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At least 541 records · Page 30

Nonthermal Plasma-Stimulated C–N Coupling from CH 4 and N 2 Depends on the Presence of Surface CH x and Plasma-Phase CN Species

Formation of C–N containing compounds from plasma-catalytic coupling of CH 4 and N 2 over various transition metals (Ni, Pd, Cu, Ag, and Au) is investigated using a multimodal spectroscopic approach, combining polarization-modulation infrared reflection–absorption spectroscopy (PM-IRAS) and optical emission spectroscopy (OES). Through sequential experiments utilizing CH 4 and N 2 nonthermal plasmas, we minimize plasma-phase reactions and identify key intermediates for C–N coupling on metal surfaces. Results show that simultaneous CH 4 and N 2 exposure with plasma stimulation produces surface C–N species. However, N 2 –CH 4 sequential exposure does not lead to C–N species formation, while CH 4 –N 2 sequential exposure reveals the presence of CH x surface species and CN radical species as key precursors to C–N species formation. From further analysis using X-ray photoelectron spectroscopy and liquid chromatography–mass spectrometry, the influence of exposure conditions on the degree of nitrogen incorporation and the nature of C–N species formed were revealed. The work highlights the importance of surface chemistry and exposure conditions in surface C–N coupling with plasma stimulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of methane mass transfer and sorption in Marcellus shale under variable net-stress

Natural gas in shale exists as free and adsorbed gas, subject to prevailing pore pressures and stress conditions. Accordingly, to accurately estimate/predict the shale gas recovery potential, a central requirement is to represent gas transport and sorption behavior under varying stress conditions. The objective of this work is to facilitate the interpretation of laboratory-scale experiments, at relevant conditions, in an attempt to bridge the gap in scales between laboratory- and field-scale observations. We have conducted a series of high-pressure experiments on a full-diameter core sample from the Marcellus shale. These include gas loading (pressure-decay) and depletion (production) experiments with pure methane (CH 4 ) at variable stress conditions to characterize transport and sorption behavior under reservoir-relevant conditions. Here we have formulated and applied a novel integral model for mass transfer and storage in multi-porosity shale systems that allows us to effectively investigate transport and sorption phenomena: We delineate gas transport by interpreting helium (He) pressure-decay experiments and demonstrate how to use the information gained to calculate the relevant transport coefficients of CH 4 and other gases. A separate measurement of the CH 4 sorption isotherm on a smaller sample (a shale cube) was interpreted and combined with the transport description to predict the production behavior of CH 4 from the experiments with the full-diameter core. Our experiments demonstrate that the representation of sorption hysteresis is crucial for predicting and guiding shale gas production: At the end of both gas production experiments, approximately 20% of the initial gas in place remained in the core. Without accounting for sorption hysteresis, our modeling demonstrates that the CH 4 production could be overestimated by 10%. We demonstrate that our integral, triple-porosity model provides an effective approach for the interpretation and prediction of gas transport and sorption behavior during loading and production experiments on shale cores under variable net-stress conditions. In summary, our work combines measurements and modeling of mass transfer and sorption in shales at different scales to validate a characterization approach that facilitates an improved understanding of shale gas production. Furthermore, the triple-porosity model utilized in our work defines a potential pathway for the translation of laboratory-scale experimentation to larger-scale applications.

58 GEOSCIENCES↗

The fate of carbon utilized by the subterranean termite Reticulitermes flavipes

Abstract Subterranean termites are ecosystem engineers that modulate the flow of carbon from dead wood to the atmosphere and soil, yet their contributions to the latter pool are largely unaccounted for in carbon cycling models. The fate of C from wood utilized by Reticulitermes flavipes (Kollar) was determined using a reductionist design in a closed system with δ 13 C labeled wood as a stable isotope tracer. The percentage of wood‐based carbon in termite respiratory gases, tissues, and organic deposits (frass and construction materials) was measured for five colonies to budget wood‐C mass distributed into metabolic and behavioral pathways during a 160‐h incubation period. We found that termites emitted 42% of the C from wood as gas (largely as carbon dioxide), returned 40% to the environment as organic deposits (frass and construction materials), and retained 18% in their tissues (whole alimentary tracts and de‐gutted bodies). Our findings affirm that termites are a source of greenhouse gases but are also ecosystem engineers that return approximately half the C from dead wood as organic deposits into their surrounding environment.

54 ENVIRONMENTAL SCIENCES↗

Advancing hydrogen production: A comprehensive review of wastewater reforming techniques, feedstocks, and opportunities

Wastewater is produced across nearly all human activities and requires treatment to safeguard human health and the natural environment. Treatment of wastewater often requires a large amount of thermal energy, resulting in wasted heat after the treatment process. Because hydrocarbon reforming needs both water and heat, the integration of wastewater treatment with hydrocarbon reforming, a process that produces synthesis gas rich in hydrogen, offers an excellent opportunity to utilize this waste heat and the impurities in wastewater to produce valuable hydrogen gas, to minimize waste from industrial processes, and to integrate water treatment with the hydrogen economy. Yet, no comprehensive literature review has been conducted to examine the integration of reforming and wastewater. To address this lack, we summarize the variety of catalytic reforming techniques available in the open literature and review the current literature on wastewater reforming with these techniques. Subsequently, we conduct a review of common types of wastewater contaminants and their possible effects on reforming catalyst performance and life. Lastly, three underexamined wastewater sources are identified, namely, oilfield wastewater, geothermal water, and mining and mineral processing wastewater, and their potential for future study as a reforming feedstock is examined.

08 HYDROGEN↗

Preliminary Kinetic Analysis of Non-Equilibrium Plasma- Assisted Methanol Pyrolysis and Oxidation Experiments

Efforts to enhance power generation efficiency and reduce emissions have driven interest in novel combustion techniques, including non-equilibrium plasma (NEP) ignitors. NEP ignitors show promise in improving energy conversion efficiency, fuel reforming, emission control, and lean-flammability limits. However, their adoption is hindered by a limited understanding of the interplay between plasma-enhanced combustion and thermal chemistry, particularly for complex fuels under engine-relevant conditions. Developing experimentally validated kinetic mechanisms is therefore critical. Additionally, the increasing interest in renewable biofuels like ethanol and methanol, coupled with the desirable qualities of NEP ignitors, presents a compelling opportunity for study. Therefore, this work acts as an extension of a previous work (Bopaiah et al., 2023) pertaining to the experimental results of NEP-assisted methanol pyrolysis and oxidation. Experiments were performed with a custom-built plasma flow reactor at 0.5 atm and temperatures from 523-1203 K. All reactive mixtures are extremely diluted to minimize exothermicity due to reactivity, allowing isothermal assumptions and the isolation of plasma chemistry from thermal chemistry. A dielectric barrier discharge plasma, at 14 kV and 15 ns full-width half maximum, was applied to the reactive mixture at varying frequencies to maintain the number of pulses with increasing temperature. Steady-state product speciation was performed downstream of the reactor with ex-situ GC/MS diagnostics. The attained experimental results were examined through in-depth analysis performed by means of an in-development plasma-coupled kinetic mechanism. As discussed in the previous work, the plasma significantly accelerates methanol pyrolysis, increasing stable intermediate production, including oxygenated and nitrile species. Plasma-assisted oxidation shows even faster fuel consumption compared to pyrolysis and a 200 K ignition shift compared to thermal oxidation. For plasma-assisted pyrolysis, the model demonstrates that accelerated fuel consumption stems from dissociative quenching of excited N2 states with fuel and H2, generating H radicals that react to rapidly form CH3 and CH2OH radicals. At low temperatures, these radicals recombine to produce oxygenates, while CH3 drives nitrile and hydrocarbon formation at higher temperatures. While the model captures pyrolysis trends well, discrepancies in methane, ethylene, and ethanol predictions are present. Similarly, the model faces challenges in accurately representing plasma-assisted oxidation, predicting a much steeper fuel gradient and ignition 100 K earlier than the experiment. While a similar scheme to pyrolysis is nested in the reaction pathway, the enhancement of the O and H radical fluxes and their initiation of the OH and HO2 radical pools dominate fuel and intermediate oxidation. The overestimation of these processes is shown to be responsible for the divergence of model from experiment. While the modelling predictions of this preliminary mechanism are not perfect, they serve as a valuable starting point. Primarily, they elicited new reaction pathways that are not otherwise possible in thermal chemistry induced reaction kinetics. The results also provide a basis for the future work that should be performed. For example, theoretical and experimental studies on excited nitrogen species and fuel/fuel radical interactions, quantification of the NOx production, and the kinetics behind the slow ignition observed in oxidation should be emphasized.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Approach-Phase Precision Landing with Hazard Relative Navigation: Terrestrial Test Campaign Results of the Morpheus/ALHAT Project

The Morpheus Project began in late 2009 as an ambitious e ort code-named Project M to integrate three ongoing multi-center NASA technology developments: humanoid robotics, liquid oxygen/liquid methane (LOX/LCH4) propulsion and Autonomous Precision Landing and Hazard Avoidance Technology (ALHAT) into a single engineering demonstration mission to be own to the Moon by 2013. The humanoid robot e ort was redirected to a deploy- ment of Robonaut 2 on the International Space Station in February of 2011 while Morpheus continued as a terrestrial eld test project integrating the existing ALHAT Project's tech- nologies into a sub-orbital ight system using the world's rst LOX/LCH4 main propulsion and reaction control system fed from the same blowdown tanks. A series of 33 tethered tests with the Morpheus 1.0 vehicle and Morpheus 1.5 vehicle were conducted from April 2011 - December 2013 before successful, sustained free ights with the primary Vertical Testbed (VTB) navigation con guration began with Free Flight 3 on December 10, 2013. Over the course of the following 12 free ights and 3 tethered ights, components of the ALHAT navigation system were integrated into the Morpheus vehicle, operations, and ight control loop. The ALHAT navigation system was integrated and run concurrently with the VTB navigation system as a reference and fail-safe option in ight (see touchdown position esti- mate comparisons in Fig. 1). Flight testing completed with Free Flight 15 on December 15, 2014 with a completely autonomous Hazard Detection and Avoidance (HDA), integration of surface relative and Hazard Relative Navigation (HRN) measurements into the onboard dual-state inertial estimator Kalman lter software, and landing within 2 meters of the VTB GPS-based navigation solution at the safe landing site target. This paper describes the Mor- pheus joint VTB/ALHAT navigation architecture, the sensors utilized during the terrestrial ight campaign, issues resolved during testing, and the navigation results from the ight tests.

Crain, Timothy P.↗

A shift between mineral and nonmineral sources of iron and sulfur causes proteome-wide changes in Methanosarcina barkeri

ABSTRACT Iron (Fe) and sulfur (S) are required elements for life, and changes in their availability can limit the ecological distribution and function of microorganisms. In anoxic environments, soluble Fe typically exists as ferrous iron [Fe(II)] and S as sulfide (HS − ). These species exhibit a strong affinity that ultimately drives the formation of sedimentary pyrite (FeS 2 ). Recently, paradigm-shifting studies indicate that Fe and S in FeS 2 can be made bioavailable by methanogens through a reductive dissolution process. However, the impact of the utilization of FeS 2 , as opposed to canonical Fe and S sources, on the phenotype of cells is not fully understood. Here, shotgun proteomics was utilized to measure changes in the phenotype of Methanosarcina barkeri MS grown with FeS 2 , Fe(II)/HS − , or Fe(II)/cysteine. Shotgun proteomics tracked 1,019 proteins overall, with 307 observed to change between growth conditions. Functional characterization and pathway analyses revealed these changes to be systemic and largely tangential to Fe/S metabolism. As a final step, the proteomics data were viewed with respect to previously collected transcriptomics data to deepen the analysis. Presented here is evidence that M. barkeri adopts distinct phenotypes to exploit specific sources of Fe and S in its environment. This is supported by observed protein abundance changes across broad categories of cellular biology. DNA adjacent metabolism, central carbon metabolism methanogenesis, metal trafficking, quorum sensing, and porphyrin biosynthesis pathways are all features in the phenotypic differentiation. Differences in trace metal availability attributed to complexation with HS − , either as a component of the growth medium [Fe(II)/HS − ] or generated through reduction of FeS 2 , were likely a major factor underpinning these phenotypic differences. IMPORTANCE The methanogenic archaeon Methanosarcina barkeri holds great potential for industrial bio-mining and energy generation technologies. Much of the biochemistry of this microbe is poorly understood, and its characterization will provide a glimpse into biological processes that evolved close to life’s origin. The discovery of its ability to extract iron and sulfur from bulk, solid-phase minerals shifted a longstanding paradigm that these elements were inaccessible to biological systems. The full elucidation of this process has the potential to help scientists and engineers extract valuable metals from low-grade ore and mine waste generating energy in the form of methane while doing so.

59 BASIC BIOLOGICAL SCIENCES↗

Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal–Organic Framework

Conversion of methane (CH 4 ) to ethylene (C 2 H 4 ) and/or acetylene (C 2 H 2 ) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH 4 controllably, and separating C 2+ products from unreacted CH 4 can be challenging. Here, we report the direct conversion of CH 4 to C 2 H 4 and C 2 H 2 driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal–organic framework material, MFM-300(Fe). The selectivity for the formation of C 2 H 4 and C 2 H 2 reaches 96% with a high time yield of 334 μmol g cat –1 h –1 . At a conversion of 10%, the selectivity to C 2+ hydrocarbons and time yield exceed 98% and 2056 μmol g cat –1 h –1 , respectively, representing a new benchmark for conversion of CH 4 . In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe–O(H)–Fe sites in activating CH 4 and stabilizing reaction intermediates via the formation of an Fe–O(CH 3 )–Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C 2 H 4 and C 2 H 2 from unreacted CH 4 for direct use. Integrating the processes of CH 4 activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the Surface Structure and Catalytic Activity of SnO x /Au(111) Inverse Catalysts for CO 2 and H 2 Activation

Carbon dioxide hydrogenation is a promising approach for the reduction of greenhouse gas pollution via the production of fuels and high-value chemicals utilizing C1 chemistry. In this process, the activation of nonpolar molecules, CO 2 and H 2 , at mild conditions is challenging. In this study, we report a well-defined inverse SnO x /Au(111) catalyst that shows the ability to activate both CO 2 and H 2 at room temperature. Scanning tunneling microscopy (STM) and ambient pressure X-ray photoemission spectroscopy (AP-XPS) are combined to understand the surface structure, growth mode, chemical state, and activity of SnO x /Au(111) surfaces. Nanostructures of SnO x at the sub-monolayer level were prepared by depositing Sn on Au(111) followed by O 2 oxidation. For the as-prepared SnO x /Au(111), two-dimensionally formed SnO x thin films on a Au(111) substrate were observed with STM of two different moieties, discernible based on their height: clusters (~0.4 Å) and nanoparticles (NPs, 1–2.5 Å), which are assigned to Sn–Au alloys and SnO x , respectively, in corroboration with XPS analysis. Furthermore, SnO x /Au(111) was annealed under UHV to test its thermal stability. Upon annealing at 400–600 K, a disappearance of SnO x NPs and reappearance of highly dispersed Sn clusters were clearly noticeable from the STM and XPS results, identifying the thermal decomposition of SnO x and subsequent formation of Sn–Au alloys on the surface due to the recombination of Sn clusters with Au. We investigated the reactivity of the SnO x /Au(111) surfaces toward CH 4 , CO 2 , and H 2 . The SnO x /Au(111) surfaces have excellent CO 2 and H 2 activation abilities even at room temperature with negligible reactivity for methane activation. Our AP-XPS results show that H 2 can be activated on the SnO x NPs by the reduction to Sn. For CO 2 , the activation and further dissociation are identified by a reoxidation of Sn with newly formed Sn–O bonds and the formation of surface carbon. Therefore, we propose that SnO x is a potential catalyst or additive to achieve CO 2 hydrogenation under mild conditions.

36 MATERIALS SCIENCE↗

Scale and Regionality of Nonelectric Markets for U.S. Nuclear Light Water Reactors

This study assesses existing and potential industries that could conceivably be directly coupled to existing nuclear reactors. The goal is to identify the scale, location, and accessibility of the candidate industrial-product markets, as well as process feedstocks that are available near the plants to establish new industries. For example, CO 2 as a feedstock can be combined with H 2 to produce formic acid (FA), transportation fuels, and lubricants. These new plants can be entirely supported with the heat and electricity provided by a nearby NPP. The potential demand for nonelectric industrial products was assessed by documenting current and possible growth of nonelectricity product markets considered. This assessment used DOE- and industry-supported tools, data, and projections to capture regional industrial market opportunities. Electricity-capacity markets that reward large and reliable generators, such as NPPs, were considered because the electricity market will likely continue to be an important revenue source to NPPs. The key is to balance the needs of energy customers so as to optimize revenue for the affiliated energy customers or partners. In most cases, flexible plant energy delivery and power generation for the grid will require either energy storage or a stock of intermediate products to sustain the industrial customers when the NPP dispatches electricity to the grid. A diverse mix of temperate regions with operating NPPs around the U.S.—representing a variety of operating markets, local generation mix, and seasonal climates—were chosen for this market study. Both current and future market opportunities for candidate industrial-product markets surrounding these NPPs were studied. Figure 2 illustrates the regions chosen for this study. The success of developing nonelectric industrial-product markets as alternative revenue-generating sources for LWRs depends, not only on demand from growing existing markets, such as petroleum refining and NH 3 production, but also on the development of new markets such as light-duty (LD) and heavy-duty (HD) hydrogen FCEVs, synfuels, chemical production, biofuels, metal refining, injection of hydrogen into NG pipelines for gas power-generating units, FA, polymers, and close-coupled industrial heat applications, all of which can significantly increase demand relative to current levels while decarbonizing energy sectors. This study also presents a sample analysis of the economics of hydrogen production in an area of Minnesota, considering the capital and operating costs of a hydrogen plant as well as the local market demand for hydrogen. It includes some assumptions on electricity-grid pricing, showing how hydrogen could be integrated with an NPP and be competitive with the incumbent hydrogen-production process, steam methane reforming (SMR). The objectives of this study include: Provide U.S. NPP operators a robust sampling of the market demand location, scale, and accessibility (including storage and transportation) of the wide variety of industrial-product choices that can be produced using nuclear thermal energy and electricity proximate to a subset of U.S. NPPs to inform the industry of the potential opportunity; show examples and trade-off analyses of how U.S. LWR operators can access these markets, including storage and transportation of industrial products to their intended markets; and present a general analysis example for one industrial product (hydrogen) in one region (Minnesota area), including production, storage, and transportation, to show how nuclear-hybrid integrated energy systems (IESs) could access local markets and improve the profitability of an NPP.

03 NATURAL GAS↗

Chemical looping conversion of CH4/CO2 to syngas on 5wt.%Ni@Ce0.6Zr0.4O2 catalyst: Impact of dynamic accumulation of surface carbon and oxygen vacancies

Syngas, a combination of carbon monoxide (CO) and hydrogen (H2), is a precursor to many chemicals and fuels, contributing to the billion-dollar global hydrocarbon industry. Chemical looping reforming (CLR) of the greenhouse gases methane (CH4) and carbon dioxide (CO2) allows for energy-efficient production of syngas. 5wt.% nickel (Ni) on ceria-zirconia (5wt%Ni@Ce0.6Zr0.4O2) mixed metal oxide catalyst was investigated here to explore pathways for enhanced syngas production on sustainable earth-abundant transition metal supported catalysts. The role of reduction-oxidation (redox) state of the catalyst, and carbon formation on the catalyst surface during chemical looping is explored to drive superior reaction kinetics, conversions, selectivity, and syngas ratios (H2/CO). The bulk and surface structure of the catalyst, along with carbon deposition features were characterized by electron microscopy, X-Ray diffraction, and ex situ Raman spectroscopy. The dynamic evolution of catalysts under CLR reaction conditions and the intrinsic reaction mechanisms were probed with in situ Raman spectroscopy, in situ Fourier transform spectroscopy, dynamic oxygen storage capacity (DOSC), and the Temporal Analysis of Products (TAP) reactor studies. Intrinsic kinetics of syngas production via CLR was correlated to the redox state of catalyst and the participation of nickel-catalyzed multiwalled carbon nanotube (CNT) growth, allowing enhanced CLR reaction performance.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Single-Cell Genomics of Novel Actinobacteria With the Wood–Ljungdahl Pathway Discovered in a Serpentinizing System

Serpentinite-hosted systems represent modern-day analogs of early Earth environments. In these systems, water-rock interactions generate highly alkaline and reducing fluids that can contain hydrogen, methane, and low-molecular-weight hydrocarbons-potent reductants capable of fueling microbial metabolism. In this study, we investigated the microbiota of Hakuba Happo hot springs (~50°C; pH~10.5–11), located in Nagano (Japan), which are impacted by the serpentinization process. Analysis of the 16S rRNA gene amplicon sequences revealed that the bacterial community comprises Nitrospirae (47%), “Parcubacteria” (19%), Deinococcus-Thermus (16%), and Actinobacteria (9%), among others. Notably, only 57 amplicon sequence variants (ASV) were detected, and fifteen of these accounted for 90% of the amplicons. Among the abundant ASVs, an early-branching, uncultivated actinobacterial clade identified as RBG-16-55-12 in the SILVA database was detected. Ten single-cell genomes (average pairwise nucleotide identity: 0.98–1.00; estimated completeness: 33–93%; estimated genome size: ~2.3 Mb) that affiliated with this clade were obtained. Taxonomic classification using single copy genes indicates that the genomes belong to the actinobacterial class-level clade UBA1414 in the Genome Taxonomy Database. Based on metabolic pathway predictions, these actinobacteria are anaerobes, capable of glycolysis, dissimilatory nitrate reduction and CO 2 fixation via the Wood–Ljungdahl (WL) pathway. Several other genomes within UBA1414 and two related class-level clades also encode the WL pathway, which has not yet been reported for the Actinobacteria phylum. For the Hakuba actinobacterium, the energy metabolism related to the WL pathway is likely supported by a combination of the Rnf complex, group 3b and 3d [NiFe]-hydrogenases, [FeFe]-hydrogenases, and V-type (H + /Na + pump) ATPase. The genomes also harbor a form IV ribulose 1,5-bisphosphate carboxylase/oxygenase (RubisCO) complex, also known as a RubisCO-like protein, and contain signatures of interactions with viruses, including clustered regularly interspaced short palindromic repeat (CRISPR) regions and several phage integrases. This is the first report and detailed genome analysis of a bacterium within the Actinobacteria phylum capable of utilizing the WL pathway. The Hakuba actinobacterium is a member of the clade UBA1414/RBG-16-55-12, formerly within the group “OPB41.” We propose to name this bacterium ‘Candidatus Hakubanella thermoalkaliphilus.'

59 BASIC BIOLOGICAL SCIENCES↗

Fuels Containing Methane of Natural Gas in Solution

While exploring ways of producing better fuels for propulsion of a spacecraft on the Mars sample return mission, a researcher at Johnson Space Center (JSC) devised a way of blending fuel by combining methane or natural gas with a second fuel to produce a fuel that can be maintained in liquid form at ambient temperature and under moderate pressure. The use of such a blended fuel would be a departure for both spacecraft engines and terrestrial internal combustion engines. For spacecraft, it would enable reduction of weights on long flights. For the automotive industry on Earth, such a fuel could be easily distributed and could be a less expensive, more efficient, and cleaner-burning alternative to conventional fossil fuels. The concept of blending fuels is not new: for example, the production of gasoline includes the addition of liquid octane enhancers. For the future, it has been commonly suggested to substitute methane or compressed natural gas for octane-enhanced gasoline as a fuel for internal-combustion engines. Unfortunately, methane or natural gas must be stored either as a compressed gas (if kept at ambient temperature) or as a cryogenic liquid. The ranges of automobiles would be reduced from their present values because of limitations on the capacities for storage of these fuels. Moreover, technical challenges are posed by the need to develop equipment to handle these fuels and, especially, to fill tanks acceptably rapidly. The JSC alternative to provide a blended fuel that can be maintained in liquid form at moderate pressure at ambient temperature has not been previously tried. A blended automotive fuel according to this approach would be made by dissolving natural gas in gasoline. The autogenous pressure of this fuel would eliminate the need for a vehicle fuel pump, but a pressure and/or flow regulator would be needed to moderate the effects of temperature and to respond to changing engine power demands. Because the fuel would flash as it entered engine cylinders, relative to gasoline, it would disperse more readily and therefore would mix with air more nearly completely. As a consequence, this fuel would burn more nearly completely (and, hence, more cleanly) than gasoline does. The storage density of this fuel would be similar to that of gasoline, but its energy density would be such that the mileage (more precisely, the distance traveled per unit volume of fuel) would be greater than that of either gasoline or compressed natural gas. Because the pressure needed to maintain the fuel in liquid form would be more nearly constant and generally lower than that needed to maintain compressed natural gas in liquid form, the pressure rating of a tank used to hold this fuel could be lower than that of a tank used to hold compressed natural gas. A mixture of natural gas and gasoline could be distributed more easily than could some alternative fuels. A massive investment in new equipment would not be necessary: One could utilize the present fuel-distribution infrastructure and could blend the gasoline and natural gas at almost any place in the production or distribution process - perhaps even at the retail fuel pump. Yet another advantage afforded by use of a blend of gasoline and natural gas would be a reduction in the amount of gasoline consumed. Because natural gas costs less than gasoline does and is in abundant supply in the United States, the cost of automotive fuel and the demand for imported oil could be reduced.

Sullivan, Thomas A.↗

Catalyzed Combustion In Micro-Propulsion Devices: Project Status

In recent years, there has been a tendency toward shrinking the size of spacecraft. New classes of spacecraft called micro-spacecraft have been defined by their mass, power, and size ranges. Spacecraft in the range of 20 to 100 kg represent the class most likely to be utilized by most small sat users in the near future. There are also efforts to develop 10 to 20 kg class spacecraft for use in satellite constellations. More ambitious efforts will be to develop spacecraft less than 10 kg, in which MEMS fabrication technology is required. These new micro-spacecraft will require new micro-propulsion technology. Although micro-propulsion includes electric propulsion approaches, the focus of this proposed program is micro-chemical propulsion which requires the development of microcombustors. As combustors are scaled down, the surface to volume ratio increases. The heat release rate in the combustor scales with volume, while heat loss rate scales with surface area. Consequently, heat loss eventually dominates over heat release when the combustor size becomes smaller, thereby leading to flame quenching. The limitations imposed on chamber length and diameter has an immediate impact on the degree of miniaturization of a micro-combustor. Before micro-combustors can be realized, such a difficulty must be overcome. One viable combustion alternative is to take advantage of surface catalysis. Micro-chemical propulsion for small spacecraft can be used for primary thrust, orbit insertion, trajectory-control, and attitude control. Grouping micro-propulsion devices in arrays will allow their use for larger thrust applications. By using an array composed of hundreds or thousands of micro-thruster units, a particular configuration can be arranged to be best suited for a specific application. Moreover, different thruster sizes would provide for a range of thrust levels (from N s to mN s) within the same array. Several thrusters could be fired simultaneously for thrust levels higher than the basic units, or in a rapid sequence in order to provide gradual but steady low-g acceleration. These arrays of micro-propulsion systems would offer unprecedented flexibility and redundancy for satellite propulsion and reaction control for launch vehicles. A high-pressure bi-propellant micro-rocket engine is already being developed using MEMS technology. High pressure turbopumps and valves are to be incorporated onto the rocket chip . High pressure combustion of methane and O2 in a micro-combustor has been demonstrated without catalysis, but ignition was established with a spark. This combustor has rectangular dimensions of 1.5 mm by 8 mm (hydraulic diameter 3.9 mm) and a length of 4.5 mm and was operated at 1250 kPa with plans to operate it at 12.7 MPa. These high operating pressures enable the combustion process in these devices, but these pressures are not practical for pressure fed satellite propulsion systems. Note that the use of these propellants requires an ignition system and that the use of a spark would impose a size limitation to this micro-propulsion device because the spark unit cannot be shrunk proportionately with the thruster. Results presented in this paper consist of an experimental evaluation of the minimum catalyst temperature for initiating/supporting combustion in sub-millimeter diameter tubes. The tubes are resistively heated and reactive premixed gases are passed through the tubes. Tube temperature and inlet pressure are monitored for an indication of exothermic reactions and composition changes in the gases.

Sung, C. J.↗

Nano Icy Moons Propellant Harvester

As one of just a few bodies identified in the solar system with a liquid ocean, Europa has become a top priority in the search for life outside of Earth. However, cost estimates for exploring Europa have been prohibitively expensive, with estimates of a NASA Flagship class orbiter and lander approaching $5 billion. ExoTerra's NIMPH offers an affordable solution that can not only land, but return a sample from the surface to Earth. NIMPH combines solar electric propulsion (SEP) technologies being developed for the asteroid redirect mission and microsatellite electronics to reduce the cost of a full sample return mission below $500 million. A key to achieving this order-of-magnitude cost reduction is minimizing the initial mass of the system. The cost of any mission is directly proportional to its mass. By keeping the mission within the constraints of an Atlas V 551 launch vehicle versus an SLS, we can significantly reduce launch costs. To achieve this we reduce the landed mass of the sample return lander, which is the largest multiplier of mission mass, and shrink propellant mass through high efficiency SEP and gravity assists. The NIMPH projects first step in reducing landed mass focuses on development of a micro-In Situ Resource Utilization (micro-ISRU) system. ISRU allows us to minimize landed mass of a sample return mission by converting local ice into propellants. The project reduces the ISRU system to a CubeSat-scale package that weighs just 1.74 kg and consumes just 242 W of power. We estimate that use of this ISRU vs. an identical micro-lander without ISRU reduces fuel mass by 45 kg. As the dry mass of the lander grows for larger missions, these savings scale exponentially. Taking full advantage of the micro-ISRU system requires the development of a micro-liquid oxygen-liquid hydrogen engine. The micro-liquid oxygen-liquid hydrogen engine is tailored for the mission by scaling it to match the scale of the micro-lander and the low gravity of the target moon. We also tailor the engine for a near stoichiometric mixture ratio of 7.5. Most high-performance liquid oxygen-liquid hydrogen engines inject extra liquid hydrogen to lower the average molecular weight of the exhaust, which improves specific impulse. However, this extra liquid hydroden requires additional power and processing time on the surface for the ISRU to create. This increases mission cost, and on missions within high radiation environments such as Europa, increases radiation shielding mass. The resulting engine weighs just 1.36 kg and produces 71.5 newton of thrust at 364 s specific impulse. Finally, the mission reduces landed mass by taking advantage of the SEP modules solar power to beam energy to the surface using a collimated laser. This allows us to replace an 45 kg MMRTG with a 2.5 kg resonant array. By using the combination of ISRU, a liquid oxygen-liquid hydrogen engine, and beamed power, we reduce the initial mass of the lander to just 51.5 kg. When combined with an SEP module to ferry the lander to Europa the initial mission mass is just 6397 kg - low enough to be placed on an Earth escape trajectory using an Atlas V 551 launch vehicle. By comparison, we estimate a duplicate lander using an MMRTG and semi-storable propellants such as liquid oxygen-methane would result in an order of magnitude increase in initial lander mass to 445 kg. Attempting to perform the trajectory with a 450 s liquid oxygen-liquid hydrogen engine would increase initial mass to approximately 135,000 kg. Using an Atlas V 1 U.S. Dollar per kg rate to Earth escape value of $27.7k per kg, just the launch savings are over $3.5 billion.

liquid↗

Smart Methane Emission Detection System Development (Final Report)

Working with the Department of Energy's National Energy Technology Laboratory, Southwest Research Institute® (SwRI®) developed a system to identify methane leaks reliably, accurately, and autonomously at critical midstream sections of the natural gas distribution network in real-time for the purpose of mitigating methane emissions using Optical Gas Imaging (OGI) cameras. SwRI's Smart Leak Detection – Methane (SLED/M) adds a high degree of automation to the process of methane leak detection to minimize sources of human error, minimize response time to a leak event, and maximize midstream visibility. Furthermore, SwRI has been working towards integrating Quantitative OGI (QOGI) capabilities into this existing technology. By leveraging Deep Learning, SwRI now has the capability to estimate fugitive emission leak rates quickly and reliably, which allows operators to detect emissions, quantify leak rate, prioritize repairs, and validate the repairs in a single instrument. The next generation QOGI technology leverages the same cameras used in Leak Detection and Repair (LDAR) programs, with improvements in safety and speed for traditional quantification-based repairs, ultimately leading to less overhead cost for the operators. The goals for this research were to develop two types of models with the following goals: Run in real-time on the edge (≥ 12 Hz), Classification: Achieve less than 5% false positive detection, Classification: Achieve ≥ 95% methane plume detection rate, Regression: achieve ≤ 10 standard cubic feet per hour (scfh) prediction > 70% of the time. In order to achieve these results, multiple infrared (IR) and other sensors were investigated in tandem with the midwave IR (MWIR) OGI to provide additional information to train the underlying models. Information on atmospheric conditions including humidity, temperature, pressure, and solar radiation was provided by a weather station. Several machine learning and deep learning architectures and methods, including looking at quantized classification networks and regressions networks, were explored. As further data was collected, curated, and labeled, it allowed for more refined regressive networks to be adequately trained, leading to better insight into the true flow rates being observed. An important valuable deliverable of this research effort was the development of an advanced network which underwent multiple iterations capable of giving a continuous output. The current network has a predicted mean average percentage error (MAPE) of 12.3% just outside our target goal of 10.00%, but an accuracy of 97.78% at ±50 scfh, well within the overall goal for the Department of Energy (DOE) program. Upon closer inspection, it was observed that more than 10% of datapoints contributing to the MAPE predictions were the result of low flow rate predictions and are beyond the sensitivity of instrument measurement as a result of normal operational variation and noise.

03 NATURAL GAS↗

Overview of the Dragonfly Entry Aerosciences Measurements (DrEAM) Suite

NASA Ames and Langley arepartnering with DLR to propose acomprehensive instrumentation suite known as the Dragonfly Entry Aerosciences Meas-urements (DrEAM). DrEAM being the first competed mission to fly EDL instrumentation as part of NASA’s Engineering Science Investigation (ESI).DrEAM will provide key aerothermodynamicdata and performance analysisfor Dragonfly’s forebody and backshell therma lprotection system (TPS),and also includes a DLR-provided Data Acquisition System(DAS).Titan’s atmosphere predominantly consists of nitro-gen (~98% by mole) with small amounts of methane(~2% by mole)and other trace gases. CN is a strong ra-diator and is found in nonequilibriumconcentrationsfor Titan entry. The accurate modeling of nonequilibrium CN radiation has proven to be a difficult task. Prompted by the Huygensmission, many experimental campaigns and analyses were performed to better understand the aerothermal environments experience by the probe dur-ing Titan entry[1].However, the Huygens probe carried no heatshieldinstrumentation. Therefore,the DrEAM instrumentation suite will significantly advance the state-of-the-art not only by documenting theenviron-ment and performance of Dragonfly’sentry system but also by making keymeasurements in Titan’s atmos-phere for thefirst time, thus providing new benchmark dataapplicable to entry science more generally. Current Measurement Goals: Aerothermal envi-ronments and TPS responsewill be measured using sen-sors similarto the Mars Entry, Descent, and Landing In-strumentation2 (MEDLI2) Integrated Sensor Plug(MISP) and the COMbined Aerothermaland Radiome-ter Sensor (COMARS)suite[2], with the latter supplied by DLR.For MEDLI2, MISP usedembedded thermo-couples (TCs) todirectly measure in-depth temperature of theTPS at several locations,which can also be used to infer surface environmentsvia inverse analysis. For DrEAM, the MISPstyle plugswill be known as Drag-onfly Sensors for Aero-Thermal Reconstruction (Drag-STR)plugs. On Schiaparelli, the COMARSsuite in-cludedthree total surface-mounted heatflux sensors, three pressure sensors, and one radiometer. For DrEAM, the COMARS package will be known as COmbined Sensor System for Titan Atmosphere (COSSTA). Atmospheric density measurements and capsuleaerodynamic data will be obtained throughthe onboard Inertial Measurement Unit (IMU),supple-mented by pressure transducers similar tothose used by the MEDLI Mars Entry AtmosphericData System (MEADS).The DrEAM pressure sensors will be known as Dragonfly Atmospheric Flight Transducers(DrAFT) Both DragSTR and DrAFThave flight heritagefrom MISP and MEADS on the MSLand Mars 2020mis-sions, and the COMARS suite successfullyflew on the ESA Schiaparelli EDMlander. A preliminary layout of the sensors is shown in Fig. 1. Because Dragonflyuses the same aeroshell provider (i.e., LockheedMartin) and materials for the TPS,with what are expected to be sim-ilar thicknesses as MSL and Mars 2020on both the heat shield and backshell, theDrEAMinstrumentation will look to utilize the same techniques and processes as de-veloped byMEDLI and MEDLI2for vehicle integra-tion. This commonality alsoenables DrEAMto lever-age the extensiveground test qualifications performed forMEDLI and MEDLI2 and claim substantial heritagefor this system.

A Brandis↗

Results of the 2018 Wood Stove Design Challenge

The 2018 Wood Stove Design Challenge was an international design competition which sought to identify top performing residential wood stoves based on automation. To prepare for the event, the Northeast States for Coordinated Air Use Management (NESCAUM) developed a testing protocol that challenged the stoves by testing them in more field-like conditions—capturing emissions from start-up, reloading a stove, and the use of larger piece sizes. Flue gas emissions were measured using a combination of in-stack and novel dilution sampling methods, as the event occurred on the National Mall in Washington D.C. in a non-laboratory setting. Particulate matter (PM), carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4) were measured from three stoves in real-time. A combustion efficiency was also calculated for each stove in real-time. Measured PM emission rates ranged between 1.8 and 8.0 g/hr for all stoves and operating conditions, with the highest emissions being measured during cold start in all cases. The test average PM emission rates were 2.4, 4.0, and 2.4 g/hr for stoves A, B, and C, respectively. Results showed emissions measured during transient operations, which are often excluded in current certification methods, can be significantly higher than steady-state periods—echoing other studies and highlighting the importance of testing in various operational modes for more realistic emission estimates. Additionally, the stoves had overall CO emission rates of 48.8, 284.8, and 100.8 g/hr, for stoves A, B and C, respectively. Calculated PM and CO emission factors overall were low considering the testing protocol sought to follow more challenging yet realistic practices in terms of fuel loading and operating procedures. The overall estimated combustion efficiency for stoves A, B, and C was 85%, 78%, 76%, respectively and in all cases was lowest during the cold start period.This report details the successfully proposed and assembled instrumentation that was relatively portable for field-site testing and the results of the emissions measurements for the 2018 Wood Stove Design Challenge competition. Overall, the repeatability of each stove was favorable with coefficients of variation (COV) ranging from 7 to 15% for measured PM concentrations.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗