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At least 883 records · Page 49

A Dual-Line Detection Rayleigh Scattering Diagnostic Technique for the Combustion of Hydrocarbon Fuels and Filtered UV Rayleigh Scattering for Gas Velocity Measurements

Non-intrusive techniques for the dynamic measurement of gas flow properties such as density, temperature and velocity, are needed in the research leading to the development of new generation high-speed aircraft. Accurate velocity, temperature and density data obtained in ground testing and in-flight measurements can help understand the flow physics leading to transition and turbulence in supersonic, high-altitude flight. Such non-intrusive measurement techniques can also be used to study combustion processes of hydrocarbon fuels in aircraft engines. Reliable, time and space resolved temperature measurements in various combustor configurations can lead to a better understanding of high temperature chemical reaction dynamics thus leading to improved modeling and better prediction of such flows. In view of this, a research program was initiated at Polytechnic University's Aerodynamics Laboratory with support from NASA Lewis Research Center through grants NAG3-1301 and NAG3-1690. The overall objective of this program has been to develop laser-based, non-contact, space- and time-resolved temperature and velocity measurement techniques. In the initial phase of the program a ND:YAG laser-based dual-line Rayleigh scattering technique was developed and tested for the accurate measurement of gas temperature in the presence of background laser glare. Effort was next directed towards the development of a filtered, spectrally-resolved Rayleigh/Mie scattering technique with the objective of developing an interferometric method for time-frozen velocity measurements in high-speed flows utilizing the uv line of an ND:YAG laser and an appropriate molecular absorption filter. This effort included both a search for an appropriate filter material for the 266 nm laser line and the development and testing of several image processing techniques for the fast processing of Fabry-Perot images for velocity and temperature information. Finally, work was also carried out for the development of a new laser-based strain-rate and vorticity technique for the time-resolved measurement of vorticity and strain-rates in turbulent flows.

Otugen, M. Volkan↗

Pool Boiling Experiment Has Five Successful Flights

The Pool Boiling Experiment (PBE) is designed to improve understanding of the fundamental mechanisms that constitute nucleate pool boiling. Nucleate pool boiling is a process wherein a stagnant pool of liquid is in contact with a surface that can supply heat to the liquid. If the liquid absorbs enough heat, a vapor bubble can be formed. This process occurs when a pot of water boils. On Earth, gravity tends to remove the vapor bubble from the heating surface because it is dominated by buoyant convection. In the orbiting space shuttle, however, buoyant convection has much less of an effect because the forces of gravity are very small. The Pool Boiling Experiment was initiated to provide insight into this nucleate boiling process, which has many earthbound applications in steamgeneration power plants, petroleum plants, and other chemical plants. In addition, by using the test fluid R-113, the Pool Boiling Experiment can provide some basic understanding of the boiling behavior of cryogenic fluids without the large cost of an experiment using an actual cryogen.

Chiaramonte, Fran↗

Conversion Coatings for Aluminum Alloys by Chemical Vapor Deposition Mechanisms

With the rise of environmental awareness and the renewed importance of environmentally friendly processes, the United States Environmental Protection Agency has targeted surface pre-treatment processes based on chromates. Indeed, this process has been subject to regulations under the Clean Water Act as well as other environmental initiatives, and there is today a marked movement to phase the process out in the near future. Therefore, there is a clear need for new advances in coating technology that could provide practical options for replacing present industrial practices. Depending on the final application, such coatings might be required to be resistant to corrosion, act as chemically resistant coatings, or both. This research examined a chemical vapor deposition (CVD) mechanism to deposit uniform conversion coatings onto aluminum alloy substrates. Robust protocols based on solutions of aryl phosphate ester and multi-oxide conversion coating (submicron) films were successfully grown onto the aluminum alloy samples. These films were characterized by X-ray Photoelectron Spectroscopy (XPS). Preliminary results indicate the potential of this technology to replace aqueous-based chromate processes.

Reye, John T.↗

Sorption-enhanced steam reforming of toluene using multifunctional perovskite phase transition sorbents in a chemical looping scheme

Abstract Sorption-enhanced steam reforming (SESR) of toluene (SESRT) using catalytic CO 2 sorbents is a promising route to convert the aromatic tar byproducts formed in lignocellulosic biomass gasification into hydrogen (H 2 ) or H 2 -rich syngas. Commonly used sorbents such as CaO are effective in capturing CO 2 initially but are prone to lose their sorption capacity over repeated cycles due to sintering at high temperatures. Herein, we present a demonstration of SESRT using A- and B-site doped Sr 1− x A’ x Fe 1− y B’ y O 3− δ (A’ = Ba, Ca; B’ = Co) perovskites in a chemical looping scheme. We found that surface impregnation of 5–10 mol% Ni on the perovskite was effective in improving toluene conversion. However, upon cycling, the impregnated Ni tends to migrate into the bulk and lose activity. This prompted the adoption of a dual bed configuration using a pre-bed of NiO/ γ –Al 2 O 3 catalyst upstream of the sorbent. A comparison is made between isothermal operation and a more traditional temperature-swing mode, where for the latter, an average sorption capacity of ∼38% was witnessed over five SESR cycles with H 2 -rich product syngas evidenced by a ratio of H 2 : CO x > 4.0. XRD analysis of fresh and cycled samples of Sr 0.25 Ba 0.75 Fe 0.375 Co 0.625 O 3- δ reveal that this material is an effective phase transition sorbent—capable of cyclically capturing and releasing CO 2 without irreversible phase changes occurring.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reflectance Spectroscopy and Lunar Sample Science: Finally a Marriage After Far Too Long an Engagement

Inferences about the igneous and impact evolution of planetary bodies are based upon spectral remote sensing of their surfaces. However, it is not the rocks of a body that are seen by the remote sensing, but rather the regolith, that may contain small pieces of rock but also many other phases as well. Indeed, recent flybys of objects even as small as asteroid Ida have shown that these objects are covered by a regolith. Thus, spectral properties cannot be directly converted into information about the igneous history of the object. It is imperative to fully understand the nature of the regolith, particularly its finer fraction termed "soil," to appreciate the possible effects of "space weathering" on the reflectance spectra. We have initiated a study of our nearest, regolith-bearing body, the Moon, as "ground truth" for further probes of planetary and asteroidal surfaces. the foundation for remote chemical and mineralogical analyses lies in the physics underlying optical absorption and the linking of spectral properties of materials measured in the laboratory to well understood mineral species and their mixtures. From this statement, it is obvious that there should be a thorough integration of the material science of lunar rocks and soils with the remote-sensing observations. That is, the lunar samples returned by the Apollo missions provide a direct means for evaluation of spectral characteristics of the Moon. However, this marriage of the remote-sensing and lunar sample communities has suffered from a prolonged unconsummated betrothal, nurtured by an obvious complacency by both parties. To make more direct and quantitative links between soil chemistry/mineralogy and spectral properties, we have initiated a program to (1) obtain accurate characterization of the petrography of lunar soils (in terms relevant to remote analyses), coupled with (2) measurement of precise reflectance spectra, with testing and use of appropriate analytical tools that identify and characterize individual mineral and glass components. It is the finest-sized fractions of the bulk lunar soil that dominate the observed spectral signatures.

Taylor, Lawrence A.↗

Post-detonation fireball modeling: Validation of freeze out approximations

A numerical simulation study was performed to examine the post-detonation reaction processes produced by the detonation of a 12 mm diameter hemispherical pentaerythritol tetranitrate (PETN) explosive charge. The simulations used a finite rate detailed chemical reaction model consisting of 59 species and 368 reactions to capture post-detonation reaction processes including air dissociation from Mach 19+ shock waves that initially break out of the PETN charge, reactions within the detonation products during expansion, and afterburning when the detonation products mix with the shock heated air. The multi-species and thermodynamically complete Becker-Kistiakowsky-Wilson real-gas equation of state is used for the gaseous phase to allow for the mixing of reactive species. A recent simplified reactive burn model is used to propagate the detonation through the charge and allow for detailed post-detonation reaction processes. The computed blast, shock structures, and mole fractions of species within the detonation products agree well with experimental measurements. A comparison of the simulation results to equilibrium calculations indicates that the assumption of a local equilibrium is fairly accurate until the detonation products rapidly cool to temperatures in the range of 1500-1900 K by expansion waves. Below this range, the computed results show mole fractions that are nearly chemically frozen within the detonation products for a significant portion of expansion. In conclusion, these results are consistent with the freeze out approximation used in the blast modeling community.

97 MATHEMATICS AND COMPUTING↗

Investigating Sulfur-Rich Mercury Analogs Exposed to Simulated Micrometeoroid Bombardment in the Laboratory

Space weathering (SW) continually alters the spectral, microstructural, and chemical characteristics of the surface of airless bodies across the solar system. The effects of SW vary depending on the heliocentric distance and the initial composition of the target surface. While SW on the Moon and S-type asteroids is well documented, our understanding of how this process affects Mercury is at an early stage. Mercury’s interplanetary environment is harsh, with the surface of the planet experiencing an intense solar wind flux as well as a higher flux and velocity of micrometeoroid impactors compared to the Moon and S-type asteroids. In addition, Mercury is also a geochemical endmember, with a surface composition low in Fe (<2 wt.%) and enriched in volatile components, such as sulfur (up to 4 wt.% in the low reflectance material (LRM)). These volatile components are thought to play a major role in the formation of hollows via their sublimation. Sulfur has been hypothesized to occur at the surface of Mercury as sulfide minerals (MgS, CaS) based on its correlation with Mg and Ca in remote sensing data. However, recent observations of chaotic terrains in the north polar area of Mercury and of glacier-like features at lower latitudes indicated that octasulfur (S 8 , elemental sulfur) is another likely constituent of a volatile-rich layer in Mercury’s crust. Its behavior on Mercury may result in a complex cycle of enrichment and depletion. While S is often depleted on small body surfaces, Mercury’s gravity could result in ejected S subsequently returning to the surface and coating regolith grains. Further, the reaction of reduced S-rich gas with glasses of a Mercury-like composition also produced S-rich coatings. However, the precise behavior and evolution of S-rich species exposed to the harsh SW on Mercury remains poorly understood and needs to be further investigated in the laboratory. Here, we present the results of our analyses of the spectral, microstructural, and chemical characteristics of S-rich Mercury analogs irradiated by pulsed laser to simulate the short duration, high temperature events associated with micrometeoroid impacts.

N Bott↗

Actuating Liquid Crystals Rapidly and Reversibly by Using Chemical Catalysis

Abstract Microtubules and catalytic motor proteins underlie the microscale actuation of living materials, and they have been used in reconstituted systems to harness chemical energy to drive new states of organization of soft matter (e.g., liquid crystals (LCs)). Such materials, however, are fragile and challenging to translate to technological contexts. Rapid (sub‐second) and reversible changes in the orientations of LCs at room temperature using reactions between gaseous hydrogen and oxygen that are catalyzed by Pd/Au surfaces are reported. Surface chemical analysis and computational chemistry studies confirm that dissociative adsorption of H 2 on the Pd/Au films reduces preadsorbed O and generates 1 ML of adsorbed H, driving nitrile‐containing LCs from a perpendicular to a planar orientation. Subsequent exposure to O 2 leads to oxidation of the adsorbed H, reformation of adsorbed O on the Pd/Au surface, and a return of the LC to its initial orientation. The roles of surface composition and reaction kinetics in determining the LC dynamics are described along with a proof‐of‐concept demonstration of microactuation of beads. These results provide fresh ideas for utilizing chemical energy and catalysis to reversibly actuate functional LCs on the microscale.

Chemistry↗

Relevant biochar characteristics influencing compressive strength of biochar-cement mortars

To counteract the contribution of CO 2 emissions by cement production and utilization, biochar is being harnessed as a carbon-negative additive in concrete. Increasing the cement replacement and biochar dosage will increase the carbon offset, but there is large variability in methods being used and many researchers report strength decreases at cement replacements beyond 5%. This work presents a reliable method to replace 10% of the cement mass with a vast selection of biochars without decreasing ultimate compressive strength, and in many cases significantly improving it. By carefully quantifying the physical and chemical properties of each biochar used, machine learning algorithms were used to elucidate the three most influential biochar characteristics that control mortar strength: initial saturation percentage, oxygen-to-carbon ratio, and soluble silicon. These results provide additional research avenues for utilizing several potential biomass waste streams to increase the biochar dosage in cement mixes without decreasing mechanical properties.

97 MATHEMATICS AND COMPUTING↗

A Comment on “Deep Proteogenomics of a Photosynthetic Cyanobacterium”

Proteomic researchers strive to achieve complete annotation of protein-coding DNA sequences to provide a foundational context for their relevant biological data. A recent deep proteogenomic study using a photosynthetic cyanobacterium Synechocystis sp. PCC 6803 by Spät et al. proposed 64 refined open reading frames (ORFs). By searching LC-MS/MS data from affinity chromatography-isolated protein complexes, our laboratory identified that six of these high-abundance ORFs possess Nterminal initiation start sites that differ than those proposed in the alternative models. Our findings are supported by highly confident MS2 data, phylogenetic analysis, chemical labeling, and established data from two independent research groups. Based on these highquality experimental identifications, we subsequently propose a standardized strategy and set of criteria for future deep proteogenomic efforts to ensure accurate and stringent proteogenomic annotation.

cyanobacteria↗

Quantum electron transport in degenerate donor–acceptor systems

In this work, we develop a mathematically rigorous theory for the quantum transfer processes in degenerate donor–acceptor dimers in contact with a thermal environment. We explicitly calculate the transfer rates and the acceptor population efficiency. The latter depends critically on the initial donor state. Additionally, we show that quantum coherence in the initial state enhances the transfer process. If the electron is initially shared coherently by the donor levels, then the efficiency can reach values close to 100%, while an incoherent initial donor state will significantly suppress the efficiency. The results are useful for a better understanding of the quantum electron transport in many chemical, solid state, and biological systems with complex degenerate and quasi-degenerate energy landscapes.

36 MATERIALS SCIENCE↗

Material Characterization of Hierarchical Tunable Pore Size Polymer Foams Used in the MARBLE Mix Morphology Experiment

One of the great challenges of inertial confinement fusion and high energy density experiments is understanding the effects of mix on thermonuclear burn. The MARBLE campaign, conceived at Los Alamos National Laboratory, aims to gather new insights into this issue by utilizing unique target capsules containing polymer foams of variable pore sizes, tunable over an order of magnitude. Such capsules allow the degree of initial heterogeneity to be controlled experimentally for the first time. Here, we describe the various characterization efforts used to gain understanding of the chemical structure and behavior of the foam. Previous experiments were not sensitive to foam physical properties, and the MARBLE platform has aided in the development of techniques to measure foam properties such as deuterium content, density variation, hydrogen adsorption, and pore size and volume distribution.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The impact of environment on the lives of disc galaxies as revealed by SDSS-IV MaNGA

Environment has long been known to have significant impact on the evolution of galaxies, but here we seek to quantify the subtler differences that might be found in disc galaxies, depending on whether they are isolated, the most massive galaxy in a group (centrals), or a lesser member (satellites). The MaNGA survey allows us to define a large mass-matched sample of 574 galaxies with high-quality integrated spectra in each category. Initial examination of their spectral indices indicates significant differences, particularly in low-mass galaxies. Semi-analytic spectral fitting of a full chemical evolution model to these spectra confirms these differences, with low-mass satellites having a shorter period of star formation and chemical enrichment typical of a closed box, while central galaxies have more extended histories, with evidence of ongoing gas accretion over their lifetimes. The derived parameters for gas infall time-scale and wind strength suggest that low-mass satellite galaxies have their hot haloes of gas effectively removed, while central galaxies retain a larger fraction of gas than isolated galaxies due to the deeper group potential well in which they sit. S0 galaxies form a distinct subset within the sample, particularly at higher masses, but do not bias the inferred lower mass environmental impact significantly. The consistent picture that emerges underlines the wealth of archaeological information that can be extracted from high-quality spectral data using techniques like semi-analytic spectral fitting.

79 ASTRONOMY AND ASTROPHYSICS↗

Milestone 1.2.10: Steady-state H 2 “roll over” point data for aluminum alloys 1100 and 6061

Extended (> 50 years) dry storage is being evaluated by the U.S. Department of Energy (DOE) for the disposition of ~ 18 metric tons of aluminum-clad spent nuclear fuel (ASNF). Transition of the current ASNF inventory into dry storage—using the standard DOE canister—necessitates a rigorous, predictive understanding of the long-term physical and chemical factors that may influence the integrity of the proposed storage canister, including radiolytic molecular hydrogen (H 2 ) generation. Current model predictions employ initial radiolytic yields of H 2 , the values of which change as the cladding’s H 2 -precursor inventory is depleted and H 2 itself becomes progressively more involved in radiolytic and surface dissociation processes. Consequently, the absorbed radiation dose that this steady-state H 2 yield corresponds to is essential for the evaluation and improvement of model predictions. Here, we report our findings on the long-term generation of H 2 from the gamma irradiation (≤ 36 MGy) of corroded AA1100 and AA6061 coupons in helium environments at ambient temperature and ~ 50% RH. Our findings show that AA1100 systems reached steady-state by ~ 36 MGy, while higher doses were necessary for AA6061 systems. This discrepancy was attributed to the AA6061 coupons developing a thicker corrosion layer that led to the trapping of H 2 and its precursors, and potentially additional chemistries, ultimately delaying the depletion of H 2 precursors and the system’s “roll over” point. Further, current model predictions—based on previous AA1100 data—do not show steady-state attainment until above 120 MGy, which is not the case for the AA1100 data collected here. Consequently, the new alloy dependent data presented here are important for the continued improvement of predictive computer models for evaluating the feasibility of extended storage of ASNF in helium backfilled canisters.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Post-irradiation Examination Status for the BSU-269 Project

High-density uranium inter-metallic uranium silicide (U 3 Si 2 ) was initially considered as a potential advanced nuclear fuel for light water reactor (LWR) systems due to several advantages it demonstrated in thermophysical properties, chemical, and irradiation stability. In addition to understanding the basic thermophysical and mechanical properties of U 3 Si 2 under LWR irradiation conditions, it is important to assess its performance with advanced claddings such as FeCrAl, SiC, or conventional Zr-based claddings. Several aspects of the fuel cycle and fuel performance are being evaluated for U 3 Si 2 coupled with different types of claddings. To thoroughly characterize the U 3 Si 2 -cladding system, their chemical compatibilities and the potential for fuel-cladding chemical interaction (FCCI) must be addressed. Interdiffusion studies have been performed between U 3 Si 2 /Zry-4 and U 3 Si 2 /FeCrAl using diffusion couples. For the U 3 Si 2 /Zry-4 system, ZrSi 2 was the primary interdiffusion product observed at 800°C in addition to other secondary phases from the Zr alloying elements such as Fe and Cr. Low melting point U 6 Fe was also observed at 1000°C. For the U 3 Si 2 /FeCrAl system, at temperatures above 500°C, chemical diffusion Fe-U and Fe-U-Si was observed, increasing with rising temperatures. Although information from these non-irradiated tests is a fundamental first assessment, follow-up with focused irradiation tests is necessary. Irradiation can significantly alter the structure and evolution of the FCCI layers compared to the non-irradiated conditions.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Polymerization of perfluorobutadiene at near-ambient conditions

Peroxide catalyst under mild conditions initiates homopolymerization of perfluoro butadiene to new linear perfluoro polyenes and vulcanizable fluoro elastomers. Resulting polyperfluoro butadiene serves as hard elastomer for good chemical resistance, as intermediate in graft polymerizations, and as crosslink for high molecular weight materials.

Toy, M. S.↗

Two-phase working fluids for the temperature range 100-350 C

The decomposition and corrosion of two-phase heat transfer liquids and metal envelopes have been investigated on the basis of molecular, bond strengths and chemical thermodynamics. Potentially stable heat transfer fluids for the temperature range 100 to 350 C have been identified, and reflux heat pipe tests initiated with 10 fluids and carbon steel and aluminum envelopes to experimentally establish corrosion behavior and noncondensable gas generation rates.

Saaski, E. W.↗