 10 Be ( 10 Be m ) from grain coatings of sand-sized stream sediment at each site, which we normalize to measured concentrations of reactive 9 Be and use to estimate 10 Be m -based denudation rates for the George River. 10 Bem/ 9 Be reac denudation rates replicate 10 Be i erosion rates within a factor of 3 but are highly sensitive to the value of 9 Be that is found in bedrock ( 9 Be parent ), which was unmeasured in this study. 10 Bem/ 9 Be reac denudation rates seem sensitive to recent mining, forestry, and agricultural land use, all of which resulted in widespread topsoil disturbance. Our findings suggest that 10 Bem/ 9 Be reac denudation metrics will be most useful in drainage basins that are geologically homogeneous, where recent disturbances to topsoil profiles are minimal, and where 9 Be parent is well constrained.

58 GEOSCIENCES↗
NASA NTRS2024

Analysis of faults and pit chains in Noctis Labyrinthus: Implications for early extension and possible magmatic plumbing

Noctis Labyrinthus has been a region of disputed origin due to its complexity and poor understanding of how various processes and mechanisms may have combined to form it. The surface is an integrated record of intensive tectonic activity expressed by a multiple extended sets of dip-slip faults oriented in different directions, and thought to have acted on this region over its history. These faults are always coalescent to pits and pit chains displaying a complicated geological history in the region. To understand this geological history, we mapped the surface features in Noctis Labyrinthus using the High-Resolution Stereo Camera (HRSC) onboard Mars Express ND2 nadir channel basemaps, and we adapted the Digital Terrain Map (DTM) from the Mission Experiment Gridded Data Record (MEGDR) of Mars Orbiter Laser Altimeter (MOLA) onboard Mars Global Surveyor (MGS) for the topography. We have investigated the spatial distribution and trend of fault systems, the pit chains' morphology, and the correlation between these two types of features. Our results show three fault systems: i) NS and NNE-SSW, ii) EW and ENE-WSW, and iii) NNW-SSE and NW. The analysis of the faults trending, cross-cutting correlation and the superimposition led to identify multiple intersections between these faults that have been alongside with the reactivations of some inherited faults. We interpreted the first system of fault to be related to coeval lateral extension, generated by regional stress tensor, which is probably related to the slight bending of Valles Marineris within two phases of bidirectional extension. The second system of faults has been generated by the radial oblate stress tensor related to the formation of the small shield volcanoes in Syria Planum. However, the third system is likely related to the external driving process, probably in the Tharsis province. We classified pits in four evolutionary stages based on their morphometric attributes. We believe that the formation of the pit chains in Noctis Labyrinthus is related to a surface collapse after a pressure drop related to the magma chamber deflation associated with Syria Planum volcanic province. We propose a deformational model based on early extension and magmatic plumbing as driving processes for the formation of Noctis Labyrinthus.

Mayssa El Yazidi↗
DOE OSTI2025

Gas-phase synthesis of naphthalene through an unconventional thermal alkyne–alkene [2 + 2] cycloaddition mechanism

Exotic cycloaddition entrance channels were discovered for the bimolecular gas-phase reactions of the phenylethynyl radical (C 6 H 5 CC, X 2 A 1 ) with ethylene-d 4 (C 2 D 4 ) and propylene (C 3 H 6 ) as explored under single-collision conditions utilizing the crossed molecular beams technique combined with electronic structure and statistical calculations. Connecting the concepts of barrierless entrance channels, excited states, and facile non-photochemically activated cycloadditions, the reaction pathway features an unconventional thermal [2 + 2] cycloaddition forming a four-membered ring collision complex followed by multiple isomerizations prior to unimolecular decomposition via atomic hydrogen loss to (un)substituted naphthalenes—naphthalene-d 4 (C 10 H 4 D 4 ) and 1-/2-methylnaphthalene (C 11 H 10 ). The small energy gap between the singly-occupied a 1 highest occupied molecular orbital (HOMO) with a σ-character and the underlying doubly-occupied b 1 molecular orbital with a π-character allows a facile promotion of an electron. This in turn enables a versatile low-temperature reactivity of phenylethynyl, where the end-on and side-on barrierless approaches of ethylene are due to its interaction with the σ and π orbitals, respectively, thus suggesting this mechanism as a possible method for tuning substituents in polycyclic aromatic hydrocarbon (PAH) formation and highlighting its versatility as a probe of fundamental carbon chemistry via counterintuitive cycloaddition reactions under single-collision conditions.

Goettl, Shane J. [University of Hawaii at Manoa, H↗
NASA NTRS2018

Demonstration of Subscale Cermet Fuel Specimen Fabrication Approach Using Spark Plasma Sintering and Diffusion Bonding

Nuclear thermal propulsion (NTP) has the potential to expand the limits of human space exploration by enabling crewed missions to Mars and beyond. The viability of NTP hinges on the development of a robust nuclear fuel material that can perform in the harsh operating environment (> or = 2500K, reactive hydrogen) of a nuclear thermal rocket (NTR) engine. Efforts are ongoing to develop fuel material and to assemble fuel elements that will be stable during the service life of an NTR. Ceramic-metal (cermet) fuels are being actively pursued by NASA Marshall Space Flight Center (MSFC) due to their demonstrated high-temperature stability and hydrogen compatibility. Building on past cermet fuel development research, experiments were conducted to investigate a modern fabrication approach for cermet fuel elements. The experiments used consolidated tungsten (W)-60vol%zirconia (ZrO2) compacts that were formed via spark plasma sintering (SPS). The consolidated compacts were stacked and diffusion bonded to assess the integrity of the bond lines and internal cooling channel cladding. The assessment included hot hydrogen testing of the manufactured surrogate fuel and pure W for 45 minutes at 2500 K in the compact fuel element environmental test (CFEET) system. Performance of bonded W-ZrO2 rods was compared to bonded pure W rods to access bond line integrity and composite stability. Bonded surrogate fuels retained structural integrity throughout testing and incurred minimal mass loss.

Barnes, Marvin W.↗
NASA NTRS2005

New Species of Fire Discovered: Fingering Flamelets Form a Dynamic Population

Poets and artists have long used fire as a metaphor for life. At the NASA Glenn Research Center, recent experiments in a subcritical Rayleigh number flow channel demonstrated that this analogy holds up surprisingly well when tools developed to characterize a biological population are applied to a class of fire that occurs in near-extinction, weakly convective environments (such as microgravity) or in vertically confined spaces (such as our apparatus). Under these conditions, the flame breaks into numerous 'flamelets" that form a Turing-type reaction-diffusion fingering pattern as they spread across the fuel. It is standard practice on U.S. spacecraft for the astronaut crew to turn off the ventilation to help extinguish a fire, both to eliminate the fresh oxygen supply and to reduce the distribution of the smoke. When crew members think that the fire is fully extinguished, they reactivate the ventilation system to clear the smoke. However, some flamelets can survive, and our experiments have demonstrated that flamelets quickly grow into a large fire when ventilation increases.

Olson, Sandra L.↗