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At least 775 records · Page 43

Real-Time Elemental and Isotopic Measurements of Molten Salt Systems through Laser-Induced Breakdown Spectroscopy

Molten salt reactors are an emerging advanced nuclear reactor concept in which the fuel is dissolved into the working fluid in the form of a high-temperature molten salt. The complex, mobile, and corrosive nature of this fluid presents a fundamental challenge for analytical measurements. Tracking species throughout the reactor is important for ensuring proper operation. This article presents laser-induced breakdown spectroscopy (LIBS) used to monitor the elemental composition of a molten salt and corresponding hydrogen isotopic shifts in real-time. A NaNO 3 –KNO 3 eutectic salt was saturated with protium and deuterium gases, then the effluent aerosol stream formed using an argon sparging vessel was monitored with LIBS. This modular LIBS system permitted several spectrometers to be used simultaneously to capture high-resolution isotopic shifts and provide broadband elemental coverage. Further, the results exhibit how LIBS can be used to understand salt–gas chemical and physical interactions such as diffusion. Furthermore, LIBS’ broad elemental coverage can provide greater insight into the chemical reactions within the salt vessel such as the formation of water vapor by monitoring hydrogen and oxygen signatures simultaneously. Ultimately, this study demonstrates the analytical possibilities of LIBS for real-time monitoring of isotopes and elemental composition in molten salt systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rocket and spacecraft studies of ultraviolet emissions from astrophysical targets

Rocket and spacecraft far-UV spectral measurements of several astrophysical targets are reviewed. These include observations of Ly-alpha emissions from Arcturus, Apollo-17 far-UV spectrometry of eta UMa and five other stars, Apollo-17 observations of the lunar atmosphere and the diffuse UV background, and far-UV spectral studies of Venus, Jupiter, and Comet Kohoutek. The Arcturus observations indicated a chromosphere with neutral atomic-hydrogen and atomic-oxygen emissions as well as a very weak atomic-carbon line. The planetary studies revealed O I and C I emissions in the Venusian spectrum as well as large Ly-alpha emissions and possible molecular-hydrogen emissions in that of Jupiter. The lunar observations demonstrated that solar protons do not produce an atomic-hydrogen atmosphere on the moon.

Fastie, W. G.↗

Forced cocurrent smoldering combustion

An analytical model of cocurrent smoldering combustion through a very porous solid fuel is developed. Smoldering is initiated at the top of a long radially insulated uniform fuel cylinder, so that the smolder wave propagates downward, opposing an upward-forced flow of oxidizer, with the solid fuel and the gaseous oxidizer entering the reaction zone from the same direction (hence, cocurrent). Radiative heat transfer was incorporated using a diffusion approximation, and smoldering was modeled using a one-step reaction mechanism. The results indicate that, for a given fuel, the final temperature depends only on the initial oxygen mass flux, increasing logarithmically with the mass flux. The smolder velocity is linearly dependent on the initial oxygen mass flux, and, at a fixed value of the flux, increases with initial oxygen mass fraction. The mathematical relationship determining the conditions for steady smolder propagation is presented.

Dosanjh, Sudip S.↗

Evaporation and combustion of LOX under supercritical and subcritical conditions

The objective is to study the evaporation and combustion of LOX under supercritical and subcritical conditions both experimentally and theoretically. In the evaporation studies, evaporation rate and surface temperature were measured when LOX vaporizing in helium environments at pressures ranging from 5 to 68 atm. A Varian 3700 gas chromatograph was employed to measure the oxygen concentration above the LOX surface. For the combustion tests, high-magnification video photography was used to record direct images of the flame shape of a LOX/H2/He laminar diffusion flame. The gas composition in the post-flame region is also being measured with the gas sampling and chromatography analysis. These data are being used to validate the theoretical model. A comprehensive theoretical model with the consideration of the solubility of ambient gases as well as variable thermophysical properties was formulated and solved numerically to study the gasification and burning of LOX at elevated pressures. The calculated flame shape agreed reasonably well with the edge of the observed luminous flame surface. The effect of gravity on the flame structure of laminar diffusion flames was found to be significant. In addition, the predicted results using the flame-sheet model were compared with those based upon full equilibrium calculations (which considered the formation of intermediate species) at supercritical pressures. Except at the flame front where temperature exceeded 2,800 K, the flame-sheet and equilibrium solutions in terms of temperature distributions were in very close agreement. The temperature deviation in the neighborhood of the flame front is caused by the effect of high-temperature dissociation.

Yang, A. S.↗

X-ray constraints on the intergalactic medium

We use ROSAT Position Sensitive Proportional Counter (PSPC) spectra of z approximately equal 3 quasars to constrain the density and temperature of the intergalactic medium (IGM). Strong low-energy cutoffs in PSPC spectra of high-redshift quasars are common. However, the absence of absorption toward some high-redshift quasars can be used to put limits on the possible cosmological density, Omega(sub G), of a hot diffuse intergalactic medium (IGM), via an X-ray Gunn-Peterson test using edge and line opacity in the soft X-rays. The K-edges of oxygen, neon, and carbon and the L-edge of iron produce most of the absorption which is spread out by the redshift of the source. We assume an isotropic, isothermal, nonevolving model of the IGM and calculate the optical depth of this absorption. We find that this test can constrain an enriched IGM at temperatures near 10(exp 5) - 10(exp 6) K, intermediate between the hot IGM ruled out by COBE, and the cold IGM ruled out by the traditional Ly alpha Gunn -Peterson test. Photoionization if the IGM by the ultraviolet and X-ray background has a large effect. We give results for three z approximately equal 3 quasars and discuss how the various trade-offs among temperature, abundance, and backgroud radiation strength affect the limits on Omega (sub G). In addition to the high-redshift case, we discuss techniques for constraining the IGM using X-ray spectra of low-redhift quasars (z approximately equal 0.1 - 0.3). Currently available X-ray spectral data have insufficient energy resolution to constrain the IGM umambiguously, and so expected detection limits for future high-resolution spectrometers are presented. We find that with a large effective area (approximately 2000 sq cm), it is possible to substantially constrain or detect the IGM at the densities which are typically predicted.

Aldcroft, Thomas↗

Fuel Cells Utilizing Oxygen From Air at Low Pressures

A fuel cell stack has been developed to supply power for a high-altitude aircraft with a minimum of air handling. The fuel cell is capable of utilizing oxygen from ambient air at low pressure with no need for compression. For such an application, it is advantageous to take oxygen from the air (in contradistinction to carrying a supply of oxygen onboard), but it is a challenging problem to design a fuel-cell stack of reasonable weight that can generate sufficient power while operating at reduced pressures. The present fuel-cell design is a response to this challenge. The design features a novel bipolar plate structure in combination with a gas-diffusion structure based on a conductive metal core and a carbon gas-diffusion matrix. This combination makes it possible for the flow fields in the stack to have a large open fraction (ratio between open volume and total volume) to permit large volumes of air to flow through with exceptionally low backpressure. Operations at reduced pressure require a corresponding increase in the volume of air that must be handled to deliver the same number of moles of oxygen to the anodes. Moreover, the increase in the open fraction, relative to that of a comparable prior fuel-cell design, reduces the mass of the stack. The fuel cell has been demonstrated to operate at a power density as high as 105 W/cm2 at an air pressure as low as 2 psia (absolute pressure 14 kPa), which is the atmospheric pressure at an altitude of about 50,000 ft ( 15.2 km). The improvements in the design of this fuel cell could be incorporated into designs of other fuel cells to make them lighter in weight and effective at altitudes higher than those of prior designs. Potential commercial applications for these improvements include most applications now under consideration for fuel cells.

Cisar, Alan↗

Influence of Gel Formation on the Heterogeneous Oxidation of Organic Aerosol

Recent work has shown that divalent cations can perturb the viscosity and phase state of oxygenated organic particles in unexpected ways, sometimes leading to the formation of gel states. Despite the prevalence of divalent cations and oxygenated organic molecules in atmospheric aerosol, particularly in marine environments, the influence of gel states on the reaction rates is not well established. Here, in this work, we measure and compare the impact of viscosity and gel formation on the ozonolysis chemistry of aerosol particles containing the unsaturated, oxygenated organic species ascorbic acid (AA). AA serves as an excellent proxy compound for highly oxidized molecules in the atmosphere. We measured the hygroscopic growth, phase state, viscosity, and water diffusion rate in binary particles containing AA and water and in ternary particles with an additional co-solute of either ammonium sulfate or CaCl 2 . These measurements reveal gel formation in particles mixed with CaCl 2 , as particles become rigid but allow for relatively rapid diffusion rates of water, consistent with previous observations of gel behavior. We measured the rate of ozonolysis of these particles under a range of relative humidity (RH) conditions, showing a clear decrease in the rate with decreasing RH, consistent with the increase in viscosity and slowed diffusion. Notably, we measured the rate of ozonolysis of particles existing in a gel state, showing that following an initial period of decay, the rate of reaction arrests, indicating that the organic material in the solid state is protected from the reaction. This work shows that viscous particles and gel particles exhibit different reactivity toward heterogeneous oxidants, with significant implications for how we understand the chemical evolution of aerosol particles in the atmosphere.

gels↗

Doping a bad metal: Origin of suppression of the metal-insulator transition in nonstoichiometric VO 2

Rutile ( R ) phase VO 2 is a quintessential example of a strongly correlated bad metal, which undergoes a metal-insulator transition (MIT) concomitant with a structural transition to a V-V dimerized monoclinic ( M 1 ) phase below T MIT ~ 340 K . It has been experimentally illustrated that one can control this transition by doping VO 2 . In particular, doping with oxygen vacancies ( V O ) has been shown to completely suppress this MIT without any structural transition. We explain this suppression by elucidating the influence of oxygen vacancies on the electronic structure of the metallic R phase VO 2 , explicitly treating strong electron-electron correlations using dynamical mean-field theory (DMFT) as well as diffusion Monte Carlo (DMC) flavor of quantum Monte Carlo (QMC) techniques. DMC calculations show a gap closure in the M 1 phase when vacancies are present, suggesting that when vacancies are introduced in the high-temperature rutile phase, the dimerized insulating phase cannot be reached when temperature is lowered. Both DMFT and DMC calculations of nonstoichiometric metallic rutile phase shows that this tendency not to dimerize in the presence of vacancies is because V O 's tend to change the V - 3 d filling away from its nominal half-filled value, with the e g π orbitals competing with the otherwise dominant a 1 g orbital. Loss of this near orbital polarization of the a 1 g orbital is associated with a weakening of electron correlations, especially along the V-V dimerization direction. This removes a charge-density wave (CDW) instability along this direction above a critical doping concentration, which further suppresses the metal-insulator transition. Our research further suggests that the MIT is predominantly driven by a correlation-induced CDW instability along the V-V dimerization direction.

36 MATERIALS SCIENCE↗

Time dispersion of energetic solar particles - Unexpected velocity and species dependence

The intensity-time behavior for protons and alpha-particles, as well as for carbon, oxygen, and iron ions, has been measured following the solar flare of September 19, 1974, for energies between 0.5 and about 5 MeV per nucleon. The profiles display a time dispersion which is inversely proportional to velocity for each individual species. In addition, at a given velocity the time dispersion also depends on the charge-to-mass ratio of the ion. Based on this latter dependence, it is concluded that while carbon and oxygen are essentially fully stripped, iron nuclei are not, having an effective charge of 10 plus or minus 5. The observed dispersion cannot be explained by purely rigidity-dependent diffusive propagation.

Ogallagher, J. J.↗

Compatibility experiments of facilities, materials, and propellants for electrothermal thrusters

Experiments were performed to determine the compatibility of materials and propellants for electro-thermal thrusters. Candidate propellants for resistojet propulsion include carbon dioxide, methane, hydrogen, ammonia, and hydrazine. The materials being examined are grain stabilized platinum for resistojets for Space station and rhenium for high performance resistojets for satellites. Heater mass loss and deterioration of materials were evaluated. A coiled tube of platinum, with yttria dispersed throughout the base material to inhibit grain growth, was tested in carbon dioxide at 1300 C for 2000 hr. Post-test examination indicated the platinum-yttria heater would last over 100 000 hr with less than 10 percent mass loss. Short-term compatibility tests were conducted to test the integrity of the platinum-yttria in hydrogen, methane, carbon dioxide/methane mixtures and ammonia environments. In each of these 100 hr tests, the platinum-yttria mass change indicated a minimum coil life of 100 000 hr. Facility related effects were investigated in materials tests using rhenium heated to high tempertures. Vacuum facility water reduction was monitored using a mass spectrometer. In vacuum environments obtained using only diffusion pumping and those obtained with the assistance of cryogenic equipment there were mass gains in the rhenium heaters. These mass gains were the result of the high amount of oxygen and water contained in the gas. Propellant purity and preferred test facility environments are discussed.

Whalen, M. V.↗

Compatibility experiments of facilities, materials, and propellants for electrothermal thrusters

Experiments were performed to determine the compatibility of materials and propellants for electro-thermal thrusters. Candidate propellants for resistojet propulsion include carbon dioxide, methane, hydrogen, ammonia, and hydrazine. The materials being examined are grain stabilized platinum for resistojets for space station and rhenium for high performance resistojets for satellites. Heater mass loss and deterioration of materials were evaluated. A coiled tube of platinum, with yttria dispersed throughout the base material to inhibit grain growth, was tested in carbon dioxide at 1300 C for 2000 hr. Post-test examination indicated the platinum-yttria heater would last over 100,000 hr with less than 10 percent mass loss. Short-term compatibility tests were conducted to test the integrity of the platinum-yttria in hydrogen, methane, carbon dioxide/methane mixtures and ammonia environments. In each of these 100 hr tests, the platinum-yttria mass change indicated a minimum coil life of 100,000 hr. Facility related effects were investigated in materials tests using rhenium heated to high temperatures. Vacuum facility water reduction was monitored using a mass spectrometer. In vacuum environments obtained using only diffusion pumping and those obtained with the assistance of cryogenic equipment there were mass gains in the rhenium heaters. These mass gains were the result of the high amount of oxygen and water contained in the gas. Propellant purity and preferred test facility environments are discussed.

Whalen, M. V.↗

Flame Spray Strain Gages with Improved Durability and Lifetimes

The focus of this APP research program was to improve the bond coats used in the fabrication of flame sprayed instrumentation. Typically. a bond coat is applied to a superalloy surface prior to the application of a thin dielectric coating onto which instrumentation is placed. After affixing the instrumentation, a much thicker ceramic topcoat is typically applied to protect the instrumentation from harsh environments. The fatigue life of NiCoCrAlY coated superalloys was extended beyond current state-of-the-art by relatively simple and cost effective means. Heat treatment in reduced oxygen partial pressures at 1750 to 1800 F effectively doubled the fatigue life of NiCoCrAlY coated substrates relative to as-sprayed substrates and when used in conjunction with platinum diffusion barriers yielded a four fold increase in the fatigue life of NiCoCrAlY coated substrates. Further improvements in the fatigue life of thermally sprayed coatings were made by employing intermediate coatings, which minimized thermal expansion differences between the bond coat and top coat. Combinatorial chemistry experiments yielded an optimum composition for an intermediate TCE matching coating that showed considerable promise in extending the fatigue life of thermal spray instrumentation. The intermediate coating had two functions: to reduce the surface roughness of the peaks and valleys associated with the as-sprayed NiCoCrAlY bond coat, and to produce a thin layer of a mixture of Al2O3 and NiCoCrAlY that exhibited an intermediate TCE. The optimal composition of the intermediate coating consisted of 60 wt% Al2O3 and 40 wt% NiCoCrAlY, as determined by energy dispersive analysis of x-rays (EDS). Intermediate coatings having this composition were prepared by physical vapor deposition and the resulting coating systems are being evaluated in our test facility.

Fralick, Gustave↗

Lunar and Planetary Science XXXVI, Part 20

The topics include: 1) Virtual Reality Technology as a Tool to Enhance Collaboration Between Space Exploration and Public Outreach: The Case Using the Mars Exploration Rover Images; 2) Atmospheric Electron-induced X-Ray Spectrometer (AEXS) Instrument Development; 3) Impact of Low Thermal Conductivity Layers on the Bulk Conductivity of a Martian Crustal Column; 4) Impacting Classroom Teachers Through Long-Term Professional Development; 5) Oxygen, Ca, and Ti Isotopic Compositions of Hibonite-bearing Inclusions; 6) Phenomenological Excitation Functions of Xe Isotopes with Protons on Nuclei of Cs, La and Ce; 7) Double-Diffusive Convection and Other Modes of Salinity-modulated Heat and Material Transport in Europa s Ocean; 8) Slope Morphologies of the Hellas Mensae Constructs, Eastern Hellas Planitia, Mars; 9) Development of Polygonal Thermal Contraction Patterns in a South Polar Trough, Mars 3 Years of Observations; 10) Martian Relevance of Dehydration and Rehydration in the Mg-Sulfate System; 11) Formation of Martian Volcanic Provinces by Lower Mantle Flushing? 12) Can Glasses Help Us to Unravel the Origin of Barred Olivine Chondrules? 13) Loki Patera: A Magma Sea Story; 14) Compositions of Partly Altered Olivine and Replacement Serpentine in the CM2 Chondrite QUE93005; 15) Model of Light Scattering by Lunar Regolith at Moderate Phase Angles: New Results; 16) Radiation Resistance of a Silicone Polymer Grease Based Regolith Collector for the HERA Near-Earth Asteroid Sample Return Mission; 17) Analysis of the Tectonic Lineaments in the Ganiki Planitia (V14) Quadrangle, Venus; 18) Nanometer-sized Diamonds from AGB Stars; 19) Quantifying Exact Motions Along Lineaments on Europa; 20) Geometry of Thrust Faults Beneath Amenthes Rupes, Mars; 21) Mapping of the Physical Characteristics and Mineral Composition of a Superficial Layer of the Moon or Mars and Ultra-Violet Polarimetry from the Orbital Station; 22) Negative Searches for Evidence of Aqueous Alteration on Asteroid Surfaces; 23) What Processes Have Shaped Basalt Boulders on Earth and Mars? Studies of Feature Persistence Using Facet Mapping and Fractal Analysis; 24) The Popigai Fluidizites: Dense Water Inclusions in Lechatelierite; Evidence for Shock-generated Carbonate and Hydrous Silicate Melts; 25) Missing Xenon Problem and Climate of the Early Earth; and 26) More on Magnetic Spectra from Correlated Crustal Sources on Mars

Source record↗

Ionomer Optimization for Water Uptake and Swelling in Anion Exchange Membrane Electrolyzer: Oxygen Evolution Electrode

Water electrolysis using an anion conductive, solid polymer electrolyte is an attractive method for point-of-use hydrogen production. Recent advances in catalysts and anion exchange membranes (AEM) have made alkaline devices increasingly competitive with their acidic counterparts. However, less attention has been paid to the anion conductive ionomers (ACI) used in the fabrication of electrodes for AEM electrolyzers. The ACI contributes to ion conduction between the catalyst and bulk electrolyte and serves as a binder for adhering the catalyst to the gas diffusion layer and AEM. Ionic conductivity, water uptake and ionomer swelling are critical properties for electrode performance. High ion exchange capacity (IEC) in the ionomer is desired for reduced electrode resistance, however, it can lead to excess water uptake (WU) and disruptive ACI swelling. In this study, a series of poly(norbornene)-based ionomers were synthesized, characterized and used to fabricate oxygen evolving anodes for low-temperature AEM water electrolysis. The IEC of the ionomers (0 to 4.73 meq g −1 ) was adjusted by controlling the ratio of ion conducting to non-ion conducting norbornene monomers in the ACI tetrablock copolymers. Low conductivity ionomers are shown to yield the best-performing oxygen evolution electrodes, in the absence of ACI polymer cross-linking because they do not experience excessive water swelling. Light cross-linking within the anode ACI was used as a means to independently lower WU of the ionomer without compromising ionic conductivity. This control over water swelling allows higher ionic conductivity within the ACI to be used in water-fed electrolyzer applications. Other methods of water management were compared including the use of hydrophobic additives and adjustment of the ionomer concentration in the electrode. As a result, it was shown that the cell performance greatly benefits from a highly conductive ionomer in the oxygen evolution reaction electrode if the WU is managed.

08 HYDROGEN↗

Experimental measurement of the rapid mixing of fuel and air in a multi-element diffusion (Hencken) burner

Flat flame burners are valuable tools for studying complex combustion phenomena like particle synthesis due to the well-controlled and well-behaved initial and boundary conditions. In this study, the methane/air flame temperature and tracer density profiles of a multi-element diffusion burner equipped with a central tube were characterized using krypton (Kr) x-ray fluorescence at the Advanced Photon Source at Argonne National Laboratory. The experiments were performed using a fuel-to-oxygen equivalence ratio of 0.8 and 3.3% Kr by volume was added to the reactant gases. One- and two-dimensional scans of non-combusting (i.e., cold flow) and combusting conditions, both with and without flow through the central tube were performed. Spatially-resolved Kr number density profiles were obtained at different planar locations and heights above the surface of the burner. The results show rapid mixing occurred near the exit-plane of the burner and increased spatial uniformity was achieved from 0.1 mm to 0.5 mm above the surface of the burner. Further, the data also showed the impact of the central tube flow on the main methane/air flame, including evidence of the central tube flow mixing with the main flow. Flame temperatures were calculated from the fluorescence measurements at various heights above the burner surface and were in good agreement with model predictions for a burner stabilized flame. These high-fidelity measurements provide accurate baseline data that are particularly valuable for understanding the effects of fuel and air mixing on downstream phenomena, such as the formation of condensed-phase products.

42 ENGINEERING↗

Pulmonary function in men after oxygen breathing at 3.0 ATA for 3.5 h

A complete description of pulmonary measurements obtained after continuous O2 exposure of 13 healthy men at 3.0 ATA for 3.5 h is presented. Measurements included flow-volume loops, spirometry, and airway resistance(n = 12); CO diffusing capacity (n = 11); closing volumes (n= 6); and air vs. HeO2 forced vital capacity maneuvers (n = 5). The average difference in maximum mid expiratory flows at 50 percent vital capacity on air and HeO2 was found to be significantly reduced postexposure by 18 percent. Raw and CO diffusing capacity were not changed postexposure. It is concluded that the relatively large change in forced expiratory flow at 25-75 percent of vital capacity compared with the mean forced expiratory volume in 1 s, the reduction in density dependence of flow, and the normal Raw postexposure are all consistent with flow limitation in peripheral airways as a major cause of the observed reduction in expiratory flow.

Clark, J. M.↗

Cobalt-free and high-rate stable 5V lithium nickel manganese oxide spinel cathodes enabled via surface oxygen vacancies

Spinel LiNi 0.5 Mn 1.5 O 4 offers both the high-rate, low-cost and safety advantages of LiFePO 4 and the high energy density of LiNiₓMnᵧCo₁₋ₓ₋ᵧO₂ and LiNiₓCoᵧAlzO₂ cathodes. However, the large operating voltage of these materials induces electrolyte oxidation, which degrades the interface and drives Mn dissolution. These reactions are further exacerbated at high rates due to temperature rise. In this study, we discover that ammoniacal treatment followed by annealing introduces a high density of oxygen vacancies in the “near-surface region” of LiNi 0.5 Mn 1.5 O 4 particles. These vacancies release electrons changing the oxidation state of Mn and suppressing its tendency to oxidize the electrolyte. Further, these vacancies enhance the electrode’s electronic conductivity (by ∼3-fold) and Li + diffusivity (by ∼2-fold) greatly improving charge transport, especially when operated at high rates. This results in an across-the-board improvement in self-discharge, specific capacity, energy density, rate capability, coulombic efficiency and cycling stability. When cycled at ∼200 mA g −1 , the capacity fade averaged over 3000 cycles for the surface vacancy-enriched material is ∼0.0167% per cycle compared to an order of magnitude higher fade rate for the baseline material. In conclusion, these findings reveal the potential of targeted surface oxygen vacancy doping to develop cobalt-free and high energy density cathodes that tolerate fast charging and deliver improved cycle life.

Cobalt-free cathodes↗