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At least 235 records · Page 13

Below Band-Gap Laser Ablation of Diamond for Transmission Electron Microscopy

A 248-nm excimer laser was used to thin naturally occurring type 1a diamond substrates at normal and glancing (22 deg) incidence. Perforation of a 250 micron thick substrate was achieved in about 15 minutes at normal incidence. Whilst the substrate thinned at glancing incidence was found to have large electron-transparent areas, that thinned at normal incidence required additional argon milling to achieve electron transparency. X-ray photoelectron spectroscopy of the back surface of the diamond failed to detect any graphite or glassy carbon, confirming that damage due to laser ablation occurs only at the incident surface. Samples prepared using this technique imaged in the transmission electron microscope were observed to have retained the nitrogen platelets

Posthill, J. B.↗

Below band-gap laser ablation of diamond for transmission electron microscopy

A 248 nm excimer laser was used to thin naturally occurring type 1a diamond substrates at normal and glancing (22 deg) incidence. Perforation of a 250-micron-thick substrate was achieved in about 15 min at normal incidence. While the substrate thinned at glancing incidence was found to have large electron-transparent areas, that thinned at normal incidence required additional argon-ion milling to achieve electron transparency. X-ray photoelectron spectroscopy of the back surface of the diamond failed to detect any graphite or glassy carbon, confirming that damage due to laser ablation occurs only at the incident surface. Samples prepared using this technique imaged in the transmission electron microscope were observed to have retained the nitrogen platelets characteristic of such type 1a diamonds.

George, T.↗

Investigation of stimulated Brillouin scattering switching in mid infrared fibers

Backward stimulated Brillouin scattering (SBS) has been experimentally studied in midinfrared transparent AgCl and KRS-5 fibers. In the present scheme, pump transmission through the fibers and acoustooptic radiative effects are simultaneously observed. The SBS shifted scattered light spectrum is investigated by laser heterodyne spectroscopy using HgCdTe and very fast metal-oxide-metal diode broadband mixers. The results suggest that reflection under high incident laser power departs from simple Fresnel surface reflection.

Yu, Chung↗

Low Temperature Ohmic Contact Formation of Ni2Si on N-type 4H-SiC and 6H-SiC

Nickel Silicide (Ni2Si) is investigated as possible ohmic contact to heavily nitrogen-doped N-type 4H-SiC and 6H-SiC. Nickel Silicide was deposited via electron gun with various thicknesses on both Si and C faces of the SiC substrates. The Ni2Si contacts were formed at room temperature as well as at elevated temperatures (400 to 1000 K). Contact resistivities and I-V characteristics were measured at temperatures between 100 and 700 C. To investigate the electric properties, I-V characteristics were studied and the Transmission Line Method (TLM) was used to determine the specific contact resistance for the samples at each annealing temperature. Both Rutherford Backscattering Spectroscopy (RBS) and Auger Electron Spectroscopy (AES) were used for depth profiling of the Ni2Si, Si, and C. X-ray Photoemission Spectroscopy (XPS) was used to study the chemical structure of the Ni2Si/SiC interface.

Elsamadicy, A. M.↗

Absorption of solar radiation by O2 - Implications for O3 and lifetimes of N2O, CFCl3, and CF2Cl2

An accurate line-by-line model is used to evaluate effects of absorption in the Schumann-Runge bands of O2 on transmission of UV radiation. The model is used to evaluate rates of photolysis for N2O, CFCl3, and CF2Cl2, and to infer global loss rates and instantaneous lifetimes appropriate for 1980. A parameterized version of the line-by-line model enabling rapid evaluation of transmission in the Schumann-Runge region is described. Photochemical calculations employing the parameterization and constrained by data from the Atmospheric Trace Molecule Spectroscopy experiment are used to examine the budget of odd oxygen. Consistent with previous studies, it is shown that photochemical loss of odd oxygen exceeds production by photolysis of O2 for altitudes above 40 km. The imbalance between production and loss is shown to be consistent with a source of odd oxygen proportional to the product of the mixing ratio and photolysis rate of ozone, which suggests that processes involving vibrationally excited O2 may play an important role in production of odd oxygen.

Minschwaner, K.↗

A Characterization Of Alcohol Fuel Vapor For Wavelength Modulation Spectroscopy Applied To Microgravity Flame Spread

A diode laser diagnostic is being developed for use in an ongoing investigation of flame spread in microgravity at NASA Glenn Research Center. Flame spread rates through non-homogenous gas mixtures are significantly different in a microgravity environment because of buoyancy and possibly hydrostatic pressure effects. These effects contribute to the fuel vapor concentration ahead of the flame being altered so that flame spread is more rapid in microgravity. This paper describes spectral transmission measurements made through mixtures of alcohol, water vapor, and nitrogen in a gas cell that was designed and built to allow measurements at temperatures up to 500 C. The alcohols considered are methanol, ethanol, and n-propanol. The basic technique of wavelength modulation spectroscopy for gas species measurements in microgravity was developed by Silver et al. For this technique to be applicable, one must carefully choose the spectral features over which the diode laser is modulated to provide good sensitivity and minimize interference from other molecular lines such as those in water. Because the methanol spectrum was not known with sufficient resolution in the wavelength region of interest, our first task was to perform high-resolution transmission measurements with an FTIR spectrometer for methanol vapor in nitrogen, followed recently by ethanol and n-propanol. A computer program was written to generate synthesized data to mimic that expected from the experiment using the laser diode, and results from that simulation are also presented.

Kulis, Michael J.↗

Interstellar X-Ray Absorption Spectroscopy of the Crab Pulsar with the LETGS

We study the interstellar X-ray absorption along the line of sight to the Crab Pulsar. The Crab was observed with the Low Energy Transmission Grating Spectrometer on the Chandra X-ray Observatory, and the pulsar, a point source, produces a full resolution spectrum. The continuum spectrum appears smooth, and we compare its parameters with other measurements of the pulsar spectrum. The spectrum clearly shows absorption edges due to interstellar Ne, Fe, and O. The O edge shows spectral structure that is probably due to O bound in molecules or dust. We search for near-edge structure (EXAFS) in the O absorption spectrum. The Fe L absorption spectrum is largely due to a set of unresolved discrete n=2-3 transitions in neutral or near-neutral Fe, and we analyze it using a new set of dedicated atomic structure calculations, which provide absolute cross sections. In addition to being interesting in its own right, the ISM absorption needs to be understood in quantitative detail in order to derive spectroscopic constraints on possible soft thermal radiation from the pulsar.

Paerels, Frits↗

Characterization of the surfaces of platinum/tin oxide based catalysts by Fourier Transform Infrared Spectroscopy (FTIR)

A Pt/SnO2 catalyst has been developed at NASA Langley that is effective for the oxidation of CO at room temperature (1). A mechanism has been proposed to explain the effectiveness of this catalyst (2), but most of the species involved in this mechanism have not been observed under actual catalytic conditions. A number of these species are potentially detectable by Fourier Transform Infrared Spectroscopy (FTIR), e.g., HOSnO sub x, HO sub y PtO sub z, Pt-CO, and SnHCO3. Therefore a preliminary investigation was conducted to determine what might be learned about this particular catalyst by transmission FTIR. The main advantage of FTIR for this work is that the catalyst can be examined under conditions similar to the actual catalytic conditions. This can be of critical importance since some surface species may exist only when the reaction gases are present. Another advantage of the infrared approach is that since vibrations are probed, subtle chemical details may be obtained. The main disadvantage of this approach is that FTIR is not nearly as sensitive as the Ultra High Vacuum (UHV) surface analytical techniques such as Auger, Electron Spectroscopy for Chemical Analysis (ESCA), Electron Energy Loss Spectroscopy (EELS), etc. Another problem is that the assignment of the observed infrared bands may be difficult.

Keiser, Joseph T.↗

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.↗

Characterization of 4H <000-1> Silicon Carbide Films Grown by Solvent-Laser Heated Floating Zone

Commercially available bulk silicon carbide (SiC) has a high number (>2000/sq cm) of screw dislocations (SD) that have been linked to degradation of high-field power device electrical performance properties. Researchers at the NASA Glenn Research Center have proposed a method to mass-produce significantly higher quality bulk SiC. In order for this bulk growth method to become reality, growth of long single crystal SiC fibers must first be achieved. Therefore, a new growth method, Solvent-Laser Heated Floating Zone (Solvent-LHFZ), has been implemented. While some of the initial Solvent-LHFZ results have recently been reported, this paper focuses on further characterization of grown crystals and their growth fronts. To this end, secondary ion mass spectroscopy (SIMS) depth profiles, cross section analysis by focused ion beam (FIB) milling and mechanical polishing, and orientation and structural characterization by x-ray transmission Laue diffraction patterns and x-ray topography were used. Results paint a picture of a chaotic growth front, with Fe incorporation dependant on C concentration.

Woodworth, Andrew, A↗

Evidence of Collisional Histories of Asteroids, Comets and Meteorites: Comparisons with Shocked Minerals

Evidence of the collisional history of comets and asteroids has been emerging from analyses of cometary forsterite and enstatite returned from Comet Wild 2 by the Stardust mission (Keller et al.Geochim. Cosmochim. Acta 72, 2008; Tomeoka et al. MAPS 43, 2008; Jacobs et al. MAPS 44, 2009). Likewise, shock metamorphism is observed in many meteoritic forsterites and enstatites (McCausland et al. AGU, 2010), suggesting similar collisional histories for asteroids. Further exploration of the effects of collisions is slated for the upcoming Asteroid Impact Mission/Double Asteroid Redirection Test (AIM/DART) mission, expected for launch in 2020. DART will impact Didymoon, the companion of the larger 65803 Didymos (1996 G2) asteroid, and AIM will use its instrumentation to characterize the impact. A suite of relevant impact experiments have been carried out in the Experimental Impact Laboratory at the NASA Johnson Space Center at velocities ranging from approx. 2.0 - 2.8 km/s and temperatures from 25 C to -100 C. Targets include a suite of minerals typically found in cometary dust and in asteroids and meteorites: Mg-rich forsterite (olivine), enstatite (orthopyroxene), diopside (clinopyroxene), magnesite (Mg-rich carbonate), and serpentine (phyllosilicate). Transmission Electron Microscope (TEM) imaging indicates evidence of shock similar to that seen in forsterite and enstatite from Comet Wild 2. Fourier Transform Infrared (FTIR) Spectroscopy will also be used for comparisons with meteorite spectra. A quantitative analysis of the shock pressures required to induce planar dislocations and spectral effects with respect to wavelength will also be presented.

Lederer, Susan M.↗

On the Use of Fourier Transform Infrared (FT-IR) Spectroscopy and Synthetic Calibration Spectra to Quantify Gas Concentrations in a Fischer-Tropsch Catalyst System

One possible origin of prebiotic organic material is that these compounds were formed via Fischer-Tropsch-type (FTT) reactions of carbon monoxide and hydrogen on silicate and oxide grains in the warm, inner-solar nebula. To investigate this possibility, an experimental system has been built in which the catalytic efficiency of different grain-analog materials can be tested. During such runs, the gas phase above these grain analogs is sampled using Fourier transform infrared (FT-IR) spectroscopy. To provide quantitative estimates of the concentration of these gases, a technique in which high-resolution spectra of the gases are calculated using the high-resolution transmission molecular absorption (HITRAN) database is used. Next, these spectra are processed via a method that mimics the processes giving rise to the instrumental line shape of the FT-IR spectrometer, including apodization, self-apodization, and broadening due to the finite resolution. The result is a very close match between the measured and computed spectra. This technique was tested using four major gases found in the FTT reactions: carbon monoxide, methane, carbon dioxide, and water. For the ranges typical of the FTT reactions, the carbon monoxide results were found to be accurate to within 5% and the remaining gases accurate to within 10%. These spectra can then be used to generate synthetic calibration data, allowing the rapid computation of the gas concentrations in the FTT experiments.

Infrared Spectroscopy↗

The application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes

Electrochemical impedance spectra of rolled and bonded and sintered porous nickel battery electrodes were recorded periodically during charge/discharge cycling in concentrated KOH solution at various temperatures. A transmission line model (TLM) was adopted to represent the impedance of the porous electrodes, and various model parameters were adjusted in a curve fitting routine to reproduce the experimental impedances. Degradation processes for rolled and bonded electrodes were deduced from changes in model parameters with electrode cycling time. In developing the TLM, impedance spectra of planar (non-porous) electrodes were used to represent the pore wall and backing plate interfacial impedances. These data were measured over a range of potentials and temperatures, and an equivalent circuit model was adopted to represent the planar electrode data. Cyclic voltammetry was used to study the characteristics of the oxygen evolution reaction on planar nickel electrodes during charging, since oxygen evolution can affect battery electrode charging efficiency and ultimately electrode cycle life if the overpotential for oxygen evolution is sufficiently low. Transmission line modeling results suggest that porous rolled and bonded nickel electrodes undergo restructuring during charge/discharge cycling prior to failure.

Macdonald, D. D.↗

New Method Developed To Purify Single Wall Carbon Nanotubes for Aerospace Applications

Single wall carbon nanotubes have attracted considerable attention because of their remarkable mechanical properties and electrical and thermal conductivities. Use of these materials as primary or secondary reinforcements in polymers or ceramics could lead to new materials with significantly enhanced mechanical strength and electrical and thermal conductivity. Use of carbon-nanotube-reinforced materials in aerospace components will enable substantial reductions in component weight and improvements in durability and safety. Potential applications for single wall carbon nanotubes include lightweight components for vehicle structures and propulsion systems, fuel cell components (bipolar plates and electrodes) and battery electrodes, and ultra-lightweight materials for use in solar sails. A major barrier to the successful use of carbon nanotubes in these components is the need for methods to economically produce pure carbon nanotubes in large enough quantities to not only evaluate their suitability for certain applications but also produce actual components. Most carbon nanotube synthesis methods, including the HiPCO (high pressure carbon monoxide) method developed by Smalley and others, employ metal catalysts that remain trapped in the final product. These catalyst impurities can affect nanotube properties and accelerate their decomposition. The development of techniques to remove most, if not all, of these impurities is essential to their successful use in practical applications. A new method has been developed at the NASA Glenn Research Center to purify gram-scale quantities of single wall carbon nanotubes. This method, a modification of a gas phase purification technique previously reported by Smalley and others, uses a combination of high-temperature oxidations and repeated extractions with nitric and hydrochloric acid. This improved procedure significantly reduces the amount of impurities (catalyst and nonnanotube forms of carbon) within the nanotubes, increasing their stability significantly. The onset of decomposition of the purified nanotubes (determined by thermal gravimetric analysis in air) is more than 300 C higher than that of the crude nanotubes. Transmission electron microscopy analysis of nanotubes purified by this method reveals near complete removal of iron catalyst particles. Analysis of the nanotubes using inductively coupled plasma spectroscopy revealed that the iron content of the nanotubes was reduced from 22.7 wt% in the crude nanotubes to less than 0.02 wt%. X-ray photoelectron spectroscopy revealed a decrease in iron content after purification as well as an increase in oxygen content due to the formation of carboxylic acid groups on the surface of the nanotubes. Nanotubes purified by this improved method can be readily dispersed in common organic solvents, in particular N,N-dimethylformamide, using prolonged ultrasonic treatment. These dispersions can then be used to incorporate single wall carbon nanotubes into polymer films.

Lebron, Marisabel↗

High-Efficiency Flexible Multilevel Photon Sieves by Single-Step Laser-Based Fabrication and Optical Analysis

Over the past several decades, the need for high-resolution, high-efficiency, lightweight, high contrast focusing optics has continued to increase due to their applications in fields such as astronomy, spectroscopy, free-space optical communications, defense, and remote sensing. In recent years, photon sieve planar diffractive optics have been developed on flexible, lightweight polyimide substrates. However, transmission efficiencies have continuously been very low (~1-4%), thus impeding the widespread use of photon sieves in practical applications. Here, we present a flexible, lightweight, N = 4 level phase photon sieve with over 25% transmission efficiency; nearly triple that of any other photon sieve reported thus far. In this study, the photon sieve was fabricated via a novel pulsed laser ablation method using an ultraviolet source, and the total time to fabricate a ~3 sq cm sample was tens of seconds. Theoretical analysis of the photon sieve was carried out via the FDTD method, and was in very good agreement with experimental results. We also calculated via FDTD modeling the behavior of higher step (N = 8, 16, 32) photon sieves for further enhanced efficiencies, and show a fundamental limit on photon sieve efficiency of 70% in the limit of increasing step number. This multilevel photon sieve represents a new step in high-resolution diffractive optics, moving towards efficiencies suitable for widespread applications.

Julian, Matthew N.↗

Decomposition of ethylene on small Pd particles

New results have been obtained which contribute to the understanding of hydrocarbon reactions on the surface of highly dispersed metal systems. Small particle of Pd were grown by electron beam evaporation on cleavage planes of high purity natural mica under ultrahigh vacuum conditions. Samples were subsequently characterized by transmission electron microscopy. Average particle sizes ranged from about 1 to 10 nm diameter. The chemisoption and decomposition of C2H4 on the Pd particles was studied using Auger electron spectroscopy and flash thermal desorption. It is shown that (a) C2H4 decomposes on Pd particles at room temperature, (b) specific surface sites are causing decomposition, and (c) the proportion of such active sites is significantly greater for the smaller metal particles. This enhanced reactivity may be due to an increase in the density of step, corner, and edge sites with a decrease in particle size.

Durrer, W. G.↗

Method and apparatus for enhancing laser absorption sensitivity

A simple optomechanical method and apparatus is described for substantially reducing the amplitude of unwanted multiple interference fringes which often limit the sensitivities of tunable laser absorption spectrometers. An exterior cavity is defined by partially transmissible surfaces such as a laser exit plate, a detector input, etc. That cavity is spoiled by placing an oscillating plate in the laser beam. For tunable diode laser spectroscopy in the mid-infrared region, a Brewster-plate spoiler allows the harmonic detection of absorptances of less than 10 to the -5 in a single laser scan. Improved operation is achieved without subtraction techniques, without complex laser frequency modulation, and without distortion of the molecular lineshape signal. The technique is applicable to tunable lasers operating from UV to IR wavelengths and in spectrometers which employ either short or long pathlengths, including the use of retroreflectors or multipass cells.

Webster, Christopher R.↗

The application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes

The use of wide-band electrochemical impedance spectroscopy is described for characterizing the degradation of porous Ni(OH)2/NiOOH electrodes in concentrated KOH electrolyte solutions. The impedance spectra are interpreted in terms of a finite electrical transmission line and the changes in the components of the electrical analog are followed as a function of cycle number. The degradation of the capacity of rolled and bonded Ni(OH)2/NiOOH electrodes is caused by rupture of ohmic contacts within the active mass and by restructuring which results in a decrease in the number of active pores.

Macdonald, Digby D.↗