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At least 487 records · Page 27

Spectroscopic chemical analysis methods and apparatus

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. Chemical analysis instruments employed in some embodiments include capillary and gel plane electrophoresis, capillary electrochromatography, high performance liquid chromatography, flow cytometry, flow cells for liquids and aerosols, and surface detection instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted simultaneously with native fluorescence spectroscopy to provide high levels of sensitivity and specificity in the same instrument.

Hug, William F.↗

Survey of measurements of flow properties in arc jets

This paper reviews techniques for determining flow properties in low density arc jets used for materials and structures testing. Properties measured include flow total enthalpy, pressures, heat fluxes, static temperatures, electron density, species concentrations, and flow velocity. The probe techniques covered are pressure, heat flux, electrostatic, and mass sampling. Nonintrusive techniques include emission spectroscopy, laser-induced fluorescence, laser Thomson scattering, and Raman scattering. It is concluded that several techniques must be used in a single facility to obtain all of the flow field properties necessary to predict heat fluxes in a nonequilibrium expansion.

Scott, Carl D.↗

Effects of Surface Treatments on Secondary Electron Emission from CVD Diamond Films

Secondary electron emission (SEE) properties of polycrystalline diamond films grown by chemical vapor deposition (CVD) were measured. The total secondary yield (sigma) from as-grown samples was observed to be as high as 20 at room temperature and 48 while heating at 700 K in vacuum. Electron-beam-activated, alkali-terminated diamond films have shown stable values of sigma as high as 60 when coated with CsI and similarly high values when coated with other alkali halides. Diamond coated with BaF2 had a stable sigma of 6, but no enhancement of the SEE properties was observed with coatings of Ti or Au. Hydrogen was identified to give rise to this effect in as-grown films. However, electron beam exposure led to a reduction in sigma values as low as 2. Exposure to a molecular hydrogen environment restored sigma to its original value after degradation, and enabled stable secondary emission during electron beam exposure. Atomic hydrogen and hydrogen plasma treatments were performed on diamond/Mo samples in an attempt to increase the near-surface hydrogen concentration which might lead to increased stability in the secondary emission. Raman scattering analysis, scanning electron microscopy, and Auger electron spectroscopy (AES) confirmed that hydrogen plasma and atomic hydrogen treatments improved the quality of the CVD diamond significantly. Elastic recoil detection (ERD) showed that heating as-grown diamond targets to 7OO K, which was correlated with an increase in sigma, removed contaminants from the surface but did not drive hydrogen from the diamond bulk. ERD showed that the hydrogen plasma treatment produced an increase in the hydrogen concentration in the near-surface region which did not decrease while heating in vacuum at 700 K, but no improvement in the SEE properties was observed.

Mearini, G. T.↗

Characterization of devices, circuits, and high-temperature superconductor transmission lines by electro-optic testing

The development of a capability for testing transmission lines, devices, and circuits using the optically-based technique of electro-optics sampling was the goal of this project. Electro-optic network analysis of a high-speed device was demonstrated. The project involved research on all of the facets necessary in order to realize this result, including the discovery of the optimum electronic pulse source, development of an adequate test fixture, improvement of the electro-optic probe tip, and identification of a device which responded at high frequency but did not oscillate in the test fixture. In addition, during the process of investigating patterned high-critical-temperature superconductors, several non-contacting techniques for the determination of the transport properties of high T(sub c) films were developed and implemented. These are a transient, optical pump-probe, time-resolved reflectivity experiment, an impulsive-stimulated Raman scattering experiment, and a terahertz-beam coherent-spectroscopy experiment. The latter technique has enabled us to measure both the complex refractive index of an MgO substrate used for high-T(sub c) films and the complex conductivity of a YBa2Cu3O(7-x) sample. This information was acquired across an extremely wide frequency range: from the microwave to the submillimeter-wave regime. The experiments on the YBCO were conducted without patterning of, or contact to, the thin film. Thus, the need for the more difficult transmission-line experiments was eliminated. Progress in all of these areas was made and is documented in a number of papers. These papers may be found in the section listing the abstracts of the publications that were issued during the course of the research.

Whitaker, John F.↗

Investigating Si Bonding Environments in Mercurian Melts

Mercury’s low oxygen fugacity results in lavas with extraordinarily high sulfur contents (> 1 wt%). The high S lowers melt viscosity, but why this occurs is unclear (Mouser et al., 2021). The detection of Si-S bonds (using NMR) in such highly reduced basaltic glasses, suggest that the decreased viscosity is due to changes in the Si bonding environment (Pommier et al., 2023). To investigate further, we synthesized a series of Mercurian glasses at 1 GPa, with S contents ranging from 0-6 wt% and oxygen fugacities from IW-4 to IW-6. The experimental glasses were analyzed by Si K-edge X-ray Absorption Near Edge Structure (XANES) spectroscopy and 29Si Nuclear Magnetic Resonance (NMR). Ongoing analyses will include Raman and Fourier Transform Infrared (FTIR). The 29Si NMR analyses suggest the presence of Si-S bonds in the melts, in agreement with Pommier et al. (2023). The Si K-edge XANES spectra show a decrease in K-edge position of 0.4 to 0.6 eV from terrestrial basalts (at ~IW+3) to the experimental melts at IW-4 to IW-6. This shift suggests a moderate (<20 mole %) amount of Si has shifted to lower valence states (Boujibar et al, 2019). The melts contain 0-6 wt% S, so if the K-edge shifts are the results of Si-S bonding, it implies that the majority of the S in the melts is bonded to Si. However, S K-edge XANES analyses indicate that much of the S is also bonded with Mg and Ca at these low oxygen fugacities (Anzures et al, 2020). The implication is that non-bridging Si-S-(Mg,Ca) bonds are prevalent in the reduced melts, consistent with the decrease in viscosity of the melts being due to melt depolymerization. Overall, our results suggest that dissolution of S into the melts at low fO2 is accomplished through bonding with Si, and is accompanied by significant structural changes that lower melt viscosity. Lower melt viscosities will affect many aspects of Mercury’s evolution, from magma ocean dynamics, to melt migration in the mantle, to eruption dynamics and degassing.

Emily L Fischer↗

Elucidation of Free Radical and Optogalvanic Spectroscopy Associated with Microgravity Combustion via Conventional and Novel Laser Platforms

Combustion studies under both normal gravity and microgravity conditions depend a great deal on the availability and quality of the diagnostic systems used for such investigations. Microgravity phenomena are specially susceptible to even small perturbations and therefore non-intrusive diagnostic techniques are of paramount importance for successful understanding of reduced-gravity combustion phenomena. Several non-intrusive diagnostic techniques are available for probing and delineating normal as well as reduced gravity combustion processes, such as Rayleigh scattering, Raman scattering, Mie scattering, velocimetry, interferometric and Schlieren techniques, emission and laser-induced fluorescence (LIF) spectroscopy. Our approach is to use the LIF technique as a non-intrusive diagnostic tool for the study of combustion-associated free radicals and use the concomitant optogalvanic transitions to accomplish precise calibration of the laser wavelengths used for recording the excitation spectra of transient molecular species. In attempting to perform spectroscopic measurements on chemical intermediates, we have used conventional laser sources as well as new and novel platforms employing rare-earth doped solid-state lasers. Conventional (commercially available) sources of tunable UV laser radiation are extremely cumbersome and energy-consuming devices that are not very suitable for either in-space or in-flight (or microgravity drop tower) experiments. Traditional LIF sources of tunable UV laser radiation involve in addition to a pump laser (usually a Nd:YAG laser with an attached frequency-doubling stage), a tunable dye laser. In turn, the dye laser has to be provided with a dye circulation system and a subsequent stage for frequency-doubling of the dye laser radiation, together with a servo-tuning system (termed the 'Autotracker') to follow the wavelength changes and also an optical system (called the 'Frequency Separator') for separation of the emanating visible and UV beams. In contrast to this approach, we have devised an alternate arrangement for recording LIF excitation spectra of free radicals (following appropriate precursor fragmentation) that utilizes a tunable rare-earth doped solid state laser system with direct UV pumping. We have designed a compact and portable tunable UV laser system incorporating features necessary for both in-space and in-flight spectroscopy experiments. For the purpose of LIF excitation, we have developed an all-solid-state tunable UV laser that employs direct pumping of the solid-state UV-active medium employing UV harmonics from a Nd:YAG laser. An optical scheme with counterpropagating photolysis and excitation beams focused by suitable lenses into a reaction vacuum chamber was employed.

Misra, Prabhakar↗

Research Investigation Directed Toward Extending the Useful Range of the Electromagnetic Spectrum

The report discusses completed and proposed research in atomic and molecular physics conducted at the Columbia Radiation Laboratory from July 1972 to June 1973. Central topics described include the atomic spectra and electronic structure of alkali metals and helium, molecular microwave spectroscopy, the resonance physics of photon echoes in some solid state systems (including Raman echoes, superradiance, and two photon absorption), and liquid helium superfluidity.

Hartmann, S. R.↗

Non-intrusive flow measurements on a reentry vehicle

This study evaluates the utility of various non-intrusive techniques for the measurement of the flow field on the windward side of the Space Shuttle or a similar re-entry vehicle. Included are linear (Rayleigh, Raman, Mie, Laser Doppler Velocimetry, Resonant Doppler Velocimetry) and nonlinear (Coherent Anti-Stokes Raman, Laser Induced Fluorescence) light scattering, electron beam fluorescence, thermal emission and mass spectroscopy. Flow field properties are taken from a nonequilibrium flow model by Shinn, Moss and Simmonds at NASA Langley. Conclusions are, when possible, based on quantitative scaling of known laboratory results to the conditions projected. Detailed discussion with researchers in the field contributed further to these conclusions and provided valuable insights regarding the experimental feasibility of each of the techniques.

Miles, R. B.↗

Electron cyclotron resonance deposition of diamond-like films

Electron cyclotron resonance (ECR) microwave plasma CVD has been developed at low pressures (0.0001 - 0.01 torr) and at ambient and high substrate temperatures (up to 750 C), to achieve large-area (greater than 4 in. diameter) depositions of diamondlike amorphous carbon (a - C:H) films. The application of a RF bias to the substrate stage, which induces a negative self-bias voltage, is found to play a critical role in determining carbon bonding configurations and in modifying the film morphology. There are two distinct types of ECR-deposited diamondlike films. One type of diamondlike film exhibits a Raman spectrum consisting of broad and overlapping, graphitic D (1360/cm, line width = 280/cm) and G (1590/cm, line width 140/cm) lines, and the other type has a broad Raman peak centered at appoximately 1500/cm. Examination of plasma species by optical emission spectroscopy shows no correlation between the CH-asterisk emission intensity and the deposition rate of diamondklike films.

Shing, Y. H.↗

Monitoring spacecraft atmosphere contaminants by laser absorption spectroscopy

Laser-based spectrophotometric methods which have been proposed for the detection of trace concentrations of gaseous contaminants include Raman backscattering (LIDAR) and passive radiometry (LOPAIR). Remote sensing techniques using laser spectrometry are presented and in particular a simple long-path laser absorption method (LOLA), which is capable of resolving complex mixtures of closely related trace contaminants at ppm levels is discussed. A number of species were selected for study which are representative of those most likely to accumulate in closed environments, such as submarines or long-duration manned space flights. Computer programs were developed which will permit a real-time analysis of the monitored atmosphere. Estimates of the dynamic range of this monitoring technique for various system configurations, and comparison with other methods of analysis, are given.

Steinfeld, J. I.↗

Two-photon-excited fluorescence spectroscopy of atomic fluorine at 170 nm

Two-photon-excited fluorescence spectroscopy of atomic fluorine is reported. A doubled dye laser at 286-nm is Raman shifted in H2 to 170 nm (sixth anti-Stokes order) to excite ground-state 2P(0)J fluorine atoms to the 2D(0)J level. The fluorine atoms are detected by one of two methods: observing the fluorescence decay to the 2PJ level or observing F(+) production through the absorption of an additional photon by the excited atoms. Relative two-photon absorption cross sections to and the radiative lifetimes of the 2D(0)J states are measured.

Herring, G. C.↗

Simultaneous measurements of temperature and density in air flows using UV laser spectroscopy

The simultaneous measurement of temperature and density using laser-induced fluorescence of oxygen in combination with Q-branch Raman scattering of nitrogen and oxygen is demonstrated in a low-speed air flow. The lowest density and temperature measured in the experiment correspond to the freestream values at Mach 5 in the Ames 3.5-Foot Hypersonic Wind Tunnel for stagnation conditions of 100 atm and 1000 K. The experimental results demonstrate the viability of the optical technique for measurements that support the study of compressible turbulence and the validation of numerical codes in supersonic and hypersonic wind tunnel flows.

Fletcher, D. G.↗

Evaluation of non-intrusive flow measurement techniques for a re-entry flight experiment

This study evaluates various non-intrusive techniques for the measurement of the flow field on the windward side of the Space Shuttle orbiter or a similar reentry vehicle. Included are linear (Rayleigh, Raman, Mie, Laser Doppler Velocimetry, Resonant Doppler Velocimetry) and nonlinear (Coherent Anti-Stokes Raman, Laser-Induced Fluorescence) light scattering, electron-beam fluorescence, thermal emission, and mass spectroscopy. Flow-field properties were taken from a nonequilibrium flow model by Shinn, Moss, and Simmonds at the NASA Langley Research Center. Conclusions are, when possible, based on quantitative scaling of known laboratory results to the conditions projected. Detailed discussion with researchers in the field contributed further to these conclusions and provided valuable insights regarding the experimental feasibility of each of the techniques.

Miles, R. B.↗

Lunar and Planetary Science XXXV: Big Dust, Little Dust, and Aerogel

The titles in this section include: 1) A First Look at Graphite Grains from Orgueil: Morphology, Carbon, Nitrogen and Neon Isotopic Compositions of Individual, Chemically Separated Grains; 2) Discovery of an In-Situ Presolar Silicate Grain with GEMS-Like Composition in the Bishumpur Matrix; 3) Revised Global Accretion Rates of Micrometeorites in the Last Glacial Period; 4) Isotopic Fractionation of Potassium in Stony Cosmic Spherules; 5) Crumbs from the Crust of Vesta: Achondritic Micrometeorites from the South Pole Water Well; 6) Preservation of Micrometeoroid Remains on Solar Cells Returned from Orbit; 7) High Input Rates of Micrometeoritic Sulfur, 'Smoke' Particles and Oligoelements on the Early Earth; 8) High Resolution Confocal Raman Imaging of an IDP; 9) A micro-Raman Survey of 10 IDPs and 6 Carbonaceous Chondrites; 10) Mid- and Far-Infrared Spectroscopy at the Advanced Light Source; 11) Hypervelocity Impact Energy Loss and Track Shape in Aerogels: Theory and Experiment; 12) Fiducial Marks for Location of Particles in Aerogel.

Source record↗

Optical Spectroscopy of Stardust Samples

The Stardust spacecraft collected dust samples of the Kuiper belt comet 81P Wild-2 in aerogel and returned them to Earth January 15, 2006. Preliminary examination (PE) of the collected dust includes teams focused on mineralogy, chemical composition, isotopic measurements, organic analysis, cratering and spectroscopic properties. The main PE science goals are to provide an initial characterization of the returned samples with an emphasis on the capture process and its effects on the samples, a comparison of Stardust samples to other meteoritic materials, and the abundance of presolar materials in the Stardust samples. The science objectives of the Spectroscopy team are to obtain spectroscopic data on Stardust particles through infrared (IR), UV/Vis and Raman measurements of particles in aerogel, extracted particles, keystones, and microtome thin sections. These data will be used to answer fundamental science questions about the nature of the samples, but will also serve as preliminary mineralogical data to guide follow-on measurements that will be performed in the other preliminary examination teams. The IR characteristics of Stardust particles are measured to determine: 1) the nature of the indigenous 3.4 micron organic feature, is it detected and can it be differentiated/deconvolved from the contaminated aerogel? How does it compare to features observed in interplanetary dust particles (IDPs) and to astronomical measurements of comets and interstellar dust? 2) the shape and fine structure within the 10 micron silicate feature. Overlap with the strong Si-O stretching vibration from the aerogel complicates this analysis, but we hope to determine if the feature is dominated by amorphous silicates such as those observed in IDPs and comets and whether or not crystalline silicates (e.g. olivine, pyroxene, clays) are present, 3) the presence of secondary (alteration) phases. Deep Impact results suggest that IR observations of Stardust particles should be evaluated for the presence of hydrated materials (water bands at 3 and 6 microns) and carbonates (6.8 microns and other resonances) and 4) the detection of crystalline features in the far-IR (20-100 microns) region where crystalline silicates and other minerals have strong bands that can be used both for phase analysis and phase chemistry. It has been demonstrated that these far-IR measurements can be obtained in situ on particles in aerogel keystones.

Keller, Lindsay P.↗

Liquid Space Lubricants Examined by Vibrational Micro-Spectroscopy

Considerable effort has been expended to develop liquid lubricants for satellites and space exploration vehicles. These lubricants must often perform under a range of harsh conditions such as vacuum, radiation, and temperature extremes while in orbit or in transit and in extremely dusty environments at destinations such as the Moon and Mars. Historically, oil development was guided by terrestrial application, which did not provide adequate space lubricants. Novel fluids such as the perfluorinated polyethers provided some relief but are far from ideal. With each new fluid proposed to solve one problem, other problems have arisen. Much of the work performed at the National Aeronautics and Space Administration (NASA) Glenn Research Center (GRC) in elucidating the mechanisms by which chemical degradation of space oils occur has been done by vibrational micro-spectroscopic techniques such as infrared and Raman, which this review details. Presented are fundamental lubrication studies as well as actual case studies in which vibrational spectroscopy has led to millions of dollars in savings and potentially prevented loss of mission.

Street, Kenneth W., Jr.↗

Structural studies of gels and gel-glasses in the SiO2-GeO2 system using vibrational spectroscopy

GeO2 gel and gels in the SiO2-GeO2 system synthesized by the hydrolytic polycondensation of metal alkoxides have been studied by infrared and Raman spectroscopic techniques. The molecular structures, hydroxyl contents, and crystallinity of gels and gel-glasses in relation to the thermal history and GeO2 concentration were investigated. The binary compositions having up to 70 mol percent GeO2 were examined.

Mukherjee, Shyama P.↗