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At least 55 records · Page 3

Observations of chemical processing in the circumstellar environment

High resolution interferometer and single-dish observations of young, deeply embedded stellar systems reveal a complex chemistry in the circumstellar environments of low to intermediate mass stars. Depletions of gas-phase molecules, grain mantle evaporation, and shock interactions actively drive chemical processes in different regions around young stars. We present results for two systems, IRAS 05338-0624 and NCG 1333 IRAS 4, to illustrate the behavior found and to examine the physical processes at work.

NASA Program Exobiology↗

The effects of finite rate chemical processes on high enthalpy nozzle performance - A comparison between SPARK and SEAGULL

The generalized chemistry version of the computer code SPARK is extended to include two higher-order numerical schemes, yielding fourth-order spatial accuracy for the inviscid terms. The new and old formulations are used to study the influences of finite rate chemical processes on nozzle performance. A determination is made of the computationally optimum reaction scheme for use in high-enthalpy nozzles. Finite rate calculations are compared with the frozen and equilibrium limits to assess the validity of each formulation. In addition, the finite rate SPARK results are compared with the constant ratio of specific heats (gamma) SEAGULL code, to determine its accuracy in variable gamma flow situations. Finally, the higher-order SPARK code is used to calculate nozzle flows having species stratification. Flame quenching occurs at low nozzle pressures, while for high pressures, significant burning continues in the nozzle.

Carpenter, M. H.↗

A high-pressure premixed flat-flame burner for chemical process studies

A premixed flat-flame burner was designed and tested with methane-air mixtures at pressures from 1.1 to 20 atm and equivalence ratios from 0.7 to 1.1. Reactant velocity in the burner mixing chamber was used to characterize the range of stable flames at each pressure-equivalence-ratio condition. Color photographs of the flames were used to determine flame zone thickness and flame height. The results show that this burner can be used for chemical process studies in premixed high pressure methane-air flames up to 20 atm.

Miller, I. M.↗

Accessing bands with extended quantum metric in kagome Cs 2 Ni 3 S 4 through soft chemical processing

Flat bands that do not merely arise from weak interactions can produce exotic physical properties, such as superconductivity or correlated many-body effects. The quantum metric can differentiate whether flat bands will result in correlated physics or are merely dangling bonds. A potential avenue for achieving correlated flat bands involves leveraging geometrical constraints within specific lattice structures, such as the kagome lattice; however, materials are often more complex. In these cases, quantum geometry becomes a powerful indicator of the nature of bands with small dispersions. We present a simple, soft-chemical processing route to access a flat band with an extended quantum metric below the Fermi level. By oxidizing Ni-kagome material Cs 2 Ni 3 S 4 to CsNi 3 S 4 , we see a two orders of magnitude drop in the room temperature resistance. However, CsNi 3 S 4 is still insulating, with no evidence of a phase transition. Using experimental data, density functional theory calculations, and symmetry analysis, our results suggest the emergence of a correlated insulating state of unknown origin.

Science & Technology - Other Topics↗

A model for heterogeneous chemical processes on the surfaces of ice and nitric acid trihydrate particles

The study presents a model that incorporates the physics and physical chemistry of ice surfaces relevant to polar stratospheric clouds. Surface concentrations of H2O, HCl, HOCl, ClONO2, and N2O5 on ice and nitric acid trihydrate (NAT) crystals are computed, and surface reaction rates and reaction probabilities (sticking coefficients) are determined. For gas pressures of about 10 exp -7 torr and temperatures in the range of 180-200 K, HCl completely coats ice and water-rich NAT surfaces, while HOCl, ClOHO2, and N2O5 may cover 0.01-1 percent of these surfaces. The energy parameters are used to calculate surface temperatures such as adsorption and desorption constants, surface coverages, reaction rate coefficients, surface diffusion coefficients, and reaction probabilities for various species and chemical interactions on ice and NAT surfaces. Implications for chemical processing on polar stratospheric clouds are discussed.

Tabazadeh, Azadeh↗

Evidence for Chemical Processing of Precometary Icy Grains In Circumstellar Environments of Pre-Main-Sequence Stars

We report the detection of a broad absorption feature near 2166 cm-1 in the spectrum of the Taurus cloud source Elias 18. This pre-main-sequence source is the second in Taurus, the third in our survey, and the fifth known in the sky to show the broad 2166 cm-1 absorption feature. Of equal importance, this feature is not seen toward several other embedded sources in our survey, nor is it seen toward the source Elias 16, located behind the Taurus cloud. Laboratory experiments with interstellar ice analogs show that such a feature is associated with a complex C=-N containing compound [called X(C=-N)] that results from high-energy processing (ultraviolet irradiation or ion bombardment) of simple ice components into more complex, organic components, We find a nonlinear anticorrelation between the abundance of X(C=-N) and frozen CO in non- polar lattices. We find no correlation between the abundance of X(C=-N) and frozen CO in polar lattices. Because the abundances of frozen CO and H20 are strongly correlated with each other and with visual extinction toward sources embedded in and located behind the Taurus molecular cloud, these ice components usually are associated with intracloud material. Our results indicate that X(C=-N) molecules result from chemical processing of dust grains dominated by nonpolar icy mantles in the local environments of pre-main- sequence stars. Such processing of icy grains in the early solar system may be an important source of organic compounds observed in minor solar system bodies. The delivery of these organic compounds to the surface of the primitive Earth through comet impacts may have provided the raw materials for prebiotic chemistry.

Teglier, Stephen C.↗

Evidence for chemical processing of precometary icy grains in circumstellar environments of pre-main-sequence stars

We report the detection of a broad absorption feature near 2166/cm in the spectrum of the Taurus cloud cource Elias 18. This pre-main-sequence source is the second in Taurus, the third in our survey, and the fifth known in the sky to show the broad 2166/cm absorption feature. Of equal importance, this feature is not seen toward several other embedded sources in our survey, nor is it seen toward the source Elias 16, located behind the Taurus cloud. Laboratory experiments with interstellar ice analogs show that such a feature is associated with a complex C triple bonded to N containing compound (called X(C triple bonded to N)) that results from high-energy processing (ultraviolet irradiation or ion bombardment) of simple ice components into more complex, organic components. We find a nonlinear anticorrelation between the abundance of X(C triple bonded to N) and frozen CO components in nonpolar lattices. We find no correlation between the abundance of X(C triple bonded to N) and frozen CO in polar lattices. Because the abundances of frozen CO and H2O are strongly correlated with each other and with visual extinction toward sources embedded in and located behind the Taurus molecular cloud, these ice components usually are associated with intracloud material. Our results indicate that X(C triple bonded to N) molecules result from chemical processing of dust grains dominated by nonpolar icy mantles in the local environments of pre-main-sequence stars. Such processing of icy grains in the early solar system may be an important source of organic compounds observed in minor solar system bodies. The delivery of these organic compounds to the surface of the primitive Earth through comet impacts may have provided the raw materials for prebiotic chemistry.

Tegler, Stephen C.↗

Effects of the Mount Pinatubo eruption on the radiative and chemical processes in the troposphere and stratosphere

The Lawrence Livermore National Laboratory two-dimensional zonally-averaged chemical-radiative-transport model of the global atmosphere was used to study the effects of the 15 June 1991 eruption of the Mt. Pinatubo volcano on stratospheric processes. SAGE 2 time-dependent aerosol surface area density and optical extinction data were used as input into the model. By 22 December 1991, a maximum equatorial change of -1.8 percent in column ozone was derived from heterogeneous chemical processes that convert NO(x) into HNO3 on sulfuric acid aerosols. Radiative feedbacks from increased aerosol optical thickness independently changes column ozone by approximately -3.5 percent for the same period. This occurs from increasing the net heating of the lower stratosphere, which indirectly increases chemical reaction rates via their temperature dependence and from changes in actinic fluxes, which directly modify photodissociation rates. Including both heterogeneous and radiative effects changes column ozone by -5.5 percent. The model-derived change overestimates the decrease in column ozone relative to the TOMS instrument on the Nimbus 7 satellite. Maximum local ozone decreases of 12 percent were derived in the equatorial region, at 25 km. Model-derived column NO2 peaked (-14 percent) at 30 deg S in October 1991. The timing of the NO2 peak is consistent with observation, but the model underestimates the magnitude of the decrease. Local concentrations of NO(x) (NO + NO2), ClO(x) (Cl + ClO), and HO(x) (OH + HO2), in the lower stratosphere between 30 deg S and 30 deg N, were calculated to have changed by -40 percent, +100 to +160 percent, and +120 to +140 percent respectively.

Kinnison, Douglas E.↗

A Model for Formation of Dust, Soil and Rock Coatings on Mars: Physical and Chemical Processes on the Martian Surface

This model is one of many possible scenarios to explain the generation of the current surface material on Mars using chemical, magnetic and spectroscopic data From Mars and geologic analogs from terrestrial sites. One basic premise of this model is that the dust/soil units are not derived exclusively from local rocks, but are rather a product of global, and possibly remote, weathering processes. Another assumption in this model is that there are physical and chemical interactions of the atmospheric dust particles and that these two processes create distinctly different results on the surface. Physical processes distribute dust particles on rocks and drift units, forming physically-aggregated layers; these are reversible processes. Chemical reactions of the dust/soil particles create alteration rinds on rock surfaces and cohesive, crusted surface units between rocks, both of which are relatively permanent materials. According to this model the dominant components of the dust/soil particles are derived from alteration of volcanic ash and tephra, and contain primarily nanophase and poorly crystalline ferric oxides/oxyhydroxide phases as well as silicates. These phases are the alteration products that formed in a low moisture environment. These dust/soil particles also contain a smaller amount of material that was exposed to more water and contains crystalline ferric oxides/oxyhydroxides, sulfates and clay silicates. These components could have formed through hydrothermal alteration at steam vents or fumeroles, thermal fluids, or through evaporite deposits. Wet/dry cycling experiments are presented here on mixtures containing poorly crystalline and crystalline ferric oxides/oxyhydroxides, sulfates and silicates that range in size from nanophase to 1-2 pm diameter particles. Cemented products of these soil mixtures are formed in these experiments and variation in the surface texture was observed for samples containing smectites, non-hydrated silicates or sulfates. Reflectance spectra were measured of the initial particulate mixtures, the cemented products and ground versions of the cemented material. The spectral contrast in the visible/near-infrared and mid-infrared regions is significantly reduced for the cemented material compared to the initial soil, and somewhat reduced for the ground, cemented soil compared to the initial soil. The results of this study suggest that diurnal and seasonal cycling on Mars will have a profound effect on the texture and spectral properties of the dust/soil particles on the surface. The model developed in this study provides an explanation for the generation of cemented or crusted soil units and rock coatings on Mars and may explain albedo variations on the surface observed near large rocks or crater rims.

Bishop, Janice↗

Conditions of early chemical processing of matter - Explosive exhalations of supernovae

The chemical and isotopic stratifications of supernova exhalations are discussed, with reference to a number of theoretical estimates. Particular attention is given to the theoretical models of the major chemical zones of explosive exhalation of isotopes of Mg, Si, and Ti in intermediate size supernovae. The contribution of supernova exhalations to oxygen anomalies in the solar system is also discussed within the framework of the theoretical models of Clayton et al. (1977, 1978, 1979, 1981). The initial stratigraphy of the major elements in the explosive exhalation of a progenitor star of 25 solar mass is illustrated in a graph, on the basis of the theoretical estimates of Waver et al. (1978), and Weaver and Woolsey (1980).

Heymann, D.↗

Formation and Microwave Losses of Hydrides in Superconducting Niobium Thin Films Resulting from Fluoride Chemical Processing

Abstract Superconducting niobium (Nb) thin films have recently attracted significant attention due to their utility for quantum information technologies. In the processing of Nb thin films, fluoride‐based chemical etchants are commonly used to remove surface oxides that are known to affect superconducting quantum devices adversely. However, these same etchants can also introduce hydrogen to form Nb hydrides, potentially negatively impacting microwave loss performance. Here, comprehensive materials characterization of Nb hydrides formed in Nb thin films as a function of fluoride chemical treatments is presented. In particular, secondary‐ion mass spectrometry, X‐ray scattering, and transmission electron microscopy reveal the spatial distribution and phase transformation of Nb hydrides. The rate of hydride formation is determined by the fluoride solution acidity and the etch rate of Nb 2 O 5, which acts as a diffusion barrier for hydrogen into Nb. The resulting Nb hydrides are detrimental to Nb superconducting properties and lead to increased power‐independent microwave loss in coplanar waveguide resonators. However, Nb hydrides do not correlate with two‐level system loss or device aging mechanisms. Overall, this work provides insight into the formation of Nb hydrides and their role in microwave loss, thus guiding ongoing efforts to maximize coherence time in superconducting quantum devices.

36 MATERIALS SCIENCE↗

Laboratory Studies of Heterogeneous Chemical Processes of Atmospheric Importance

The objective of this study is to conduct measurements of chemical kinetics parameters for heterogeneous reactions of importance in the stratosphere and the troposphere. It involves the elucidation of the mechanism of the interaction of HC1 vapor with ice surfaces, which is the first step in the heterogeneous chlorine activation processes, as well as the investigation of the atmospheric oxidation mechanism of soot particles emitted by biomass and fossil fuels. The techniques being employed include turbulent flow- chemical ionization mass spectrometry and optical ellipsometry, among others. The next section summarizes our research activities during the first year of the project, and the section that follows consists of the statement of work for the second year.

Molina, Mario J.↗

Laboratory Studies of Heterogeneous Chemical Processes of Atmospheric Importance

The objective of this study is to conduct measurements of chemical kinetics parameters for heterogeneous reactions of importance in the stratosphere and the troposphere. It involves the elucidation of the mechanism of the interaction of HCl vapor with ice surfaces, which is the first step in the heterogeneous chlorine activation processes, as well as the investigation of the atmospheric oxidation mechanism of soot particles emitted by biomass and fossil fuels. The techniques being employed include turbulent flow-chemical ionization mass spectrometry and optical ellipsometry, among others.

Molina, Mario J.↗