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36 records · Page 2

Chemical kinetic studies of atmospheric reactions using tunable diode laser spectroscopy

IR absorption using tunable diode laser spectroscopy provides a sensitive and quantitative detection method for laboratory kinetic studies of atmospheric trace gases. Improvements in multipass cell design, real time signal processing, and computer controlled data acquisition and analysis have extended the applicability of the technique. We have developed several optical systems using off-axis resonator mirror designs which maximize path length while minimizing both the sample volume and the interference fringes inherent in conventional 'White' cells. Computerized signal processing using rapid scan (300 kHz), sweep integration with 100 percent duty cycle allows substantial noise reduction while retaining the advantages of using direct absorption for absolute absorbance measurements and simultaneous detection of multiple species. Peak heights and areas are determined by curve fitting using nonlinear least square methods. We have applied these techniques to measurements of: (1) heterogeneous uptake chemistry of atmospheric trace gases (HCl, H2O2, and N2O5) on aqueous and sulfuric acid droplets; (2) vapor pressure measurements of nitric acid and water over prototypical stratospheric aerosol (nitric acid trihydrate) surfaces; and (3) discharge flow tube kinetic studies of the HO2 radical using isotopic labeling for product channel and mechanistic analysis. Results from each of these areas demonstrate the versatility of TDL absorption spectroscopy for atmospheric chemistry applications.

Worsnop, Douglas R.↗

Local fluctuations of ozone from 16 km to 45 km deduced from in situ vertical ozone profile

A vertical ozone profile obtained by an in situ ozone sonde from 16 km to 45 km, has allowed to observe local ozone concentration variations. These variations can be observed, thanks to a fast measurement system based on a UV absorption KrF excimer laser beam in a multipass cell. Ozone standard deviation versus altitude calculated from the mean is derived. Ozone variations or fluctuations are correlated with the different dynamic zones of the stratosphere.

Moreau, G.↗

FTIR studies of low temperature sulfuric acid aerosols

Sub-micrometer sized sulfuric acid H2SO4 particles were generated using a constant output atomizer source. The particles were then exposed to water vapor before being injected into a low temperature cell. Multipass transmission Fourier Transformation Infrared (FTIR) spectroscopy was used to determine the phase and composition of the aerosols as a function of time for periods of up to five hours. Binary H2SO4H2O aerosols with compositions from 35 to 95 wt % H2SO4 remained liquid for over 3 hours at room temperatures ranging from 189-240 K. These results suggest that it is very difficut to freeze SSAs via homogeneous nucleation. Attempts to form aerosols more dilute than 35 wt % H2SO4 resulted in ice formation.

Anthony, S. E.↗

Effective utilization of quantum-cascade distributed-feedback lasers in absorption spectroscopy

A variable duty cycle quasi-cw frequency scanning technique was applied to reduce thermal effects resulting from the high heat dissipation of type I quantum-cascade lasers. This technique was combined with a 100-m path-length multipass cell and a zero-air background-subtraction technique to enhance detection sensitivity to a parts-in-10(9) (ppb) concentration level for spectroscopic trace-gas detection of CH4, N2O, H2O, and C2H5OH in ambient air at 7.9 micrometers. A new technique for analysis of dense high resolution absorption spectra was applied to detection of ethanol in ambient air, yielding a 125-ppb detection limit.

NASA Discipline Environmental Health↗

Compact CH4 sensor based on difference frequency mixing of diode lasers in quasi-phasematched LiNbO3

A compact, portable and robust room temperature CH4 sensor is reported. By difference frequency mixing a 500 mW alpha-DFB diode laser at 1066 nm and an erbium-doped fiber amplified 1574 nm DFB diode laser in periodically poled lithium niobate up to 7 (mu)W of narrowband radiation at 3.3 microns is generated. Real-time monitoring of CH4 over a 7 day period using direct absorption in an open-path multipass cell (L = 36 m) demonstrates a detection precision of +/- 14 ppb.

NASA Discipline Environmental Health↗

High-power continuous-wave mid-infrared radiation generated by difference frequency mixing of diode-laser-seeded fiber amplifiers and its application to dual-beam spectroscopy

We report the generation of up to 0.7 mW of narrow-linewidth (<60-MHz) radiation at 3.3 micrometers by difference frequency mixing of a Nd:YAG-seeded 1.6-W Yb fiber amplifier and a 1.5-micrometers diode-laser-seeded 0.6-W Er/Yb fiber amplifier in periodically poled LiNbO3. A conversion efficiency of 0.09%/W (0.47 mWW-2 cm-1) was achieved. A room-air CH4 spectrum acquired with a compact 80-m multipass cell and a dual-beam spectroscopic configuration indicates an absorption sensitivity of +/-2.8 x 10(-5) (+/-1 sigma), corresponding to a sub-parts-in-10(9) (ppb) CH4 sensitivity (0.8 ppb).

Non-NASA Center↗

Portable Multigas Monitors for International Space Station

The Environmental Health System (EHS) on International Space Station (ISS) includes portable instruments to measure various cabin gases that acutely impact crew health. These hand-held devices measure oxygen, carbon dioxide, carbon monoxide, hydrogen chloride and hydrogen cyanide. The oxygen and carbon dioxide units also serve to back up key functions of the Major Constituent Analyzers. Wherever possible, commercial off-the-shelf (COTS) devices are employed by EHS to save development and sustaining costs. COTS hardware designed for general terrestrial applications however has limitations such as no pressure compensation, limited life of the active sensor, calibration drift, battery issues, unpredictable vendor support and obsolescence. The EHS fleet (inflight and ground inventory) of instruments is both aging and dwindling in number. With the retirement of the US Space Shuttle, maintenance of on-orbit equipment becomes all the more difficult. A project is underway to search for gas monitoring technology that is highly reliable and stable for years. Tunable Diode Laser Spectroscopy (TDLS) seems to be the front-runner technology, but generally is not yet commercially available in portable form. NASA has fostered the development of TDLS through the Small Business Innovative Research (SBIR) program. A number of gases of interest to the aerospace and submarine communities can be addressed by TDLS including the list mentioned above plus hydrogen fluoride, ammonia and water (humidity). There are several different forms of TDLS including photoacoustic and direct absorption spectroscopy using various multipass cell geometries. This paper describes the history of portable gas monitoring on NASA spacecraft and provides a status of the development of TDLS based instruments. Planned TDLS flight experiments on ISS could lead both to operational use on ISS and important roles in future Exploration spacecraft and habitats.

Mudgett, Paul D.↗

Intensities and N2 collision-broadening coefficients measured for selected H2O absorption lines between 715 and 732 nm

Intensities and N2 collision-broadening coefficients are measured for 62 water vapor absorption lines between 715 and 732 nm potentially applicable to laser remote sensing of atmospheric water vapor. Absolute line strengths and widths were determined from spectra corrected for instrument resolution, air-path absorption and Lorentz and Doppler broadening for pure water vapor and water vapor-nitrogen mixtures in a multipass absorption cell with a base path length of 25 m (White cell). Line strengths are observed to range from 4 x 10 to the -25th to 4 x 10 to the -23rd kayser/molecule per sq cm, and collision broadening coefficients are found to be approximately equal to 0.1 kayser/atm.

Wilkerson, T. D.↗

Airborne water vapor DIAL system development

A differential absorption lidar (DIAL) system developed at NASA Langley Research Center for the remote measurement of atmospheric H2O and aerosols from an aircraft is briefly discussed. This DIAL system utilizes a Nd:YAG laser-pumped dye laser as the off-line transmitter and a narrowband, tunable Alexandrite laser as the on-line transmitter. A 1-m monochromator and a multipass absorption cell are used to position the on-line laser to the center of the H2O line. The receiver system has a 14-in. diameter, f/7 Celestron telescope to collect the backscattered laser light and focus in into the detector optics. Return signals are converted to electrical signals by the optical detector and are digitalized and stored on magnetic tape. The results of fligh tests of the system are shown.

Higdon, Noah S.↗

Open-path tunable diode laser absorption for eddy correlation flux measurements of atmospheric trace gases

Biogenic emissions from and dry deposition to terrestrial surfaces are important processes determining the trace gas composition of the atmosphere. An instrument has been developed for flux measurements of gases such as CH4, N2O, and O3 based on the eddy correlation technique which combines trace gas fluctuation measurements with simultaneous windfield measurements. The instrument combines a tunable diode laser infrared light source with an open-path multipass absorption cell in order to provide the fast time response and short base pathlength required for the eddy correlation method. Initial field tests using the instrument to measure methane emissions from a local wetland demonstrate the capability for high precision eddy correlation flux measurements.

Anderson, Stuart M.↗

Differential absorption lidar measurements of atmospheric water vapor using a pseudonoise code modulated AlGaAs laser

Lidar measurements using pseudonoise code modulated AlGaAs lasers are reported. Horizontal path lidar measurements were made at night to terrestrial targets at ranges of 5 and 13 km with 35 mW of average power and integration times of one second. Cloud and aerosol lidar measurements were made to thin cirrus clouds at 13 km altitude with Rayleigh (molecular) backscatter evident up to 9 km. Average transmitter power was 35 mW and measurement integration time was 20 minutes. An AlGaAs laser was used to characterize spectral properties of water vapor absorption lines at 811.617, 816.024, and 815.769 nm in a multipass absorption cell using derivative spectroscopy techniques. Frequency locking of an AlGaAs laser to a water vapor absorption line was achieved with a laser center frequency stability measured to better than one-fifth of the water vapor Doppler linewidth over several minutes. Differential absorption lidar measurements of atmospheric water vapor were made in both integrated path and range-resolved modes using an externally modulated AlGaAs laser. Mean water vapor number density was estimated from both integrated path and range-resolved DIAL measurements and agreed with measured humidity values to within 6.5 percent and 20 percent, respectively. Error sources were identified and their effects on estimates of water vapor number density calculated.

Rall, Jonathan A. R.↗

Airborne Measurements of Formaldehyde Employing a Tunable Diode Laser Absorption Spectrometer During TRACE-P

This final report summarizes the progress achieved over the entire 3-year proposal period including two extensions spanning 1 year. These activities include: 1) Preparation for and participation in the NASA 2001 TRACE-P campaign using our airborne tunable diode laser system to acquire measurements of formaldehyde (CH2O); 2) Comprehensive data analysis and data submittal to the NASA archive; 3) Follow up data interpretation working with NASA modelers to place our ambient CH2O measurements into a broader photochemical context; 4) Publication of numerous JGR papers using this data; 5) Extensive follow up laboratory tests on the selectivity and efficiency of our CH20 scrubbing system; and 6) An extensive follow up effort to assess and study the mechanical stability of our entire optical system, particularly the multipass absorption cell, with aircraft changes in cabin pressure.

Fried, Alan↗

Multilaser Herriott Cell for Planetary Tunable Laser Spectrometers

Geometric optics and matrix methods are used to mathematically model multilaser Herriott cells for tunable laser absorption spectrometers for planetary missions. The Herriott cells presented accommodate several laser sources that follow independent optical paths but probe a single gas cell. Strategically placed output holes located in the far mirrors of the Herriott cells reduce the size of the spectrometers. A four-channel Herriott cell configuration is presented for the specific application as the sample cell of the tunable laser spectrometer instrument selected for the sample analysis at Mars analytical suite on the 2009 Mars Science Laboratory mission.

continuous-wave↗

In situ detection of tropospheric OH and HO2 by laser-induced fluorescence in a detection chamber at low pressure

Just as in the method of Hard and O'Brien, ambient air is pulled through an approximately 1 mm diameter inlet into a detection chamber that is maintained at a pressure of 2.4 torr. The ambient air stream travels through the detection chamber with a velocity of greater than 100 m sec(exp -1) in a narrow stream, constrained by the addition of an inert gas flow (0.4 torr). The OH molecule is both excited and detected in the A(exp 2)Sigma (v' = 0) yields X(exp 2)II (v'' = 0) transition at 308 nm. Light from a copper vapor-pumped dye laser (rep. rate = 10kHz; pulse length = 20 ns; linewidth = .1 cm(exp -1), and average power = 15 mW), resonant with the Q(sub 1)(3) transition, is multipassed through a White cell and intercepts the air stream as 24 non-overlapping 2mm by 5mm beams. A fast microchannel plate detector is turned off during the laser pulse to prevent saturation of the detector due to Rayleigh and chamber scattering. It is turned on 30-100 nsec after the end of the laser pulse for 300 ns to collect resonance fluorescence from OH. HO2 is detected by chemical conversion to OH by reaction with reagent NO, followed by OH detection. Both the detection sensitivity and the inlet characteristics must be understood for any in situ instrument. For the calibration of the detection sensitivity, OH is produced quantitatively by the fast H + NO2 yields OH + NO reaction in a low pressure, flowing discharge tube connected to the detection chamber. The inlet transmission of OH inlet is calibrated separately.

Brune, William H.↗

Laboratory studies of low temperature rate coefficients: The atmospheric chemistry of the outer planets

The objectives of the research are to measure low temperature laboratory rate coefficients for key reactions relevant to the atmospheres of Titan and Saturn. These reactions are, for example, C2H + H2, CH4, C2H2, and other hydrocarbons which need to be measured at low temperatures, down to approximately 150 K. The results of this work are provided to NASA specialists who study modeling of the hydrocarbon chemistry of the outer planets. The apparatus for this work consists of a pulsed laser photolysis system and a tunable F-center probe laser to monitor the disappearance of C2H. A low temperature cell with a cryogenic circulating fluid in the outer jacket provides the gas handling system for this work. These elements have been described in detail in previous reports. Several new results are completed and the publications are just being prepared. The reaction of C2H with C2H2 has been measured with an improved apparatus down to 154 K. An Arrhenius plot indicates a clear increase in the rate coefficient at the lowest temperatures, most likely because of the long-lived (C4H3) intermediate. The capability to achieve the lowest temperatures in this work was made possible by construction of a new cell and addition of a multipass arrangement for the probe laser, as well as improvements to the laser system.

Leone, Stephen R.↗

Development of a Platform for High-Resolution Ion Mobility Separations Coupled with Messenger Tagging Infrared Spectroscopy for High-Precision Structural Characterizations

The ability to uniquely identify a compound requires highly precise and orthogonal measurements. Here we describe a newly developed analytical platform that integrates high resolution ion mobility and cryogenic vibrational ion spectroscopy for high-precision structural characterizations. This platform allows for the temporal separation of isomeric/isobaric ions and provides a highly sensitive description of the ion’s adopted geometry in the gas phase. The combination of these orthogonal structural measurements yields precise descriptors that can be used to resolve between and confidently identify highly similar ions. The unique benefits of our instrument, which integrates a structures for lossless ion manipulations ion mobility (SLIM IM) device with messenger tagging infrared spectroscopy, include the ability to perform high-resolution ion mobility separations and to record the IR spectra of all ions simultaneously. The SLIM IM device, with its 13 m separation path length, allows for multipass experiments to be performed for increased resolution as needed. It is integrated with an Agilent qTOF MS where the collision cell was replaced with a cryogenically held (30 K) TW-SLIM module. The cryo-SLIM is operated in a novel manner that allows ions to be streamed through the device and collisionally cooled to a temperature where they can form noncovalently bound N 2 complexes that are maintained as they exit the device and are detected by the TOF mass analyzer. The instrument can be operated in two modes: IMS+IR where the IR spectra for mobility-selected ions can be recorded and IR-only mode where the IR spectra for all mass-resolved ions can be recorded. In IR-only mode, IR spectra (400 cm –1 spectral range) can be recorded in as short as 2 s for high throughput measurements. Further, this work details the construction of the instrument and modes of operation. It provides initial benchmarking of CCS and IR measurements to demonstrate the utility of this instrument for targeted and untargeted approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fiber-Coupled Multipass NIR Sensor for In Situ, Real-Time Water Vapor Outgassing Monitoring

This work presents the recent development of a fiber-coupled multipass near-infrared (NIR) gas sensor used to monitor water vapor desorption of small material coupons. The gas sensor design employs a White cell topology to maximize the optical path length over a compact, hand-size footprint. Water vapor concentrations are quantified over a large dynamic range by simultaneously applying wavelength modulation and tunable diode laser absorption spectroscopy techniques. A custom headspace optimized for material desorption experiments is assembled using commercially available vacuum chamber components. We provide in situ measurements of water vapor desorption from two geometries of the industrially important silicone elastomer Sylgard-184 as a case study for sensor viability. To corroborate the results, the gas sensor data are compared to numerical simulations based on a triple-mode diffusion–sorption model, consisting of Henry, Langmuir, and Pooling modes.

gas sensor↗

Seamless Nb tubes for SRF cavities

A. Executive Summary Understanding Developed Relationships between level of work, plastic strain orientation, level of annealing, grain size, strength, ductility, and texture were developed for heavily worked bulk RRR grade cast pure niobium (Nb). Technical Effectiveness of Approach Part A: The approach used for plastic deformation of bulk Nb was room temperature equal channel angular extrusion (ECAE). This approach is very effective for microstructural breakdown of worked and post-strain recrystallized Nb. A major problem with breaking down the microstructure of cast Nb is development of a consistent (repeatable) and uniform microstructure. This is most effectively accomplished by a series of orthogonal working steps (multipass ECAE (mECAE)) separated by full recrystallization. Forming tube from such material leads to a uniform microstructure in the tube. Part B: The approach developed to produce a microstructure in thin-walled tube that is very favorable for hydroforming into a superconducting radio frequency (SRF) cavity is tube-ECAE (tECAE). Tube-ECAE results in an axisymmetric circumferentially uniform microstructure with a texture more favorable for expansion hydroforming than tube formed by conventional methods such as extrusion, drawing, and ironing. Economic Feasibility of Methods Investigated and Demonstrated Although this was not demonstrated because of funding limitations, it is strongly believed that mECAE combined with intermediate recrystallization heat treatments and tECAE are economically viable approaches for producing a consistent, uniform, fine- or coarse-grained microstructure in RRR grade Nb tube starting from a large-grained and highly textured cast ingot. These methods are relatively easy to apply; the challenge is development of equipment and tooling that works well and is operator friendly. Commercially viable ECAE tooling for bulk Nb microstructure breakdown was developed; significant progress was made on the design of scaled-up equipment for tECAE. Patents on tECAE have been granted in Europe, Japan, and the United States. Public Benefit The approaches developed for fabricating RRR grade Nb tubing suitable for hydroforming into multi-cell SRF cavities have substantial public benefit because they will enable the manufacture of lower cost multicell SRF cavities for advanced linear particle accelerators. In addition, the approach developed for fabricating uniform and consistent axisymmetric microstructures in metal tubing can be applied to tubes made of metal alloys other than Nb. Applications exist in Ta tubing for superconductor wire applications, Mg alloy tubing for bio-implants, and aerospace tubing for structural hollow section components. The idea of tECAE can be applied to heal the heat affected zone (HAZ) in seam-welded tubing, thus erasing or healing the low-strength properties in the weld zone.

36 MATERIALS SCIENCE↗