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At least 127 records · Page 7

High resolution, balloon-borne emission spectroscopy of trace species in the lower stratosphere - N2O5, HNO3

A liquid-nitrogen cooled Fourier transform spectrometer (SIRIS) measures thermal limb-emission of the stratosphere from a balloon platform at a nominal altitude of 40 km, under night and day conditions, with a 3 km vertical resolution. N2O5 and HNO3 mixing ratios inferred from emission spectra are compared with previous measurements and with the predictions from a one-dimensional photochemical model.

Brasunas, J.↗

Thermal Infrared Emission Spectroscopy of Synthetic Allophane and its Potential Formation on Mars

Allophane is a poorly-crystalline, hydrous aluminosilicate with variable Si/Al ratios approx.0.5-1 and a metastable precursor of clay minerals. On Earth, it forms rapidly by aqueous alteration of volcanic glass under neutral to slightly acidic conditions [1]. Based on in situ chemical measurements and the identification of alteration phases [2-4], the Martian surface is interpreted to have been chemically weathered on local to regional scales. Chemical models of altered surfaces detected by the Mars Exploration Rover Spirit in Gusev crater suggest the presence of an allophane-like alteration product [3]. Thermal infrared (TIR) spectroscopy and spectral deconvolution models are primary tools for determining the mineralogy of the Martian surface [5]. Spectral models of data from the Thermal Emission Spectrometer (TES) indicate a global compositional dichotomy, where high latitudes tend to be enriched in a high-silica material [6,7], interpreted as high-silica, K-rich volcanic glass [6,8]. However, later interpretations proposed that the high-silica material may be an alteration product (such as amorphous silica, clay minerals, or allophane) and that high latitude surfaces are chemically weathered [9-11]. A TIR spectral library of pure minerals is available for the public [12], but it does not contain allophane spectra. The identification of allophane on the Martian surface would indicate high water activity at the time of its formation and would help constrain the aqueous alteration environment [13,14]. The addition of allophane to the spectral library is necessary to address the global compositional dichotomy. In this study, we characterize a synthetic allophane by IR spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM) to create an IR emission spectrum of pure allophane for the Mars science community to use in Martian spectral models.

Rampe, E. B.↗

U M subshell X-ray emission spectroscopy of uranium dioxide: the effect of excitation energy

There are very great differences between the non-resonant U M subshell X-ray Emission Spectra of Uranium Dioxide generated with low and high-energy excitation. Additionally, these different spectra are each supported by theoretical constructs. It will be shown that the differences between these experimental spectra can be reconciled and the utility of both theoretical approaches confirmed, including the use of FEFF in the low energy and high-energy regimes.

36 MATERIALS SCIENCE↗

Approach to SSME health monitoring. II - Exhaust plume emission spectroscopy at the DTF

The Diagnostics Testbed Facility (DTF) located at the Stennis Space Center (SSC) is used for obtaining extensive sets of H2O2 exhaust plume emission spectral data for the SSME critical components related elements and materials. The SSME related elements and materials are simulated by mixing appropriate amounts of compounds of their respective constituent elements in an aqueous solution which is injected into the combustion chamber of the DTFT. Five of the most critical components of the SSME which have experienced very severe wear and tear problems in the past are analyzed. These are high pressure turbopump (HPTP) turbine blades, HPTP turbine disks, HPTP bearing, main injector LOX posts, and the main combustion chamber structural shell. The alloys used in the manufacturing of these components are MAR-M 246 + Hf, Waspaloy X, AISI 440C, Haynes 188, and Inconel 718, respectively. The experimental setup and procedures at the DTF are described; stratospheric data for the five alloys are presented; and strategies for the material identification in the SSME exhaust plume are discussed.

Tejwani, Gopal D.↗

Investigation of PTFE transfer films by infrared emission spectroscopy and phase-locked ellipsometry

When a PTFE sheet was rubbed unidirectionally over a smooth surface of stainless steel an essentially monomolecular transfer film was formed. By ellipsometric and emission infrared spectroscopic techniques it was shown that the film was 10 to 15 A thick and birefringent. From the intensity differences of infrared bands obtained with a polarizer passing radiation polarized in mutually perpendicular planes, it was possible to deduce transfer film orientation with the direction of rubbing. After standing in air for several weeks the transfer films apparently increased in thickness by as much as threefold. At the same time both the index of refraction and the absorption index decreased. Examination of the surfaces by optical and electron microscopies showed that the films had become porous and flaky. These observations were consistent with previous tribological measurements. The coefficients of friction decreased with the formation of the transfer film but increased again as the film developed breaks. The applicability of the ellipsometric and polarized infrared emission techniques to the identification of monomolecular tribological transfer films of polymers such as PTFE has been demonstrated.

Lauer, James L.↗

Investigation of PTFE transfer films by infrared emission spectroscopy and phase-locked ellipsometry

When a PTFE sheet was rubbed unidirectionally over a smooth surface of stainless steel an essentially monomolecular transfer film was formed. by ellipsometric and emission infrared spectroscopic techniques it was shown that the film was 10 to 15 A thick and birefringent. From the intensity differences of infrared bands obtained with a polarizer passing radiation polarized in mutually perpendicular planes, it was possible to deduce transfer film orientation with the direction of rubbing. After standing in air for several weeks the transfer films apparently increased in thickness by as much as threefold. At the same time both the index of refraction and the absorption index decreased. Examination of the surfaces by optical and electron microscopies showed that the films had become porous and flaky. These observations were consistent with previous tribological measurements. The coefficients of friction decreased with the formation of the transfer film but increased again as the film developed breaks. The applicability of the ellipsometric and polarized infrared emission techniques to the identification of monomolecular tribological transfer films of polymers such as PTFE has been demonstrated.

Lauer, James L.↗

Flash Spectroscopy: Emission Lines From the Ionized Circumstellar Material Around 10-Day-Old Type II Supernovae

Supernovae (SNe) embedded in dense circumstellar material (CSM) may show prominent emission lines in their early-time spectra (< or =10 days after the explosion), owing to recombination of the CSM ionized by the shock-breakout flash. From such spectra ("flash spectroscopy"), we can measure various physical properties of the CSM, as well as the mass-loss rate of the progenitor during the year prior to its explosion. Searching through the Palomar Transient Factory (PTF and iPTF) SN spectroscopy databases from 2009 through 2014, we found 12 SNe II showing flash-ionized (FI) signatures in their first spectra. All are younger than 10 days. These events constitute 14% of all 84 SNe in our sample having a spectrum within 10 days from explosion, and 18% of SNe II observed at ages <5 days, thereby setting lower limits on the fraction of FI events. We classified as "blue/featureless" (BF) those events having a first spectrum that is similar to that of a blackbody, without any emission or absorption signatures. It is possible that some BF events had FI signatures at an earlier phase than observed, or that they lack dense CSM around the progenitor. Within 2 days after explosion, 8 out of 11 SNe in our sample are either BF events or show FI signatures. Interestingly, we found that 19 out of 21 SNe brighter than an absolute magnitude M(sub R) = −18.2 belong to the FI or BF groups, and that all FI events peaked above M(sub R) = −17.6 mag, significantly brighter than average SNe II.

supernovae: general↗

X-ray Emission Spectroscopy of Single Protein Crystals Yields Insights into Heme Enzyme Intermediates

Enzyme reactivity is often enhanced by changes in oxidation state, spin state, and metal-ligand covalency of associated metallocofactors. The development of spectroscopic methods for studying these processes coincidentally with structural rearrangements is essential for elucidating metalloenzyme mechanisms. Herein, we demonstrate the feasibility of collecting X-ray emission spectra of metalloenzyme crystals at a third-generation synchrotron source. In particular, we report the development of a von Hamos spectrometer for the collection of Fe Kβ emission optimized for analysis of dilute biological samples. Here, we further showcase its application in crystals of the immunosuppressive heme-dependent enzyme indoleamine 2,3-dioxygenase. Spectra from protein crystals in different states were compared with relevant reference compounds. Complementary density functional calculations assessing covalency support our spectroscopic analysis and identify active site conformations that correlate to high- and low-spin states. These experiments validate the suitability of an X-ray emission approach for determining spin states of previously uncharacterized metalloenzyme reaction intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Approach to SSME health monitoring. III - Exhaust plume emission spectroscopy: Recent results and detailed analysis

Spectral data for two recent A-1 test firings, 901-717 and 901-718, obtained from an Optical Multichannel Analyzer and an Optical Plume Anomaly Detector, are presented. The spectral data encompasses the database of SSME critical components and materials and the spectral database for the SSME related elements and materials. Relatively strong and continuous emissions from Cr and Fe atomic transitions were observed starting at engine start plus 494 s and persisting until the engine shut off at engine start plus 520 s. These emissions are considered to be emanated from the SSME material AISI 440C, which is traced to high pressure turbopump bearings.

Tejwani, Gopal D.↗

Probing ultrafast excited-state dynamics using EUV-IR six-wave-mixing emission spectroscopy

Non-linear processes such as four-wave-mixing have become instrumental in attosecond EUV spectroscopy. Using EUV high harmonics in conjunction with collinear near-infrared and mid-infrared fields, we extended this approach to high-order-mixing between three colors. Specifically, we find that atomic resonances in neon exhibit a significant cross section for six-wave mixing. The MIR probe frequency tunability in our multicolor scheme is employed to access several optically dark resonances and probe the quantum beat of a coherent electronic wavepacket using background-free EUV emission as a diagnostic. This technique can be easily extended to other atomic and molecular systems, and opens the door to multi-dimensional non-linear spectroscopy.

74 ATOMIC AND MOLECULAR PHYSICS↗

Diamond Analyzed by Secondary Electron Emission Spectroscopy

Diamond is a promising semiconductor material for novel electronic applications because of its chemical stability and inertness, heat conduction properties, and so-called negative electron affinity (NEA). When a surface has NEA, electrons generated inside the bulk of the material are able to come out into the vacuum without any potential barrier (work function). Such a material would have an extremely high secondary electron emission coefficient o, very high photoelectron (quantum) yield, and would probably be an efficient field emitter. Chemical-vapor-deposited (CVD) polycrystalline diamond films have even more advantages than diamond single crystals. Their fabrication is relatively easy and inexpensive, and they can be grown with high levels of doping--consequently, they can have relatively high conductivity. Because of these properties, diamond can be used for cold cathodes and photocathodes in high-power electronics and in high-frequency and high-temperature semiconductor devices.

Krainsky, Isay L.↗

Coaxial laser absorption and optical emission spectroscopy of high-pressure aluminum monoxide

This work advances laser absorption spectroscopy with measurements of aluminum monoxide (AlO) temperature and column density in extreme pressure ( P > 60 bar) and temperature ( T > 4000 K) environments. Measurements of the AlO A 2 Π i – X 2 Σ + transition are made using a microelectromechanical system, tunable vertical cavity surface emitting laser (MEMS-VCSEL). Simultaneous emission measurements of the AlO B 2 Σ + – X 2 Σ + transition are made along a line of sight that is coaxial with the laser absorption. Absorption temperature fits agree with emission spectra for a T = 3200 K, P = 9 bar case. In cases with T > 4000 K, P > 60 bar, absorption fits match the ambient temperature while emission fits over-estimate it, owing to high optical depths. These data juxtapose passive and active spectroscopic methods and demonstrate the versatility of AlO laser absorption in high-pressure and high-temperature environments where experimental data remain scarce, and engineering models will benefit from refined measurements.

Daniel, K. A.↗

Thermal infrared emission spectroscopy of natural surfaces: Application to desert varnish coatings on rocks

Thermal infrared spectroscopy has become an increasingly important tool for remote compositional analysis and geologic mapping. Most published laboratory measurements have been obtained in bidirectional reflection or transmission, whereas remotely sensed thermal infrared data are obtained by measuring the emitted energy. Section 2 of this paper describes a laboratory technique for determining calibrated emissivities of natural surfaces. Equations are developed to account for the energy reflected from the environment and to determine directly the sample temperature from measurements of hot and cold blackbody targets. Two methods for determining emissivity are developed: one in which only a hot sample measurement is made and the reflected background energy is removed by modeling, and a second in which the sample is cooled and the reflected energy is measured directly. Relative emissivity can be obtained to approximately 1% and absolute emissivities can be obtained to 2-15%, depending on the validity of the assumption that the emissivity of the sample is unity at some wavelength. The emission data agree well within the hemispherically integrated reflection data but point out probelms associated with bidirectional reflectance measurements. Section 3 applies emissivity measurements to the study of layered surfaces consisting of desert varnish coatings on granite and granodiorite rock suites. Two linear models are developed: the first assumes linear mixing of independent emission from the substrate and varnish (checkerboard model); the second models tansmission through an absorbing/emitting medium. Regardless of whether the varnish is or is not relatively transparant and strongly absorptive, the spectral effect of varnish increases linearly with varnish thickness, indicating that thick patches of varnish dominate the spectral properties. As a result, medium varnish thickness can be determined from spectral measurements. In addition, the composition of a substrate can be estimated through varnish layers up to 40-50 micrometers in median thickness, and the composition of the varnish material can be determined if the substrate material is known. The varnishes studied are composed primarily of clay materials, consistent with previous studies of varnish composition.

Christensen, Philip R.↗

Rapid evaluation of ion thruster lifetime using optical emission spectroscopy

A major life-limiting phenomenon of electric thrusters is the sputter erosion of discharge chamber components. Thrusters for space propulsion are required to operate for extended periods of time, usually in excess of 10,000 hr. Lengthy and very costly life-tests in high-vacuum facilities have been required in the past to determine the erosion rates of thruster components. Alternative methods for determining erosion rates which can be performed in relatively short periods of time at considerably lower costs are studied. An attempt to relate optical emission intensity from an ion bombarded surface (screen grid) to the sputtering rate of that surface is made. The model used a kinetic steady-state (KSS) approach, balancing the rates of population and depopulation of ten low-lying excited states of the sputtered molybdenum atom (MoI) with those of the ground state to relate the spectral intensities of the various transitions of the MoI to the population densities. Once this is accomplished, the population density can be related to the sputtering rate of the target. Radiative and collisional modes of excitation and decay are considered. Since actual data has not been published for MoI excitation rate and decay constants, semiempirical equations are used. The calculated sputtering rate and intensity is compared to the measured intensity and sputtering rates of the 8 and 30 cm ion thrusters.

Rock, B. A.↗

Rapid evaluation of ion thruster lifetime using optical emission spectroscopy

A major life-limiting phenomenon of electric thrusters is the sputter erosion of discharge chamber components. Thrusters for space propulsion are required to operate for extended periods of time, usually in excess of 10,000 hr. Lengthy and very costly life-tests in high-vacuum facilities have been required in the past to determine the erosion rates of thruster components. Alternative methods for determining erosion rates which can be performed in relatively short periods of time at considerably lower costs are studied. An attempt to relate optical emission intensity from an ion bombarded surface (screen grid) to the sputtering rate of that surface is made. The model used a kinetic steady-state (KSS) approach, balancing the rates of population and depopulation of ten low-lying excited states of the sputtered molybdenum atom (MoI) with those of the ground state to relate the spectral intensities of the various transitions of the MoI to the population densities. Once this is accomplished, the population density can be related to the sputting rate of the target. Radiative and collisional modes of excitation and decay are considered. Since actual data has not been published for MoI excitation rate and decay constants, semiempirical equations are used. The calculated sputtering rate and intensity is compared to the measured intensity and sputtering rates of the 8 and 30 cm ion thrusters.

Rock, B. A.↗

Thermal-infrared emission spectroscopy of natural surfaces: Application to coated surfaces

Thermal-infrared vibrational spectroscopy has great potential for remotely determining the composition of planetary surface materials by taking advantage of fundamental molecular vibrational modes that produce spectral features in the range from approximately 3 to greater than 50 microns. Much of the current interest in the thermal infrared wavelength region stems from the deployment of multispectral scanners, such as the Thermal Infrared Multispectral Scanner (TIMS) and the Mars Observer Thermal Emission Spectrometer (TES). In order to support these missions, it is necessary to develop an appropriate library of laboratory measurements. The purpose of this work was to develop a technique which, with a very limited set of assumptions, can be used to determine the emissivity of natural surfaces directly by using emitted energy.

Christensen, Philip R.↗

Thermal emission spectroscopy of the middle atmosphere

The general objective of this research is to obtain, via remote sensing, simultaneous measurements of the vertical distributions of stratospheric temperature, ozone, and trace constituents that participate in the catalytic destruction of ozone (NO(sub y): NO, NO2, NO3, HNO3, ClONO2, N2O5, HNO4; Cl(sub x): HOCl), and the source gases for the catalytic cycles (H2O, CH4, N2O, CF2Cl2, CFCl3, CCl4, CH3Cl, CHF2Cl, etc.). Data are collected during a complete diurnal cycle in order to test our present understanding of ozone chemistry and its associate catalytic cycles. The instrumentation employed is an emission-mode, balloon-borne, liquid-nitrogen-cooled Michelson interferometer-spectrometer (SIRIS), covering the mid-infrared range with a spectral resolution of 0.020 cm(exp -1). Cryogenic cooling combined with the use of extrinsic silicon photoconductor detectors allows the detection of weak emission features of stratospheric gaseous species. Vertical distributions of these species are inferred from scans of the thermal emission of the limb in a sequence of elevation angles. The fourth SIRIS balloon flight was carried out from Palestine, Texas on September 15-16, 1986 with 9 hours of nighttime data (40 km). High quality data with spectral resolution 0.022 cm(exp -1), were obtained for numerous limb sequences. Fifteen stratospheric species have been identified to date from this flight: five species from the NO(sub y) family (HNO3, NO2, NO, ClONO2, N2O5), plus CO2, O3, H2O, N2O, CH4, CCl3F, CCl2F2, CHF2Cl, CF4, and CCl4. The nighttime values of N2O5, ClONO2, and total odd nitrogen have been measured for the first time, and compared to model results. Analysis of the diurnal variation of N2O5 within the 1984 and 1986 data sets, and of the 1984 ClONO2 measurements, were presented in the literature. The demonstrated ability of SIRIS to measure all the major NO(sub y) species, and therefore to determine the partitioning of the nitrogen family over a continuous diurnal cycle, is a powerful tool in the verification and improvement of photochemical modeling.

Kunde, V. G.↗