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At least 325 records · Page 18

Cavity Ring Down Spectroscopy of Cold Neutral Phenanthrene and Phenanthridine in Supersonic Jets

Here we study the effect of nitrogen insertion on the electronic spectra of polycyclic aromatic hydrocarbon (PAH) molecules measured under laboratory conditions that are relevant for comparison with astronomical data. We examine the case of the substitution of carbon atoms by nitrogen atoms in the benzenoid skeleton of phenanthrene (C 14 H 10 ), a prototype non-compact PAH. The vibronic transitions of the 2 1 A 1 (S 1 )←X 1 A 1 (S 0 ) electronic absorption band system of neutral phenanthrene (C 14 H 10 ) and phenanthridine (C 13 H 9 N) molecules seeded in a supersonic free jet expansion of argon gas are measured in the 315-345 nm region using the cavity ring down spectroscopy (CRDS) technique. Additional measurements of the absorption spectra of the phenanthrene, phenanthridine, and 1,10-phenanthroline (C 12 H 8 N 2 ) molecules isolated in 10-K solid argon matrices are also presented. The results obtained confirm that laboratory spectra of cold, isolated molecules obtained under astrophysically relevant conditions are required for a direct, unambiguous comparison with astronomical observations as well as for the understanding of the physical evolution of the interstellar medium.

Absorption band↗

In-situ Raman Instrumentation and Measurements in Supercritical Water Oxidation Systems

Due to the advent of recent advances in reactor designs and operational procedures, renewed attention has been given to a host of supercritical water oxidation (SCWO) technology applications. This includes resource recovery, water reclamation, and solid waste destruction. SCWO is often recognized as a “green technology” because of its ability to extract useful energy while producing benign products from environmentally challenging waste streams (e.g., wet organic wastes, pharmaceutical wastes, military wastes). The present work was motivated by NASA’s interests in solid waste management and water recovery for long-duration space missions. To that end, the main focus of this paper is to present work on characterizing the behavior of supercritical water oxidation systems utilizing state of the art laser Raman spectroscopy. The main benefit of Raman diagnostics is its ability to identify chemical composition and to measure concentrations of the compounds involved in the reaction. Two separate Raman systems for SCWO measurements that have been developed for this study will be described. The first system is a 2-D traversing system useful for making in-situ measurements in conditions where spatial gradients of species and temperature are important and has been successfully utilized in making species (ethanol, oxygen, water, nitrogen and carbon dioxide) concentrations and temperature measurements in ethanol hydrothermal jet flames. The second system is a packaged modular Raman probe unit for portable deployment to different reactors and is more suitable for relatively homogeneous systems such as a batch reactor. The design, development, and examples of obtained results from both systems will be presented for various reactant streams. Reaction rate and fuel conversion estimates from chemistry models will also be presented.

supercritical water oxidation↗

Shock Tube Characterization of Laser Absorption Sensors for Combustion Measurements of Green Propellants

Chemical kinetic models for green spacecraft propulsion systems are needed to calculate efficiency, estimate toxic products, and mitigate plume impingement risks. Laser absorption spectroscopy (LAS) is a common technique used to measure time-resolved mole fraction for model validation. LAS was used to measure species-time history nitrous oxide (N2O) and carbon monoxide (CO) behind reflected shock waves. The diagnostics were implemented at the University of Central Florida high-pressure shock tube facility. A mixture of ethylene (0.002) and N2O (0.008) was diluted with argon gas (0.99) and shock heated 12 bar and temperatures from 1400 to 1600 K.

Marley A. Albright↗

Organic Products of Fatty Acid and Magnesium Sulfate Mixtures after Gamma Radiolysis: Implications for Missions to Europa

If ocean-derived materials are present at Europa’s surface, they would represent accessible records of ocean chemistry and habitability, but such materials would be further processed by the moon’s harsh radiation environment. In this study, saturated fatty acids were precipitated onto a Europa-relevant hydrated magnesium sulfate and exposed to gamma radiation doses up to 2 MGy at -196° C. Alkane chains, with carbon numbers one less than those of the starting fatty acids, were the most abundant radiolysis products in solvent and thermal extracts analyzed by gas chromatography mass spectrometry. Detections of monounsaturated fatty acids and combined radiolysis products were attributed to the experiment’s Europa-like parameters. Additionally, elevated concentrations of shorter-chain saturated fatty acids suggest that gamma radiation induced charge remote fragmentation of the alkyl chains of some starting fatty acids under these experimental conditions. Quantitation of fatty acid concentrations in the irradiated samples enabled the calculation of a radiolysis constant that indicated exposure to a 5 MGy dose of gamma radiation would have resulted in a ~90% loss of the initial fatty acid population. The samples were further studied by Raman spectroscopy and laser desorption and ionization mass spectrometry, which characterized the distribution of fatty acids and their radiolysis products on sulfate surfaces. The substantial loss of starting fatty acids typically seen with increasing radiation dose, along with the remarkable diversity of radiolysis products identified, suggest that the detection of fatty acids in irradiated sulfate deposits on Europa will be challenged by rapid destruction of any initial fatty acid populations and scrambling of their residual signals by a myriad of organic radiolysis products. If missions to Europa encounter sulfate deposits, targeting minimally irradiated units may still enable the detection of surviving fatty acid signatures that could inform about Europa’s subsurface chemistry and habitability.

James M T Lewis↗

Characterization of the surfaces of platinum/tin oxide based catalysts by Fourier transform spectroscopy (FTIR)

The Laser Atmospheric Wind Sounder (LAWS) Program has as one of its goals the development of a satellite based carbon dioxide laser for making wind velocity measurements. The specifications for this laser include the requirement that the laser operate at a repetition rate of 10 Hertz continuously for three years. Earth-based carbon dioxide lasers can operate for only a short time on a single charge of gas because the lasing action causes the CO2 to break down into CO and O2. Therefore, earth-based CO2 lasers are generally operated in a flow through mode in which the spent gas is continually exhausted and fresh gas is continually added. For a satellite based system, however, a recirculation system is desired because it is not practical to send up extra tanks of CO2. A catalyst which could enable a recirculating CO2 laser to function continuously for three years needs to be developed. In the development of a catalyst system there are many variables. Obviously, not all possible formulations can be tested for three years, therefore, an accurate model which is based on the reaction mechanism is needed. The construction of a multistep reaction mechanism is similar to the construction of a jigsaw puzzle. Different techniques each supply a piece of the puzzle and the researcher must put the pieces together. Transmission infrared spectroscopy was shown to be very useful in supplying some of the information needed to elucidate reaction mechanisms. The purpose was to see what kind of information might be obtained about the NASA catalyst using infrared absorption spectroscopy. Approximately 200 infrared spectra of the prototype Pt/tin oxide catalyst and its precursor components are observed under a variety of different conditions. The most significant observations are summarized.

Keiser, Joseph T.↗

20 years of Tm:Ho:YLF and LuLF Laser Development for Global Winds Measurements

NASA Langley Research Center has a long history of developing 2 micron lasers. From fundamental spectroscopy research, theoretical prediction of new materials, laser demonstration and engineering of lidar systems, it has been a very successful program spanning around two decades. This article covers the program development from the early research to the present instrumentation. A brief historical perspective of Tm:Ho work by early researchers is also given.

Singh, Upendra N.↗

Advances in High Energy Solid-State Pulsed 2-Micron Lidar Development for Ground and Airborne Wind, Water Vapor and CO2 Measurements

NASA Langley Research Center has a long history of developing 2-micron lasers. From fundamental spectroscopy research, theoretical prediction of new materials, laser demonstration and engineering of lidar systems, it has been a very successful program spanning around two decades. Successful development of 2-micron lasers has led to development of a state-of-the-art compact lidar transceiver for a pulsed coherent Doppler lidar system for wind measurement with an unprecedented laser pulse energy of 250 millijoules in a rugged package. This high pulse energy is produced by a Ho:Tm:LuLiF laser with an optical amplifier. While the lidar is meant for use as an airborne instrument, ground-based tests were carried out to characterize performance of the lidar. Atmospheric measurements will be presented, showing the lidar's capability for wind measurement in the atmospheric boundary layer and free troposphere. Lidar wind measurements are compared to a balloon sonde, showing good agreement between the two sensors. Similar architecture has been used to develop a high energy, Ho:Tm:YLF double-pulsed 2-micron Integrated Differential Absorption Lidar (IPDA) instrument based on direct detection technique that provides atmospheric column CO2 measurements. This instrument has been successfully used to measure atmospheric CO2 column density initially from a ground mobile lidar trailer, and then it was integrated on B-200 plane and 20 hours of flight measurement were made from an altitude ranging 1500 meters to 8000 meters. These measurements were compared to in-situ measurements and National Oceanic and Atmospheric Administration (NOAA) airborne flask measurement to derive the dry mixing ratio of the column CO2 by reflecting the signal by various reflecting surfaces such as land, vegetation, ocean surface, snow and sand. The lidar measurements when compared showed a very agreement with in-situ and airborne flask measurement. NASA Langley Research Center is currently developing a triple-pulsed 2-micron Integrated Differential Absorption Lidar (IPDA) instrument for simultaneous measurement of water vapor and carbon-dioxide column density measurement from an air-borne platform. This presentation will give an overview of the 2 decades of 2-micron coherent and direction detection of laser/lidar development at NASA Langley Research Center and will present the ground and airborne wind and column CO2 measurement intercomparison with in-situ, balloon and flask measurements.

Singh, Upendra N.↗

Controlled Contamination of Epoxy Composites with PDMS and Removal by Laser Ablation

Surface preparation is critical to the performance of adhesively bonded composites. During manufacturing, minute quantities of mold release compounds are inevitably deposited on faying surfaces and may compromise bond performance. To ensure safety, mechanical fasteners and other crack arrest features must be installed in the bondlines of primary structures, which negates some advantages of adhesively bonded construction. Laser ablation is an automated, repeatable, and scalable process with high potential for the surface preparation of metals and composites in critical applications such as primary airframe structures. In this study, laser ablation is evaluated on composite surfaces for the removal of polydimethylsiloxane (PDMS), a common mold release material. Composite panels were contaminated uniformly with PDMS film thicknesses as low as 6.0 nm as measured by variable angle spectroscopic ellipsometry. Bond performance was assessed by mechanical testing using a 250 F cure, epoxy adhesive and compared with pre-bond surface inspection results. Water contact angle, optically stimulated electron emission, and laser induced breakdown spectroscopy were used to characterize contaminated and laser ablated surfaces. The failure mode obtained from double cantilever beam tests correlated well with surface characterization data. The test results indicated that even low levels of PDMS were not completely removed by laser ablation.

Palmieri, Frank↗

Lunar and Planetary Science XXXV: Meteorites: Experiments and Spectroscopy

The session "Meteorites: Experiments and Spectroscopy" included the following reports:The Suitability of Laser Induced Breakdown Spectroscopy for Determining the Compositions of Extraterrestrial Material; Deconvolving Terrestrial Alteration Mineral Spectral Signatures from Meteorite Reflectance Measurements; Impacts of Ions and Micrometeorites on Mineral Surfaces: Reflectance and Chemical Changes Found in Ordinary Chondrites; FT-IR Micro-spectroscopy of Fine-grained Planetary Materials: Further Results; Effusion Cell Measurements of the Vapor Pressure of Cobalt at Temperatures up to 2000K: Comparisons with Iron and Nickel; Kinetics of Fe2+-Mg Order-Disorder in P21/c Pigeonite: Implications for Cooling Rates Calculations; Compressional and Shear Wave Velocities in Meteorites; Chemical and Mineralogical Size Segregation in the Impact Disruption of Anhydrous Stone Meteorites; and Shock Pressures of Impacts vs. Crystallization Pressures of Shock-induced Melt Veins of the chondrites.

Source record↗

Recommended Practices in Laser-Induced Fluorescence (LIF) Diagnostics for Electric Propulsion

Laser-induced fluorescence (LIF) spectroscopy uses Doppler-shifted laser photons to excite a bound electron transition in an atom or ion, with subsequent fluorescence emission detected in order to measure the local velocity distribution function (VDF) and/or particle density. Due to its non-invasive nature, high spatial resolution, and acceptable difficulty of implementation, LIF has become a favored diagnostic for electric propulsion (EP) plasmas, particularly in the study of Hall thrusters. This paper presents recommended best practices for LIF measurements in electric thrusters, drawn from over three decades of implementation heritage in the EP community. Focusing on both single-photon LIF (typically used to measure VDFs) and two-photon LIF (TALIF, typically used to determine densities), the paper covers selection of atomic transitions to target, experimental setups, and interpretation of data. A number of special topics and advanced applications are discussed, including uncertainty analysis, techniques for high-speed measurements, and applications to a variety of propellants.

plasma plume↗

Tandem LA-ICP-MS & LIBS; A New Micro-Analytical Technique for the Measurement of Every Element in the Periodic Table

Laser Ablation ICP-MS (LA-ICP-MS) has been widely accepted as a microanalytical technique for in-situ trace (ppb) elemental analysis on the micron scale in a variety of geologic materials. LA-ICP-MS (single or multi-collector) provides both elemental and isotopic measurements critical for a wide range of geological research by generating a fine grained aerosol (nm scale) during the laser ablation event and delivering that aerosol to the ICP ion source of the mass spectrometer via an inert carrier gas. LA-ICP-MS, however, suffers from limitations in analyzing high ionization potential elements as well as elements subject to atmospheric and argon based interferences. LA-ICP-MS also has limitations in analyzing major elements due to detector saturation. An alternative laser ablation technique, Laser Induced Breakdown Spectroscopy (LIBS), employs an optical spectrometer integrated into the laser ablation system that analyzes the laser induced plasma at the sample surface across the entire optical spectrum for emission lines of every element in the periodic table. Elements that are difficult or impossible to measure with LA-ICP-MS are now possible to analyze with LIBS down to low ppm levels with CCD and/or ICCD detection. We introduce a new laser based technique, “Tandem LA-LIBS”, that combines LA for ICP-MS and LIBS into one integrated laser ablation system. This system has the effect of expanding the elemental coverage and the dynamic range of the laser ablation experiment as measurements from ppb to % level matrix elements can now be analyzed in a single ablation experiment. We present both femtosecond and nanosecond Tandem LA-LIBS quantitative and qualitative data on wide range of geological materials for those elements that are difficult or impossible by traditional LA-ICP-MS techniques such as F, H, O, N, C, S, halogens, etc. We also demonstrate that the simultaneous measurement of trace, minor and major elements are now possible in a single laser ablation experiment with Tandem LA-LIBS technology.

LA-ICP-MS↗

Volume Measurements of Laser-generated Pits for In Situ Geochronology using KArLE (Potassium-Argon Laser Experiment)

The Potassium-Argon Laser Experiment( KArLE), is composed of two main instruments: a spectrometer as part of the Laser-Induced Breakdown Spectroscopy (LIBS) method and a Mass Spectrometer (MS). The LIBS laser ablates a sample and creates a plasma cloud, generating a pit in the sample. The LIBS plasma is measured for K abundance in weight percent and the released gas is measured using the MS, which calculates Ar abundance in mols. To relate the K and Ar measurements, total mass of the ablated sample is needed but can be difficult to directly measure. Instead, density and volume are used to calculate mass, where density is calculated based on the elemental composition of the rock (from the emission spectrum) and volume is determined by pit morphology. This study aims to reduce the uncertainty for KArLE by analyzing pit volume relationships in several analog materials and comparing methods of pit volume measurements and their associated uncertainties.

French, R. A.↗

Single photon infrared emission spectroscopy: a study of IR emission from UV laser excited PAHs between 3 and 15 micrometers

Single-photon infrared emission spectroscopy (SPIRES) has been used to measure emission spectra from polycyclic aromatic hydrocarbons (PAHs). A supersonic free-jet expansion has been used to provide emission spectra of rotationally cold and vibrationally excited naphthalene and benzene. Under these conditions, the observed width of the 3.3-micrometers (C-H stretch) band resembles the bandwidths observed in experiments in which emission is observed from naphthalene with higher rotational energy. To obtain complete coverage of IR wavelengths relevant to the unidentified infrared bands (UIRs), UV laser-induced desorption was used to generate gas-phase highly excited PAHs. Lorentzian band shapes were convoluted with the monochromator-slit function in order to determine the widths of PAH emission bands under astrophysically relevant conditions. Bandwidths were also extracted from bands consisting of multiple normal modes blended together. These parameters are grouped according to the functional groups mostly involved in the vibration, and mean bandwidths are obtained. These bandwidths are larger than the widths of the corresponding UIR bands. However, when the comparison is limited to the largest PAHs studied, the bandwidths are slightly smaller than the corresponding UIR bands. These parameters can be used to model emission spectra from PAH cations and cations of larger PAHs, which are better candidate carriers of the UIRs.

Non-NASA Center↗

Laer-induced Breakdown Spectroscopy Instrument for Element Analysis of Planetary Surfaces

One of the most fundamental pieces of information about any planetary body is the elemental and mineralogical composition of its surface materials. We are developing an instrument to obtain such data at ranges of up to several hundreds of meters using the technique of Laser-Induced Breakdown Spectroscopy (LIBS). We envision our instrument being used from a spacecraft in close rendezvous with small bodies such as comets and asteroids, or deployed on surface-rover vehicles on large bodies such as Mars and the Moon. The elemental analysis is based on atomic emission spectroscopy of a laser-induced plasma or spark. A pulsed, diode pumped Nd:YAG laser of several hundred millijoules optical energy is used to vaporize and electronically excite the constituent elements of a rock surface remotely located from the laser. Light emitted from the excited plasma is collected and introduced to the entrance slit of a small grating spectrometer. The spectrally dispersed spark light is detected with either a linear photo diode array or area CCD array. When the latter detector is used, the optical and spectrometer components of the LIBS instrument can also be used in a passive imaging mode to collect and integrate reflected sunlight from the same rock surface. Absorption spectral analysis of this reflected light gives mineralogical information that provides a remote geochemical characterization of the rock surface. We performed laboratory calibrations in air and in vacuum on standard rock powders to quantify the LIBS analysis. We performed preliminary field tests using commercially available components to demonstrate remote LIBS analysis of terrestrial rock surfaces at ranges of over 25 m, and we have demonstrated compatibility with a six-wheeled Russian robotic rover vehicle. Based on these results, we believe that all major and most minor elements expected on planetary surfaces can be measured with absolute accuracy of 10-15 percent and much higher relative accuracy. We have performed preliminary systems analysis of a LIBS instrument to evaluate probable mass and power requirements; results of this analysis are summarized.

Blacic, J.↗

High resolution infrared spectroscopy of planetary molecules using diode lasers and Fourier transform spectrometers

Modern observations of infrared molecular lines in planets are performed at spectral resolutions which are as high as those available in the laboratory. Analysis of such data requires laboratory measurements at the highest possible resolution, which also yield accurate line positions and intensities. For planetary purposes the spectrometer must be coupled to sample cells which can be reduced in temperature and varied in pressure. An approach which produces the full range of required molecular line parameters uses a combination of tunable diode lasers and Fourier transform spectrometers (FTS). The FTS provides board spectral coverage and good calibration accuracy, while the diode laser can be used to study those regions which are not resolved by the FTS.

Jennings, Donald E.↗

Elemental mass spectroscopy of remote surfaces from laser-induced plasmas

The elemental mass analysis of laser-produced ions from Al, Cu, Ge, Ag, and a lunar simulant target when irradiated by a 400-mJ, 8-ns, Nd: YAG laser at 1 x 10(exp 9) W/cm(exp 2), is reported. Ions traveled down a 11.1-m evacuated tube to an ion-trap 1-m time-of-flight (TOF) mass spectrometer where an elemental mass spectrum was recorded. The amount of target material removed per laser pulse and the ionization fraction were measured. The ion spatial distribution was measured at 11.1-m distance and found to be near a fourth-power cosine distribution. These results indicate the ability to mass analyze a surface over a distance of many kilometers for lunar and asteroid surface elemental mass analysis by a remote satellite or lunar rover.

Situ, W.↗