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At least 1,027 records · Page 57
All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

Universal Responses of Cyclic-Oxidation Models Studied

Oxidation is an important degradation process for materials operating in the high-temperature air or oxygen environments typical of jet turbine or rocket engines. Reaction of the combustion gases with the component material forms surface layer scales during these oxidative exposures. Typically, the instantaneous rate of reaction is inversely proportional to the existing scale thickness, giving rise to parabolic kinetics. However, more realistic applications entail periodic startup and shutdown. Some scale spallation may occur upon cooling, resulting in loss of the protective diffusion barrier provided by a fully intact scale. Upon reheating, the component will experience accelerated oxidation due to this spallation. Cyclic-oxidation testing has, therefore, been a mainstay of characterization and performance ranking for high-temperature materials. Models simulate this process by calculating how a scale spalls upon cooling and regrows upon heating (refs. 1 to 3). Recently released NASA software (COSP for Windows) allows researchers to specify a uniform layer or discrete segments of spallation (ref. 4). Families of model curves exhibit consistent regularity and trends with input parameters, and characteristic features have been empirically described in terms of these parameters. Although much insight has been gained from experimental and model curves, no equation has been derived that can describe this behavior explicitly as functions of the key oxidation parameters.

Smialek, James L.↗
DOE OSTI2020

Effect of lithium incorporation on tweaking the electrocatalytic behavior of tantalum-based oxides

To study the effect of lithium incorporation on the electrochemical properties and catalytic behavior of tantalum-based oxides, a series of mesoporous lithium-contained tantalum oxides was developed adopting an inverse micelle-based sol gel synthesis method. Four various phases of amorphous Ta 2 O 5 , polycrystalline LiTaO 3 , Li 5.04 Ta 6.16 O 17.92 , and Li 3 TaO 4 were determined for samples synthesized at Li/Ta ratios of 0.5 (LTO-0.5), 1 (LTO-1), 2 (LTO-2), and 3 (LTO-3) respectively. The surface analysis revealed that LTO-2 sample is featured with lower amount of lithium atoms at the surface rather than the bulk of the sample. The electrochemical analysis of LTO samples showed that LTO-2 possesses lower charge transfer resistance extracted from impedance spectroscopy that consequently leads to a better electrocatalytic performance. The LTO-2 electrode also showed a low open circuit potential (OCP) combined with a relatively higher electroactive surface area, thus capable of running an electrooxidation reaction at a potential lower than all other LTO samples. The more negative OCP value of LTO-2 electrode in AA solution states a more facile electron transfer between the analyte and electrode compared to other synthesized samples. Mott–Schottky plots of LTO electrodes are characterized by positive slopes which indicate n-type semiconductor behavior. The charge carrier density (5.5 × 10 19 cm -3 ) in LTO-2 sample is the lowest among all other samples. The charge carrier density is dependent on the amount of applied lithium in the synthesis confirming various lithium diffusion behaviors in LTO samples. The lower carrier concentration in LTO-2 justifies its higher activity in electrooxidation providing less populated lower unoccupied molecular orbital (LUMO) for the accommodation of electrons extracted from the analyte higher occupied molecular orbital (HOMO). Therefore, LTO-2 showed an improved electrocatalytic performance due to lower charge transfer resistance (higher conductivity) offered by lower amount of lithium atom at its surface and higher oxygen vacancies in the bulk.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1972

The chemistry of neutral species in the D and E regions.

The photodissociation of molecular species such as oxygen, nitrogen, and water vapor in the upper atmosphere leads to the formation of a reservoir of chemical energy consisting of highly reactive atomic gases. The reactions of these with each other, and with the rest of the atmosphere, give a complex neutral chemistry involving many species and reactions. Local equilibrium can rarely be assumed for these reactions; transport by the horizontal and vertical mean flow, by eddy diffusion, and by molecular diffusion has quite different effects on the various constituents, depending on the time constants. The entire subject of the neutral chemistry in the D and E regions (between 50 and 160 km altitude) is reviewed, and related to existing experimental results. Needs for further research on the subject are indicated.

Bowhill, S. A.↗
NASA NTRS1973

Atmospheric composition

The earth's atmosphere is made up of a number of gases in different relative amounts. Near sea level and up to about 90 km, the amount of these atmospheric gases in clean, relatively dry air is practically constant. Four of these gases, nitrogen, oxygen, argon, and carbon dioxide, make up 99.99 percent by volume of the atmosphere. Two gases, ozone and water vapor, change in relative amounts, but the total amount of these two is very small compared to the amount of the other gases. The atmospheric composition shown in a table can be considered valid up to 90 km geometric altitude. Above 90 km, mainly because of molecular dissociation and diffusive separation, the composition changes.

Daniels, G. E.↗
NASA NTRS1991

Space water electrolysis: Space Station through advance missions

Static Feed Electrolyzer (SFE) technology can satisfy the need for oxygen (O2) and Hydrogen (H2) in the Space Station Freedom and future advanced missions. The efficiency with which the SFE technology can be used to generate O2 and H2 is one of its major advantages. In fact, the SFE is baselined for the Oxygen Generation Assembly within the Space Station Freedom's Environmental Control and Life Support System (ECLSS). In the conventional SFE process an alkaline electrolyte is contained within the matrix and is sandwiched between two porous electrodes. The electrodes and matrix make up a unitized cell core. The electrolyte provides the necessary path for the transport of water and ions between the electrodes, and forms a barrier to the diffusion of O2 and H2. A hydrophobic, microporous membrane permits water vapor to diffuse from the feed water to the cell core. This membrane separates the liquid feed water from the product H2, and, therefore, avoids direct contact of the electrodes by the feed water. The feed water is also circulated through an external heat exchanger to control the temperature of the cell.

Ronald J Davenport↗
DOE OSTI2021

Loss and Isotopic Fractionation of Alkali Elements during Diffusion-Limited Evaporation from Molten Silicate: Theory and Experiments

Moderately volatile elements (MVEs) are variably depleted in planetary bodies, reflecting the imprints of nebular and planetary processes. Among MVEs, Na, K, and Rb are excellent tracers for unraveling the history of MVE depletion in planetary bodies because they have similar geochemical behaviors but can be chemically fractionated by evaporation and condensation processes. Furthermore, K and Rb are amenable to high-precision isotopic analyses, which can help constrain the conditions of evaporation and condensation. To quantitatively understand why Na, K, and Rb are depleted in planetary bodies, we have carried out vacuum evaporation experiments from basaltic melt at 1200 and 1400 °C to study their evaporation kinetics and isotopic fractionations. We chose this composition because it is relevant to evaporation from small differentiated planetesimals. The Rb isotopic compositions of the evaporation residues were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), and the K isotopic compositions were measured along profiles across the residues by secondary ion mass spectrometry (SIMS). In the 1400 °C run products, we found that the concentrations of both K and Rb in the run products decreased from core to rim, which was accompanied by a heavy K isotope enrichment near the surface. This indicates that, in this run, evaporation was limited by diffusion. To use those data quantitatively, we derive analytical equations that describe the evaporation rate and isotopic fractionation associated with diffusion-limited evaporation from a sphere, slab, and cylinder in transient and quasi-steady state regimes. This model is used to tease out the roles that diffusive transport in the melt and evaporation at the melt/gas interface play in setting the elemental depletion and isotopic composition of the residue. Under our experimental conditions, volatility decreases in the order of Na, Rb, and K. Using our experimental results in a thermodynamic model, we have estimated the product γΓ of activity coefficients × evaporation coefficients of Na, Rb, and K. The measured isotopic compositions of the residues are well explained using Rayleigh distillations, whereby the relative volatilities of K and Rb isotopes are given by the square root of their masses. We use our results and previously published data to predict how K and Rb could have been lost as a function of temperature, melt composition, oxygen fugacity, and saturation degree relevant to Vesta’s building blocks. We find that the K and Rb depletions, K/Rb elemental fractionation, and δ 41 K and δ 87 Rb isotopic fractionations of Vesta (as sampled by howardite-eucrite-diogenite (HED) meteorites) are best explained by evaporation of submillimeter size objects for 0.1-10 years at moderate temperatures (~1050 °C) in a medium ~98.8% saturated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1973

The drift field model applied to the lithium-containing silicon solar cell

The drift field model used by Wolf to calculate the short-circuit current was extended to permit calculations of the open-circuit voltage and the maximum power under conditions of illumination of either tungsten (2800 C) source or AMO sunlight. Voltages were calculated using an expression for the drift field diode saturation current derived here. The model, applied to the oxygen rich (C-13 group) lithium solar cells, was used to calculate the pre-and post-electron bombardment trends for lithium gradients in the range of 10 to the 18th power to 10 to the 19th power Li/cm to the 4th power. Published experimental data characterizing these cells were used to tailor the model. The calculated trends are in reasonable agreement with the empirical data of Faith. Diffusion length degradation and carrier removal effects were sufficient to predict the cell performance up to 3 x 10 to the 14th power e/sq cm. Beyond this fluence it was necessary to include drift field removal effects.

Godlewski, M. P.↗
NASA NTRS1975

A new gas lesion syndrome in man, induced by 'isobaric gas counterdiffusion'

Normal men have been found to develop pruritis and gas bubble lesions in the skin, and disruption of vestibular function, when breathing nitrogen or neon with oxygen while surrounded by helium at increased ambient pressure. This phenomenon, which occurs at stable ambient pressures, at 1 or many ATA, has been designated the isobaric gas counterdiffusion syndrome. In a series of analyses and experiments in vivo and in vitro the cause of the syndrome has been established as due to gas accumulation and development of gas bubbles in tissues as a result of differences in selective diffusivities, for various respired and ambient gases, in the tissue substances between capillary blood and the surrounding atmosphere. The phenomenon described in man is an initial stage of a process shown later in animals to progress to continuous, massive, lethal, intravascular gas embolization.

Lambertsen, C. J.↗
NASA NTRS1987

Deuterium in the daytime thermosphere

Ion concentration measurements for H(+) and D(+) from the magnetic ion mass spectrometer on the Atmosphere Explorer C satellite are used, in conjunction with other atmospheric data, to determine the concentrations of H and D in the nonpolar daytime thermosphere. The ratio of the observed D(+) to H(+) concentrations has essentially the same height dependence in the 300 to 800-km region as expected for their neutral counterparts, even in the presence of ion temperature gradients and probable large vertical ion fluxes. Rapid charge exchange with atomic oxygen ensures that D/H is about equal to D(+)/H(+) at the lower altitudes where the derived D to H concentration ratio is a factor of about 6 larger than its sea level value, for an exospheric temperature of 930 K. This relative enhancement of deuterium arises from the fact that hydrogen more readily escapes the earth, and a large vertical gradient in the H concentration relative to its diffusive equilibrium value is necessary to drive this upward flux through the lower thermosphere. If these planetary losses of hydrogen are much greater than those associated with evaporative escape, as is the current view, then correspondingly larger deuterium loss rates are also likely in order that the thermospheric D/H ratio not increase well above the observed value. The absolute winter daytime concentration of deuterium at 300 km is found to be 210 + or - 50 atoms/cu cm.

Breig, E. L.↗
NASA NTRS2000

Formation of Leading-Edge Pinholes in the Space Shuttle Wings Investigated

The space shuttle wing leading edge and nose cap are composed of a carbon/carbon composite that is protected by silicon carbide. The coefficient of thermal expansion mismatch leads to cracks in the silicon carbide. The outer coating of the silicon carbide is a sodium-silicate-based glass that becomes fluid at the shuttles high reentry temperatures and fills these cracks. Small pinholes roughly 0.1 mm in diameter have been observed on these materials after 12 or more flights. These pinholes have been investigated by researchers at the NASA Johnson Space Center, Rockwell International, the Boeing Company, Lockheed Martin Corporation, and the NASA Glenn Research Center at Lewis Field to determine the possible sources and the extent of damage. A typical pinhole is illustrated in the photomicrographs. These pinholes are found primarily on the wing leading edges and not on the nose cap, which is covered when the orbiter is on the launch pad. The pinholes are generally associated with a bead of zincrich glass. Examination of the orbiter and launch structure indicates that weathering paint on the launch structure leads to deposits of zinc-containing paint flakes on the wing leading edge. These may become embedded in the crevices of the wing leading edge and form the observed zinc-rich glass. Laboratory experiments indicate that zinc oxide reacts vigorously with the glass coating on the silicon carbide. Thus, it is likely that this is the reaction that leads to pinhole formation (Christensen, S.V.: Reinforced Carbon/Carbon Pin Hole Formation Through Zinc Oxide Attack. Rockwell International Internal Letter, RDW 96 057, May 1996). Cross-sectional examination of pinholes suggests that they are enlarged thermal expansion mismatch cracks. This is illustrated in the photomicrographs. A careful microstructural analysis indicates that the pinhole walls consist of layers of zinc-containing glass. Thus, pinholes are likely formed by zinc oxide particles lodging in crevices and forming a corrosive zinc-rich glass that enlarges existing cracks. Having established the likely source of the pinholes, we next needed to model the damage. Our concern was that if a pinhole went through the silicon carbide to the carbon/carbon substrate, oxygen would have a clear path to oxidize the carbon at high temperatures. This possibility was examined with studies in a laboratory furnace. An ultrasonic drill was used to make artificial pinholes in a sample of protected carbon/carbon. After exposure, the specimens were weighed and cross-sectioned to quantify the extent of oxidation below the pinhole. The results at higher temperatures showed good agreement with a simple diffusion-control model. This model is based on the two-step oxidation of carbon to carbon monoxide and carbon dioxide. The fluxes are illustrated in the final figure. The model indicates a strong dependence on pinhole diameter. For smaller diameters and short times, the oxidation of carbon is very limited.

Jacobson, Nathan S.↗
DOE OSTI2022

Effect of surface acidity modulation on Pt/Al 2 O 3 single atom catalyst for carbon monoxide oxidation and methanol decomposition

With ideal metal utilization efficiency and homogeneous active sites, single atom catalysts (SACs) have attracted extensive attention in heterogeneous catalysis field. The performance of SACs is highly dependent on the local coordination environment of metal single atoms. However, few works reported the effect of surface acidity modification on the performance of SACs such as Pt SACs which have been widely studied nowadays. In this work, a Pt/Al 2 O 3 SAC has been successfully prepared using a bayerite Al(OH) 3 as support through simple IWI method for Pt loading. Through post-modification of Pt/Al 2 O 3 with acidic WO 3 and basic MgO, the surface acidity of Pt/Al 2 O 3 was tuned. Here, activity of CO oxidation and methanol decomposition on the modified catalysts has been evaluated. It was found that the catalytic performance was highly related to the surface acidity of Pt SACs. Basic MgO modified Pt/Al 2 O 3 performed better in CO oxidation under the reaction condition with H 2 O. Acidic WO 3 modified Pt/Al 2 O 3 showed superior activity in methanol decomposition. Detailed characterization and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study suggested that the positive H 2 O effect on CO oxidation was due to the mitigated formation of bicarbonate species on Pt/Al 2 O 3 and WO 3 /Pt/Al 2 O 3 catalysts and the promoted desorption of carbonate species from MgO/Pt/Al 2 O 3 . The superior methanol decomposition performance on WO 3 /Pt/Al 2 O 3 was owing to its abundant oxygen vacancies and high resistance to carbonate accumulation. This study highlights the importance of surface acidity modulation of Pt SACs in heterogeneous catalysis and suggests that fine-tuning the surface acidity can be an effective strategy in new SACs development.

36 MATERIALS SCIENCE↗
NASA NTRS1989

Contamination of liquid oxygen by pressurized gaseous nitrogen

The penetration of pressurized gaseous nitrogen (GN2) into liquid oxygen (LOX) was investigated experimentally in the 7-inch High Temperature Tunnel, the pilot tunnel for the 8-foot High Temperature Tunnel (8'HTT) at Langley Research Center. A preliminary test using a nuclear monitor revealed the extent of the liquid nitrogen (LN2) build-up at the LOX interface as a function of GN2 pressure. Then an adaptation of the differential flash vaporization technique was used to determine the binary diffusivity of the LOX-LN2 system at a temperature of 90.2 K. The measured value D equals 0.000086 sq cm/s + or - 25 percent together with two prior measurements at lower temperatures revealed an excellent fit to the Arrhenius equation, yielding a pre-exponential factor D sub 0 equals 0.0452 sq cm/s and an activation enthalpy H equals 1.08 kcal/mol. At a pressure of 1700 psi and holding time of 15 min, the penetration of LN2 into LOX (to a 1 percent contamination level) was found to be 0.9 cm, indicating but minimal impact upon 8'HTT operations.

Zuckerwar, Allan J.↗
NASA NTRS2013

Does Oxygen Isotopic Heterogeneity in Refractory Inclusions and Their Wark-Lovering Rims Record Nebular Repressing?

Large systematic variations in O-isotopic compositions found within individual mineral layers of rims surrounding Ca-, Al-rich inclusions (CAIs) and at the margins of some CAIs imply formation from distinct environments [e.g., 1-3]. The O-isotope compositions of many CAIs preserve a record of the Solar nebula gas believed to initially be O-16-rich (delta O-17 less than or equal to -25%0) [4-5]. Data from a recent study of the compact Type A Allende CAI, A37, preserve a diffusion profile in the outermost ~70 micrometers of the inclusion and show greater than 25%0 variations in delta O-17 within its ~100 micrometer-thick Wark-Lovering rim (WL-rim) [3]. This and comparable heterogeneity measured in several other CAIs have been explained by isotopic mixing between the O-16-rich Solar reservoir and a second O-16-poor reservoir (probably nebular gas) with a planetary-like isotopic composition, e.g., [1,2,3,6]. However, there is mineralogical and isotopic evidence from the interiors of CAIs, in particular those from Allende, for parent body alteration. At issue is how to distinguish the record of secondary reprocessing in the nebula from that which occurred on the parent body. We have undertaken the task to study a range of CAI types with varying mineralogies, in part, to address this problem.

Simon, J. I.↗
DOE OSTI2025

Side-Chain and Ring-Size Effects on Permeability in Artificial Water Channels

Artificial water channels (AWCs) have emerged as a promising framework for stable water permeation, with water transport rates comparable to aquaporins (3.4–40.3 × 10 8 H 2 O/channel/s). In this study, we probe the influence of ring-size and side-chain length on the water permeability observed within a class of AWCs termed ligand-appended pillar[n]arenes (LAPs) that have an adjustable ring-size (m) and side-chain length (n). Through all-atom molecular dynamics simulations, we calculate the permeability of these channels using the collective diffusion model and find their permeabilities. We characterize the mechanistic influence of pillar[n]arene ring-size and side-chain length on the channel water permeability by analyzing the characteristics of the internal permeating water-wire and the surrounding channel structure. We observe that water permeability decreases as a function of increasing ring-size due to increases in hydrophilic contacts between the permeating water-wire and the oxygen groups on the channel wall. Further, we observe an increase in water permeability as a function of side-chain length due to increased partitioning of the channel terminal groups into the hydrophilic blocks of the surrounding bilayer. For the LAP6 channel, with increase in side-chain length, the distance between terminal groups increases and leads to an increase in pore size, thereby enhancing water permeability. In the case of LAP5, as side-chain length increases, the channel displays a compensatory effect between tilt and bend angle due to the flexible side-chains. Such flexibility leads to higher terminal group partitioning in the hydrophilic blocks of the bilayer and extends the permeating water-wire. Furthermore, this increase in water-wire length and hydrophilic block access overcomes the nonmonotonic pore size trend in pillar[5]arene channels.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts

Silica-supported ZnO efficiently catalyzes the nonoxidative dehydrogenation of ethanol to acetaldehyde, which is relevant for production of 1,3-butadiene from bioethanol. Characterization with in situ spectroscopies under dehydrated conditions (high sensitivity-low energy ion scattering (HS-LEIS), diffuse reflectance (DR) UV–vis, X-ray absorption spectroscopy (XAS), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), inelastic neutron scattering (INS), and UV Raman), and ammonia adsorption probed by temperature-programmed desorption followed by DRIFTS and mass spectrometry (DRIFTS-MS NH 3 -TPD), and DFT calculations revealed that the supported ZnO x phase was present as isolated surface ZnO x sites on SiO 2 , with the vast majority coordinated by two siloxane bonds and one silicon atom with two nonbridging oxygens ((≡SiO) 2 Zn 2+ O 2 Si=), anchored at 4-, 5-, and 6-membered siloxane rings. A minor fraction of surface ZnO x sites possessed Lewis acidity, and even fewer sites possessed a Bro̷nsted acidic Zn(OH) + Si moiety. Ethanol temperature-programmed surface reaction-mass spectrometry (TPSR-MS) with various oxidative or ethanol reaction pretreatments indicated that only sites with Lewis and Bro̷nsted acidic character (Zn(OH) + Si) were active for ethanol dehydrogenation, while the majority surface (≡SiO) 2 Zn 2+ O 2 Si= sites were inactive. Greater heterogeneity among all surface ZnO x sites, as assessed by in situ DR UV–vis spectroscopy, was associated with a greater number of ZnO x sites that were active for ethanol dehydrogenation as well as lower enthalpic barriers for acetaldehyde production among the most active surface ZnO x sites. Turnover frequencies and the apparent activation energy for ethanol dehydrogenation were determined from steady-state kinetics. Together, these findings suggested that anchoring inactive surface (≡SiO) 2 Zn 2+ O 2 Si= sites on the silica support caused a greater number of active surface ZnO x sites to adopt a more strained configuration, promoting ethanol dehydrogenation catalysis. Pretreatments and catalysts that promoted desorption of ethanol during TPSR, taken as a marker of surface dehydroxylation, were associated with an increased number of the most active surface (Zn(OH) + Si) sites. Such findings suggested that inactive surface ZnO x sites were activated for ethanol dehydrogenation by dehydroxylation of the support and/or decreased coordination to hemilabile siloxane ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

A flux-limited treatment for the conductive evaporation of spherical interstellar gas clouds

In this work, we present and analyze a new analytic solution for the saturated (flux-limited) thermal evaporation of a spherical cloud. This work is distinguished from earlier analytic studies by allowing the thermal conductivity to change continuously from a diffusive to a saturated form, in a manner usually employed only in numerical calculations. This closed form solution will be of interest as a computational benchmark. Using our calculated temperature profiles and mass-loss rates, we model the thermal evaporation of such a cloud under typical interstellar medium (ISM) conditions, with some restrictions. We examine the ionization structure of the cloud-ISM interface and evaluate column densities of carbon, nitrogen, oxygen, neon, and silicon ions toward the cloud. In accord with other investigations, we find that ionization equilibrium is far from satisfied under the assumed conditions. Since the inclusion of saturation effects in the heat flux narrows the thermal interface relative to its classical structure, we also find that saturation effects tend to lower predicted column densities.

Dalton, William W.↗
NASA NTRS2011

The Development of a CO2 Test Capability in the NASA JSC ARCJet for Mars Reentry Simulation

The Atmospheric Reentry Materials and Structures Evaluation Facility (ARMSEF) located at NASA Johnson Space Center is used for simulating the extreme environment experienced upon reentry for the development and certification of thermal protection systems (TPS). The facility supports a large variety of programs and was heavily leveraged for the certification and operational support of the TPS for the Orbiter and, more recently, the development of the heat shield for CEV. This paper will provide more detail into the heritage of the facility. Unique attributes of the facility include a modular aerodynamically stabilized arc heater and independently controlled O2 and N2 for the test gases. When combining the O2 and N2 in a 23:77 mass ratio respectively the Earth s atmosphere is accurately simulated and via modification of this ratio the investigation of the effects of atomic oxygen on a material s response is possible. In the summer of 2010 a development effort was started to add CO2 as a third independently controlled test gas such that, when combined with N2, opens up the possibility of accurately simulating a Martian reentry environment. This paper will discuss the test facility, especially the arc heater, in more detail. Initial testing involved relatively low concentrations of CO2 combined with N2 for the primary purpose of gathering data to answer two pressing safety concerns. The first being the rate of production of carbon monoxide (CO) within the ejector vacuum system. The main concern was that CO can be flammable and possibly explosive at high enough concentrations and pressures. The hazard control during the development phase involved the use of injecting N2 inside the test chamber diffuser to dilute and reduce the concentration of any and all CO present. A residual gas analyzer (RGA) was used to determine the relative amount of CO in the exhaust gas and provide a conversion rate of CO2 to CO. This paper will discuss in more detail the results of the RGA data and the calculated conversion rate. The second safety concern addressed is the possible formation of hydrogen cyanide (HCN) and cyanide (CN). HCN would primarily be present in the cooling water while the CN would most probably condense onto the interior surfaces of the test chamber. Water samples and wipes of the test chamber surfaces were analyzed by an industrial hygienist for the presence of HCN and CN. His paper will discuss these results in more detail. Throughout this development effort measurements of the CO2:N2 flowfield were made with heat flux and pressure probes and with laser induced fluorescence (LIF) of the atomic oxygen. This paper will discuss these results

DelPapa, Steven V.↗
DOE OSTI2020

Photodissociation and Theory to Investigate Uranium Oxide Cluster Cations

Uranium oxide cluster cations of the form U n O m + are produced by laser vaporization of a depleted uranium rod in a pulsed supersonic expansion. Ions are mass-analyzed and mass-selected with a time-of-flight spectrometer and studied with UV laser multiphoton dissociation. Cations of the stoichiometry UO 2 (UO 3 ) n + were observed as photofragments from all photodissociated cluster cations. (UO 3 ) n + clusters were also observed to result from dissociation of larger (UO 3 ) n + clusters, with UO 3 neutral as a common leaving group. Electronic structure calculations were used to investigate the stability of the prominent uranium oxide cluster cations using density functional theory (DFT) with the hybrid B3LYP exchange-correlation functional and at the CCSD(T) level and cc-pVnZ-PP basis sets (n = D,T), including diffuse orbitals as computational expense and availability permitted. Clustering energies, relative energies and dissociation energies of the cations are reported. The lowest energy neutral (UO 3 ) n clusters up to n = 3 are rings, n = 4 and 5 are chains with very low energy rings, and n = 6 is 3D. Finally, the lowest energy structures for UO 2 (UO 3 ) n + are composed of uranyl-like UO 2 + units bound by bridging oxygens to other UO 2 2+ units for n = 2 and 3, and for n = 4 a more complex 3D structure is predicted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗