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At least 1,297 records · Page 72

Carbothermal Processing of Lunar Regolith Using Methane

The processing of lunar regolith for the production of oxygen is a key component of the In-Situ Resource Utilization plans currently being developed by NASA. Among various candidate processes, the modeling of oxygen production by hydrogen reduction, molten salt electrolysis, and carbothermal processing are presently being pursued. In the carbothermal process, a portion of the surface of the regolith in a container is heated by exposure to a heat source such as a laser beam or a concentrated solar heat flux, so that a small zone of molten regolith is established. The molten zone is surrounded by solid regolith particles that are poor conductors of heat. A continuous flow of methane is maintained over the molten regolith zone. Our model is based on a mechanism where methane pyrolyzes when it comes in contact with the surface of the hot molten regolith to form solid carbon and hydrogen gas. Carbon is deposited on the surface of the melt, and hydrogen is released into the gas stream above the melt surface. We assume that the deposited carbon mixes in the molten regolith and reacts with metal oxides in a reduction reaction by which gaseous carbon monoxide is liberated. Carbon monoxide bubbles through the melt and is released into the gas stream. Oxygen is produced subsequently by (catalytically) processing the carbon monoxide downstream. In this paper, we discuss the development of a chemical conversion model of the carbothermal process to predict the rate of production of carbon monoxide.

Balasubramaniam, R.↗

Innovative techniques for the production of energetic radicals for lunar processing including cold plasma processing of local planetary ores

Hydrogen reduction of ilmenite has been studied by a number of investigators as a potential means for recovery of oxygen from lunar soil. Interest in this process has always rested with the simplicity of the flow diagram and the utilization of established technology. Effective utilization of hydrogen in the reduction process at temperatures of 1200 C and below has always been disappointing and, as such, has led other investigators to focus attention on other systems. Effective utilization of hydrogen in the reduction of ilmenite can be significantly enhanced in the presence of a non-equilibrium hydrogen plasma. Ilmenite at solid specimen temperatures of 600 C to 970 C were reacted in a hydrogen plasma. Those experiments revealed that hydrogen utilization can be significantly enhanced. At a specimen temperature of 850 C the fraction of H2 reacted was 24 percent compared to the 7 percent theoretical limit calculated with thermodynamic theory for the same temperature. An added advantage for a hydrogen plasma involves further reduction of TiO2. Reduction of the iron oxide in ilmenite yields TiO2 and metallic iron as by products. Titanium forms a number of oxides including TiO, Ti2O3, Ti3O5 and the Magneli oxides (Ti4O7 to Ti50O99). In conventional processing of ilmenite with hydrogen it is possible to reduce TiO2 to Ti7O13 within approximately an hour, but with poor utilization of hydrogen on the order of one mole of H2 per thousand. In the cold or non-equilibrium plasma TiO2 can be rapidly reduced to Ti2O3 with hydrogen utilization exceeding 10 percent. Based on design considerations of the plasma reactor greater utilization of the hydrogen in the reduction of TiO2 is possible.

Bullard, D.↗

Enhanced Groundwater Flow on and Below Vera Rubin Ridge, the Murray Formation, Gale Crater: Evidence from Thermochemical Modeling.

NASA’s Mars Science Laboratory Curiosity rover has been exploring Vera Rubin ridge (VRR), part of the Murray formation in Gale crater, Mars, between sol 1809 and 2302. Evidence for Fe-oxides and phyllosilicates in mineralogical and geochemical data for this region was returned by Curiosity [1-5]. We applied thermochemical modeling to con-strain the formation conditions of the phyllosilicate-hematite assemblage identified on and below VRR. Average alteration compositions for the Murray formation on and below VRR were derived using CheMin and APXS data. These compositions were reacted with Gale Portage Water (GPW) between 25–100 °C and for 10% and 50% Fe3+/Fetot of the host rock [6]. Here we summarize models run at 50 °C and 10% Fe3+/Fetot for alteration compositions derived from Murray host rock compositions.

Turner, S. M. R.↗

An intrinsically n-dimensional generalized flux vector splitting implicit finite element Euler algorithm

A generalized flux-vector splitting implicit Galerkin finite-element algorithm for the Euler equations in curvilinear coordinates for ideal and reacting gases is derived. For an arbitrary equation of state, the curvilinear-coordinate flux vector is split in kinematic and kinetic components, and the associated jacobian matrix eigenvalues explicitly depend on the metric data. After directional semidiscretization, the terminal ordinary differential-equation system is solved via a nonlinearly stable implicit Runge-Kutta scheme in concert with an accurate tensor matrix product factorization. The results for selected two-dimensional supersonic and axisymmetric hypersonic flows validate the algorithm and verify its robustness for curvilinear-coordinate computations. The evolution towards a steady state is achieved for large Courant numbers without indication of numerical instabilities.

Iannelli, G. S.↗

Advanced Small Rocket Chambers. Basic Program and Option 2: Fundamental Processes and Material Evaluation

Propellants, chamber materials, and processes for fabrication of small high performance radiation cooled liquid rocket engines were evaluated to determine candidates for eventual demonstration in flight-type thrusters. Both storable and cryogenic propellant systems were considered. The storable propellant systems chosen for further study were nitrogen tetroxide oxidizer with either hydrazine or monomethylhydrazine as fuel. The cryogenic propellants chosen were oxygen with either hydrogen or methane as fuel. Chamber material candidates were chemical vapor deposition (CVD) rhenium protected from oxidation by CVD iridium for the chamber hot section, and film cooled wrought platinum-rhodium or regeneratively cooled stainless steel for the front end section exposed to partially reacted propellants. Laser diagnostics of the combustion products near the hot chamber surface and measurements at the surface layer were performed in a collaborative program at Sandia National Laboratories, Livermore, CA. The Material Sample Test Apparatus, a laboratory system to simulate the combustion environment in terms of gas and material temperature, composition, and pressure up to 6 Atm, was developed for these studies. Rocket engine simulator studies were conducted to evaluate the materials under simulated combustor flow conditions, in the diagnostic test chamber. These tests used the exhaust species measurement system, a device developed to monitor optically species composition and concentration in the chamber and exhaust by emission and absorption measurements.

Jassowski, Donald M.↗

Challenges to Laser-Based Imaging Techniques in Gas Turbine Combustor Systems for Aerospace Applications

Increasingly severe constraints on emissions, noise and fuel efficiency must be met by the next generation of commercial aircraft powerplants. At NASA Lewis Research Center (LeRC) a cooperative research effort with industry is underway to design and test combustors that will meet these requirements. To accomplish these tasks, it is necessary to gain both a detailed understanding of the combustion processes and a precise knowledge of combustor and combustor sub-component performance at close to actual conditions. To that end, researchers at LeRC are engaged in a comprehensive diagnostic investigation of high pressure reacting flowfields that duplicate conditions expected within the actual engine combustors. Unique, optically accessible flame-tubes and sector rig combustors, designed especially for these tests. afford the opportunity to probe these flowfields with the most advanced, laser-based optical diagnostic techniques. However, these same techniques, tested and proven on comparatively simple bench-top gaseous flame burners, encounter numerous restrictions and challenges when applied in these facilities. These include high pressures and temperatures, large flow rates, liquid fuels, remote testing, and carbon or other material deposits on combustor windows. Results are shown that document the success and versatility of these nonintrusive optical diagnostics despite the challenges to their implementation in realistic systems.

Locke, Randy J.↗

Direct numerical simulation of a high-pressure hydrogen micromix combustor: Flame structure and stabilisation mechanism

A high-pressure hydrogen micromix combustor has been investigated using direct numerical simulation with detailed chemistry to examine the flame structure and stabilisation mechanism. The configuration of the combustor was based on the design by Schefer et al., using numerical periodicity to mimic a large square array. A precursor simulation of an opposed jet-in-crossflow was first conducted to generate appropriate partially-premixed inflow boundary conditions for the subsequent reacting simulation. The resulting flame can be described as an predominantly-lean inhomogeneously-premixed lifted jet flame. Five main zones were identified: a jet mixing region, a core flame, a peripheral flame, a recirculation zone, and combustion products. The core flame, situated over the jet mixing region, was found to burn as a thin reaction front, responsible for over 85% of the total fuel consumption. The peripheral flame shrouded the core flame, had low mean flow with high turbulence, and burned at very lean conditions (in the distributed burning regime). It was shown that turbulent premixed flame propagation was an order-of-magnitude too slow to stabilise the flame at these conditions. Stabilisation was identified to be due to ignition events resulting from turbulent mixing of fuel from the jet into mean recirculation of very lean hot products. Ignition events were found to correlate with shear-driven Kelvin-Helmholtz vortices, and increased in likelihood with streamwise distance. At the flame base, isolated events were observed, which developed into rapidly burning flame kernels that were blown downstream. Further downstream, near-simultaneous spatially-distributed ignition events were observed, which appeared more like ignition sheets. The paper concludes with a broader discussion that considers generalising from the conditions considered here.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Semiclassical dynamics on multiple electronic surfaces - Three-dimensional treatment of reactive F + H2

The role of electron transitions in collisions is studied for the F + H2 reaction by combining quasi-classical Monte Carlo trajectories with a semiclassical decoupling approximation for the electron transitions. Attention is directed at the reaction of excited state F atoms reacting to form ground state products; the reactants are initiated in either of two spin-orbit states of the atom with the diatom in the ground vibrational state and the lowest four rotational states, at relative translational energies of 0.1, 0.2 and 0.3 eV. Even if the reactants are initiated on the excited state surface, the reactive cross sections (which are classically forbidden) are significant. The major dynamical effects of the excited state reaction are the flow of reactant electronic energy into product internal energy.

Komornicki, A.↗

Kinetic Studies of Iron Deposition in Horse Spleen Ferritin Using H2O2 and O2 as Oxidants

The reaction of horse spleen ferritin (HoSF) with Fe(2+) at pH 6.5 and 7.5 using O2, H2O2 and 1:1 a mixture of both showed that the iron deposition reaction using H2O2 is approx. 20- to 50-fold faster than the reaction with O2 alone. When H2O2 was added during the iron deposition reaction initiated with O2 as oxidant, Fe(2+) was preferentially oxidized by H2O2, consistent with the above kinetic measurements. Both the O2 and H202 reactions were well defined from 15 to 40 C from which activation parameters were determined. The iron deposition reaction was also studied using O2 as oxidant in the presence and absence of catalase using both stopped-flow and pumped-flow measurements. The presence of catalase decreased the rate of iron deposition by approx. 1.5-fold, and gave slightly smaller absorbance changes than in its absence. From the rate constants for the O2 (0.044 per second) and H2O2 (0.67 per second) iron-deposition reactions at pH 7.5, simulations of steady-state H2O2 concentrations were computed to be 0.45 micromolar. This low value and reported Fe2(+)/O2 values of 2.0-2.5 are consistent with H2O2 rapidly reacting by an alternate but unidentified pathway involving a system component such as the protein shell or the mineral core as previously postulated.

Lowery, Thomas J., Jr.↗

Flowfield-Dependent Mixed Explicit-Implicit (FDMEL) Algorithm for Computational Fluid Dynamics

Despite significant achievements in computational fluid dynamics, there still remain many fluid flow phenomena not well understood. For example, the prediction of temperature distributions is inaccurate when temperature gradients are high, particularly in shock wave turbulent boundary layer interactions close to the wall. Complexities of fluid flow phenomena include transition to turbulence, relaminarization separated flows, transition between viscous and inviscid incompressible and compressible flows, among others, in all speed regimes. The purpose of this paper is to introduce a new approach, called the Flowfield-Dependent Mixed Explicit-Implicit (FDMEI) method, in an attempt to resolve these difficult issues in Computational Fluid Dynamics (CFD). In this process, a total of six implicitness parameters characteristic of the current flowfield are introduced. They are calculated from the current flowfield or changes of Mach numbers, Reynolds numbers, Peclet numbers, and Damkoehler numbers (if reacting) at each nodal point and time step. This implies that every nodal point or element is provided with different or unique numerical scheme according to their current flowfield situations, whether compressible, incompressible, viscous, inviscid, laminar, turbulent, reacting, or nonreacting. In this procedure, discontinuities or fluctuations of an variables between adjacent nodal points are determined accurately. If these implicitness parameters are fixed to certain numbers instead of being calculated from the flowfield information, then practically all currently available schemes of finite differences or finite elements arise as special cases. Some benchmark problems to be presented in this paper will show the validity, accuracy, and efficiency of the proposed methodology.

Garcia, S. M.↗

Records of our Early Biosphere Illuminate our Origins and Guide our Search for Life Beyond Earth

A scientific "mission of exploration to early Earth" will help us chart the distribution of life elsewhere. We must discriminate between attributes of biospheres that are universal versus those attributes that represent principally the outcomes of long-term survival specifically on Earth. In addition to the basic physics and chemistry of matter, the geologic evolution of rocky habitable planets and their climates might be similar elsewhere in the Universe. Certain key agents that drive long-term environmental change (e.g., stellar evolution, impacts, geothermal heat flow, tectonics, etc.) can help us to reconstruct ancient climates and to compare their evolution among populations of Earth- like planets. Early Earth was tectonically more active than today and therefore it exhaled reduced chemical species into the more oxidized surface environment at greater rates. This tectonic activity thus sustained oxidation-reduction reactions that provided the basis for the development of biochemical pathways that harvest chemical energy ("bioenergetics"). Most examples of bioenergetics today that extract energy by reacting oxidized and reduced chemicals in the environment were likely more pervasive among our microbial ancestors than are the presently known examples of photosynthesis. The geologic rock record indicates that, as early as 3.5 billion years ago (3.5 Ga), microbial biofilms were widespread within the coastal environments of small continents and tectonically unstable volcanic islands. Non oxygen-producing (non-oxygenic) photosynthesis preceded oxygenic photosynthesis, but all types of photosynthesis contributed substantially to the long-term increase in global primary biological productivity. Evidence of photosynthesis is tentative by 3.5 Ga and compelling by 2.7 Ga. Evidence of oxygenic photosynthesis is strong by 2.7 Ga and compelling by 2.3 Ga. These successive innovations transformed life from local communities that survived principally by catalyzing chemical equilibration to a globally dominant agent that created and sustained widespread chemical disequilibria in the environment and shallow crust. Major biogeochemical perturbations ca. 2.3 to 2.0 Ga, 1.3 Ga, and also 0.8 to 0.6 Ga, contributed to the irreversible oxidation of the global environment and perhaps also triggered evolutionary innovations (e.g., the development of multi-cellular biota) that became the foundations of our modern biosphere. Understanding the nature and timing of this ascent of life is crucial for discerning our o m beginnings. This understanding also empowers OUT search for the origins, evolution and distribution of life elsewhere in our solar system and beyond.

DesMarais, David J.↗

Utilizing metal cation reactions with carbonyl sulfide to remove isobaric interferences in tandem inductively coupled plasma mass spectrometry analyses

Carbonyl sulfide (OCS) was used as a reaction gas to investigate gas phase metal (M + ) ion-molecule reactions using the Agilent 8900 inductively coupled plasma tandem mass spectrometer (ICP-MS/MS) to yield insight on how this gas may be used to remove isobaric interferences in analytical measurements. The experimental work was paired with density functional theory (DFT) calculations of the reaction enthalpy to predict whether M + will react with OCS. A multi-element standard containing 46 elements ranging from 9 to 208 u was analyzed in the presence and absence of OCS. When a reaction was observed, the dominant product was the sulfide (MS + ). Oxide products were also observed for many M + but formation was less efficient with OCS than previously observed with other reaction gases. This is likely due to the weaker OC-S bond that makes MS + formation more favorable. Increasing the flow rate from 0.1 to 0.2 mL/min (corresponding to a change in reaction gas pressure from 0.35 to 0.53 Pa (2.6 to 4.0 mTorr)) generally resulted in greater MS + production, including the secondary product MS 2 + for a few cations. The early lanthanide series ions (La + , Ce + , Pr + and Nd + ) produced greater quantities of MO + at the higher pressure, although MS + products were still the dominant product. The DFT-predicted reaction enthalpies were consistent with the observed sulfide formation, with an accuracy >90%; however, model predictions were less accurate for the minor and higher order products (< 77% for MO + ). Finally, the work presented here continues a systematic study of ion-molecule reactions in ICP-MS/MS to understand and develop new and novel ways to analyze complex mixtures with minimal pre-analysis treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Combustion of Metals in Reduced-Gravity and Extraterrestrial Environment

As a result of the ongoing exploration of Mars and the several unmanned and manned missions planned for the future, increased attention has been given to the use of the natural resources of the planet for rocket propellant production and energy generation. Since the atmosphere of Mars consists of approximately 95% carbon dioxide (CO2), this gas is the resource of choice to be employed for these purposes. Unfortunately, CO2 is also a final product in most combustion reactions, requiring further processing to extract useful reactants such as carbon monoxide (CO), oxygen (O2), and hydrocarbons. An exception is the use Of CO2 as an oxidizer reacting directly with metal fuel. Since many metals burn vigorously with CO2, these may be used as an energy source and as propellants for an ascent/descent vehicle in sample-collection missions on Mars. In response to NASA's Human Exploration and Development of Space (HEDS) Enterprise to search for appropriate in-situ resource utilization techniques, this investigation will study the burning characteristics of promising metal/CO2 combinations. The use of reduced gravity is essential to eliminate the intrusive buoyant flows that plague the high-temperature metal reactions, to remove the destructive effect of gravity on the shape of molten metal samples, and to study the influence of radiative heat transfer from solid oxides undisturbed by natural convection. In studies with large metal specimens, the burning process is invariably influenced by strong convective currents that accelerate the reaction and shorten the burning times. Although these currents are nearly absent from small burning particles, the high emissivity of the flames, rapid reaction, small length scales, and intermittent explosions make the gathering of any useful information on burning rates and flame structure very difficult. This investigation has the ultimate goal of providing a careful probing of flame structure and dynamics by taking advantage of large, free-floating spherical metal samples and their corresponding long burning times available in reduced gravity. The first set of experiments has been conducted with magnesium (Mg) samples burning in the low-gravity environment generated by an aircraft flying parabolic trajectories. Owing to its high adiabatic flame temperature, oxidizer/fuel ratio, and heat per unit mass of fuel, as well as its low toxicity and low ignition temperature, Mg has been identified as a promising metal fuel with CO2 as oxidizer. The experimental effort is complemented by the development of a numerical model combining gas-phase chemical kinetics and transport mechanisms.

Abbud-Madrid, A.↗

Hydrogen Generation and Serpentinization of Olivine Under Flow Conditions

Serpentinization of olivine is often studied in the laboratory under batch conditions. Olivine conversion in situ with enhanced natural hydrogen production will likely be implemented via injection of aqueous solutions. Hence, transport is relevant to the extent of olivine reaction and, potentially, the morphology of precipitates formed. To test conditions for optimal H 2 generation and outcomes, serpentinization was induced by injecting pH = 12.5 brine at 0.015 cm 3 /min (0.5 pore volumes per day) into an olivine sand pack (250 to <355 μm grain size) at 245°C generating, at minimum 76 and 89 mol% H 2 at 35 and 57 d, respectively. Grain-coating serpentine with radiating needles cemented the reacted sand grains. Importantly, pore space was maintained between the dissolving grains and the serpentine precipitates. Hence, reactivity continued as a result of fluid access to mineral surfaces, the large grain size, and the continuous injection of undersaturated alkaline fluids.

08 HYDROGEN↗

Propellant vaporization as a criterion for rocket-engine design : experimental effect of fuel temperature on liquid-oxygen - heptane performance

Characteristic exhaust velocity of a 200-pound-thrust rocket engine was evaluated for fuel temperatures of -90 degrees, and 200 degrees f with a spray formed by two impinging heptane jets reacting in a highly atomized oxygen atmosphere. Tests covered a range of mixture ratios and chamber lengths. The characteristic exhaust-velocity efficiency increased 2 percent for a 290 degree f increase in fuel temperature. This increase in performance can be compared with that obtained by increasing chamber length by about 1/2 inch. The result agrees with the fuel-temperature effect predicted from an analysis based on droplet evaporation theory. Mixture ratio markedly affected characteristic exhaust velocity efficiency, but total flow rate and fuel temperature did not.

Heidmann, M F↗

Chemiluminescence Measurements in a Combustor Using a 7-Point Lean Direct Injector Array Configuration for Gas Turbine Engine Applications

Two different configurations of a 7-point lean direct injector array were investigated. Chemiluminescence images of C2* or CH* were collected during combustion tests for insight on flame structure for the two configurations. Several inlet conditions were tested by varying the equivalence ratio or reference velocity. For the center right-hand 60 degree and outer right-hand 52 degree outers, the chemiluminescence emanating from the central pilot appeared well isolated from the outers. At the same time, a hollow region below the pilot showed little fluctuation of chemiluminescence where a central recirculation zone was present during the non-reacting tests. The central left-hand 60 degree and outer right-hand 52 degree configuration displayed a narrower structure from the pilot compared to the flatter pilot observed in the other configuration. Additionally, the right-handed outer swirlers may be responsible for the asymmetry observed with the chemiluminescence images. Both configurations showed less variation in chemiluminescence intensity as the reference velocity was increased. This was likely due to better atomization and vaporization associated with higher fuel and air flow rates.

lean direct injection↗

Vectorial Charge Transfer across Bipolar Membrane Loaded with CdS and Au Nanoparticles

Bipolar membranes (BPMs) which consist of a cation exchange layer (CEL) and anion exchange layer (AEL) are quite effective as membranes in gas phase electrolyzers. However, such membranes can also serve as a host to embed photocatalysts and electrocatalysts. By selectively exchanging cations with Cd 2+ and anions with AuCl 4 – , we were able to synthesize CdS and Au nanoparticles in CEL and AEL layers, respectively, through sequential chemical and photocatalytic reactions. Reacting Cd 2+ with thioacetamide formed the CdS nanoparticles in CEL. The photogenerated electrons from CdS were then used to reduce AuCl4– in an H-cell configuration to produce Au nanoparticles in AEL and thus prepare a photocatalytically active BPM film (referred to as a CdS/BPM/Au film). Such a concerted design of BPM allows “vectorial” electron transfer between two layers of BPM leading to its transfer to an acceptor molecule (methyl viologen) in solution. Designing photocatalytically active BPM and understanding the vectorial electron flow between two separate ion-selective layers offer new opportunities in water splitting and CO 2 reduction.

13 HYDRO ENERGY↗

Novel High Gas-Temperature Calibration System Demonstrated

Accurate measurement of high gas temperatures, typically above 1300 K, has always presented challenges to researchers. Thermocouples often perturb the local gas flow and temperature field; they provide indirect information; and at high temperatures, they require large corrections so that actual gas temperatures can be determined. The physical and chemical stability of thermocouples to withstand the thermal loads and reactive environments prevailing at high temperatures naturally limits their life and maximum use temperature. Optical systems have their own drawbacks since accurate results depend on well-characterized emissivity, optical thickness, and gas composition information. These properties are rarely well known, especially in high-temperature, chemically reacting environments. In addition, optical systems usually require independent calibrations, which often involve the use of thermocouples, and hence, suffer from their aforementioned limitations. A new technique developed by researchers at the NASA Glenn Research Center at Lewis Field exploits an abrupt increase in the emittance of optically thin materials at their unique melting temperatures for a direct determination of gas temperature. Pure metallic-oxide fibers, varying in diameter from 60 to 400 mm, have been used in measurements over a temperature range of 2050 to 2700 K. The accuracy and reproducibility of the technique is estimated to be 15 K: that is, within the uncertainty in the melting points of the materials. Other fiber materials with different, but unique, melting points could be used to extend the technique over a larger temperature range.

Gokoglu, Suleyman A.↗