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At least 1,513 records · Page 84

A Review of LIBS for Real-Time Detection of Trace Silicone Contaminants on CFRP Surfaces

Laser ablation is the removal of material by laser pulses through photochemical, photothermal, or photophysical mechanisms, which is useful to prepare an adherend surface for adhesive bonding. Laser surface treatment is a method that has been under research for the past decade at NASA Langley Research Center (LaRC) to prepare surfaces for adhesive joining of aerospace composite materials and metallic alloys. Laser ablation of composite materials increases surface area and removes the surface contaminants introduced during material handling and fabrication processes. By adjustment of laser parameters, it is possible to obtain repeatable surface conditions, and superficial contaminants can be selectively and efficiently removed without damaging the underlying carbon fibers or the carbon fiber reinforced polymer (CFRP) substrate. Laser induced breakdown spectroscopy (LIBS) is a surface characterization and inspection technique that can be seamlessly integrated into the laser surface treatment process. At NASA LaRC, a single laser system has been used for both laser surface treatment and LIBS, which enables in-situ monitoring of surface contaminants. This work focuses on the advancements at LaRC using LIBS to detect surface silicone contaminants on aerospace CFRP materials and to provide surface quality control in adhesive bonding.

Rodolfo I Ledesma↗

A Review of LIBS for Real-Time Detection of Trace Silicone Contaminants on CFRP Surfaces

Laser ablation is the removal of material by laser pulses through photochemical, photothermal, or photophysical mechanisms, which is useful to prepare an adherend surface for adhesive bonding. Laser surface treatment is a method that has been under research for the past decade at NASA Langley Research Center (LaRC) to prepare surfaces for adhesive joining of aerospace composite materials and metallic alloys. Laser ablation of composite materials increases surface area and removes the surface contaminants introduced during material handling and fabrication processes. By adjustment of laser parameters, it is possible to obtain repeatable surface conditions, and superficial contaminants can be selectively and efficiently removed without damaging the underlying carbon fibers or the carbon fiber reinforced polymer (CFRP) substrate. Laser induced breakdown spectroscopy (LIBS) is a surface characterization and inspection technique that can be seamlessly integrated into the laser surface treatment process. At NASA LaRC, a single laser system has been used for both laser surface treatment and LIBS, which enables in-situ monitoring of surface contaminants. This work focuses on the advancements at LaRC using LIBS to detect surface silicone contaminants on aerospace CFRP materials and to provide surface quality control in adhesive bonding.

Rodolfo I Ledesma↗

Methods for multiphase laser ablation analysis

Methods of liquid and solid materials analysis by laser induced ablation spectroscopy are disclosed. The liquid and solid materials are analyzed in an instrument having one pulsed laser to produce emissive plasma plumes and ablate solid material. Liquid phase samples are aerosolized before streaming to an analysis zone where they are dissociated into a plasma plume. A large number of sites within solid phase sample structures and be analyzed using a movable x-y-z stage and displayed in a chemical map.

Bol'shakov, Alexander A.↗

Doppler optical mixing spectroscopy in multiparticle scattering fluids

We discuss the basic scheme of laser Doppler optical mixing spectroscopy for the analysis of media with multiparticle scattering. It is shown that the Rayleigh scheme, in contrast to the heterodyne and differential schemes, is insensitive to the effects of multiparticle scattering. (laser applications and other aspects of quantum electronics)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Carrier-specific dynamics in 2H-MoTe2 observed by femtosecond soft x-ray absorption spectroscopy using an x-ray free-electron laser

Femtosecond carrier dynamics in layered 2H-MoTe2 semiconductor crystals have been investigated using soft x-ray transient absorption spectroscopy at the x-ray free-electron laser (XFEL) of the Pohang Accelerator Laboratory. Following above-bandgap optical excitation of 2H-MoTe2, the photoexcited hole distribution is directly probed via short-lived transitions from the Te 3d5/2 core level (M5-edge, 572–577 eV) to transiently unoccupied states in the valence band. The optically excited electrons are separately probed via the reduced absorption probability at the Te M5-edge involving partially occupied states of the conduction band. A 400 ± 110 fs delay is observed between this transient electron signal near the conduction band minimum compared to higher-lying states within the conduction band, which we assign to hot electron relaxation. Additionally, the transient absorption signals below and above the Te M5 edge, assigned to photoexcited holes and electrons, respectively, are observed to decay concomitantly on a 1–2 ps timescale, which is interpreted as electron–hole recombination. The present work provides a benchmark for applications of XFELs for soft x-ray absorption studies of carrier-specific dynamics in semiconductors, and future opportunities enabled by this method are discussed.

2D materials↗

Protocols for x-ray transient grating pump/optical probe experiments at x-ray free electron lasers

Abstract Transient grating spectroscopy is a specialized application of the four-wave-mixing methodology and constitutes a versatile technique for investigating the dynamics of vibrational, magnetic and electronic degrees of freedom of matter in a background-free fashion. Recent developments in free-electron laser sources have enabled the extension of this technique into the extreme ultraviolet range. Ongoing efforts to expand transient grating spectroscopy into the x-ray regime promise numerous advantages: (1) substantial penetration depths that allow for probing bulk material properties, (2) element specificity via specific core-excited states, and (3) short wavelengths that allow for excitation gratings with higher momentum transfer and improved spatial resolution. In this study, we comprehensively outline the procedures for conducting x-ray transient grating pump/optical probe experiment. The process encompasses the design and alignment of the experimental setup, as well as the subsequent steps involved in data acquisition and analysis. This paper is intended as a comprehensive guide for researchers interested in implementing x-ray transient grating spectroscopy, providing valuable insights into the intricacies of the experimental workflow required for this novel technique. Furthermore, we discuss the potential for extending this methodology to an x-ray pump/x-ray probe scheme, envisioning a future direction that holds promise for enhancing the capabilities and scope of x-ray transient grating spectroscopy, opening new opportunities for studying ultrafast processes with unprecedented temporal and spatial resolutions.

Optics↗

High-speed assembly language (80386/80387) programming for laser spectra scan control and data acquisition providing improved resolution water vapor spectroscopy

An assembly language program using the Intel 80386 CPU and 80387 math co-processor chips was written to increase the speed of data gathering and processing, and provide control of a scanning CW ring dye laser system. This laser system is used in high resolution (better than 0.001 cm-1) water vapor spectroscopy experiments. Laser beam power is sensed at the input and output of white cells and the output of a Fabry-Perot. The assembly language subroutine is called from Basic, acquires the data and performs various calculations at rates greater than 150 faster than could be performed by the higher level language. The width of output control pulses generated in assembly language are 3 to 4 microsecs as compared to 2 to 3.7 millisecs for those generated in Basic (about 500 to 1000 times faster). Included are a block diagram and brief description of the spectroscopy experiment, a flow diagram of the Basic and assembly language programs, listing of the programs, scope photographs of the computer generated 5-volt pulses used for control and timing analysis, and representative water spectrum curves obtained using these programs.

Allen, Robert J.↗

Implementing an electronic sideband offset lock for isotope shift spectroscopy in radium

We demonstrate laser frequency stabilization with at least 6 GHz of offset tunability using an in-phase/quadrature (IQ) modulator to generate electronic sidebands (ESB) on a titanium sapphire laser at 714 nm and we apply this technique to perform isotope shift spectroscopy of 226 Ra and 225 Ra. By locking the laser to a single resonance of a high finesse optical cavity and adjusting the lock offset, we determine the frequency difference between the magneto-optical trap (MOT) transitions in the two isotopes to be 2630.0 ± 0.3 MHz, a factor of 29 more precise than the previously available data. Using the known value of the hyperfine splitting of the 3 P 1 level, we calculate the isotope shift for the 1 S 0 to 3 P 1 transition to be 2267.0 ± 2.2 MHz, a factor of 8 more precise than the best available value. Our technique could be applied to countless other atomic systems to provide unprecedented precision in isotope shift spectroscopy and other relative frequency comparisons.

47 OTHER INSTRUMENTATION↗

Wavelength modulation laser-induced fluorescence for plasma characterization

Laser-Induced Fluorescence (LIF) spectroscopy is an essential tool for probing ion and atom velocity distribution functions (VDFs) in complex plasmas. VDFs carry information about the kinetic properties of species that is critical for plasma characterization. Accurate interpretation of these functions is challenging due to factors such as multicomponent distributions, broadening effects, and background emissions. Our research investigates the use of Wavelength Modulation (WM) LIF to enhance the sensitivity of VDF measurements. Unlike standard Amplitude Modulation (AM) methods, WM–LIF measures the derivative of the LIF signal. This approach makes variations in VDF shape more pronounced. VDF measurements with WM–LIF were investigated with both numerical modeling and experimental measurements. The developed model enables the generation of both WM and AM signals, facilitating comparative analysis of fitting outcomes. Experiments were conducted in a weakly collisional argon plasma with magnetized electrons and non-magnetized ions. Measurements of the argon ion VDFs employed a narrow-band tunable diode laser, which scanned the 4p 4 D 7/2 –3d 4 F 9/2 transition centered at 664.553 nm in vacuum. A lock-in amplifier detected the second harmonic WM signal, which was generated by modulating the laser wavelength with an externally controlled piezo-driven mirror of the diode laser. Finally, our findings indicate that the WM–LIF signal is more sensitive to fitting parameters, allowing for better identification of VDF parameters such as the number of distribution components, their temperatures, and velocities. In addition, WM–LIF can serve as an independent method to verify AM measurements and is particularly beneficial in environments with substantial light noise or background emissions, such as those involving thermionic cathodes and reflective surfaces.

47 OTHER INSTRUMENTATION↗

Laser-Induced Plasmas of Plutonium Dioxide in a Double-Walled Cell

Plutonium research has been stifled by the significant number of administrative controls and safety procedures, space and instrumentation limitations in radiological gloveboxes, and the potential for personnel and equipment contamination. To address the limited number of spectroscopic studies in Pu-bearing compounds in the current scientific literature, this work presents the use of double-walled cells (DWCs) in “clean” buildings/laboratories as an alternative to research in radiological gloveboxes. This study reports the first laser-induced breakdown spectroscopy (LIBS) experiments of a PuO 2 pellet contained within a DWC, where the formation of elemental (atomic and ionic) species as well as the evolution from elemental to molecular products (Pu x O y ) was measured. Raman spectroscopy was also used to characterize the surface of the ablated pellet and the particulates deposited on the window of the inner cell. The full width half-maximum of the T 2g band enabled us to obtain an estimate of the temperature at the pellet surface after the ablation pulse and the particulates based on the crystal lattice disorder. Particulates deposited on the window of the DWC during laser ablation were characterized using scanning electron microscopy, where molten irregular particulates and spheroids were observed. This exciting research conducted in a DWC describes our initial attempts to incorporate LIBS in the arsenal of spectroscopic tools for nuclear forensics applications.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The effect on soot and its gas precursors of doping ethylene with 2,2,4,6,6-pentamethyl-heptane in the nitrogen-fuel stream of a laminar non-premixed Planar Mixing Layer Flame (PMLF)

Synthetic Aviation Turbine Fuels (SATFs) are promising for reducing soot emissions from the aviation sector and diversifying Jet Fuel (JF) sources. Accurately predicting the combustion and emissions behavior of SATFs (and other JFs) necessitates robust experimental databases to elucidate the chemistry of long-chain iso-paraffins, which can compose up to two-thirds of SATF blends and whose behavior is considered to be well-represented by that of iso-dodecane isomers. Here, this study characterizes two laminar non-premixed Planar Mixing Layer Flames (PMLFs) with mild soot loads fueled by nitrogen-diluted ethylene, pure and doped with 2,2,4,6,6-pentamethyl-heptane, respectively. The two PMLFs have the same stoichiometric mixture fraction and total hydrocarbon mole fraction in the fuel stream (X F,F =X C2H4,F +X C12H26,F = 0.260), resulting in nearly the same maximum temperature (T max ≈1800 K) and simple identification of the effects of doping. Importantly, any horizontal PMLF cross-section has a self-similar structure that can be modeled as an equivalent One-Dimensional Counterflow Flame (1D-CF) with vanishingly small strain rate (a). The cross-section at a Height Above the Burner (HAB) of 50 mm is characterized in terms of C 0 -C 18 gas species using capillary sampling followed by GC-MS analyses. Laser-Induced Emission Spectroscopy (LIES) quantifies the soot volume fraction (ƒ v ) profiles at HAB=25 and 50 mm where Elastic Laser Light Scattering (E-LLS) is performed to determine the a of the equivalent 1D-CFs and the profile of the E-LLS equivalent diameter ( d 6,3 ) of soot. The substitution of 1500 ppm of ethylene with 2,2,4,6,6-pentamethyl-heptane causes an increase of ≈1.5 in the concentrations of several polycyclic aromatic hydrocarbons and fv. Concurrently, the measured d 6,3 doubles in the oxidizer stream, yet remains the same in the fuel stream, at HAB=50 mm. Instead, at HAB= 25 mm, the iso-dodecane doping does not affect the d 6,3 profile in either stream. The experimental results partially validate the chemical reactions and soot formation kinetic model developed at Lawrence Livermore National Laboratory and provide directions to further improve its predictions.

Iso-dodecane (2,2,4,6,6-Pentamethyl-Heptane)↗

On the Hunt for Detectable Biosignatures in Jezero Crater: What to Look for and Where

Introduction: The Perseverance rover, which is currently exploring Jezero crater on Mars, is equipped with seven instruments that allow for observation of textures, minerals, color, structure, and chemistry of rocks and sediments in order to search for signs of ancient life, understand the geologic history of the crater, and identify candidates for sample return (Farley et al. 2020). The first of these aims includes the direct detection of potential biosignatures, including textures, organic molecules, minerals, and elemental chemistries that are of biogenic origin (Mustard et al. 2013). The presence of these biosignatures will be constrained by the habitability of the local region, the preservation potential of the host rocks, and the sensitivity of the instrument suite, and their biogenicity will be investigated after return to Earth as part of the Mars Sample Return campaign. Here, we examine key targets on the three planned campaigns, potential biosignatures that may be present, and the capabilities of key rover instruments. High Potential Biosignature Sites in Jezero: To date, measurements have been made on multiple sites that both contain minerals known in terrestrial settings to preserve biosignatures and likely were habitable settings (Williford et al. 2021). Two examples include the fine-grained rocks at the base of the delta fan and the NW inner margin of the crater. Fine-grained Rocks at Base of Delta Fan. Fine-grained, clay-bearing rocks may have been deposited as muddy lake sediments that could have hosted life and preserved biosignatures settling out of the water column. The report of organic molecules by the Curiosity rover in the Sheepbed mudstone and Murray formation has highlighted this site in particular. Potential biosignatures in mudstones, especially those rich in silica (McMahon et al. 2018), microbialites and complex organics. NW Inner Margin of Crater. This unit, located along the inner margin of the crater, contains strong carbonate signatures and may have been the littoral zone of a lake (Horgan et al. 2020). The potential biosignatures here include microfossils, microbialites, biominerals, and complex organics. Detectability of Biosignatures by the Mars 2020 Instrument Suite: The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument comprises a Deep UV spectrometer, context imager, and color camera to generate spatially resolved chemical maps (Bhartia et al. 2020). It is sensitive to trace organics as well as a range of minerals and can detect native fluorescence from aromatic organics; the WATSON and ACI cameras can be used to observe morphologies such as stromatolitic laminations or filaments ranging from the tens of micron to millimeter scale. SHERLOC can detect organics that may be present in either of the high potential biosignature targets, as well as detect carbonates in the latter. However, the presence of high amounts of iron, such as in iron-rich clays, would cause attenuation of spectral response through UV absorption. The Planetary Instrument for X-ray Lithochemistry (PIXL) comprises an X-ray fluorescence spectrometer and camera that can scan rock surfaces to generate elemental maps (Allwood et al. 2020). PIXL can detect chemical biosignatures such as spatial variations of elemental abundances that may have resulted from biological activity. PIXL would be particularly useful in detecting fine textures and elemental chemistries in either high potential biosignature target, but cannot directly detect minerals such as carbonate. The SuperCam instrument performs three types of spectroscopy, color imaging, and acoustic recording to remotely examine elemental composition, minerals, organics, and textures (Maurice et al. 2021). Using laser induced breakdown spectroscopy and time resolved luminescence spectroscopy, SuperCam can detect major elemental building blocks of organics (i.e., C, H, N, O, P, S) and conjugated organic structures, respectively, which may be found in either site. While in other contexts, luminescence is a useful tool for biosignature identification, luminescence generated by the 532 nm laser may obscure the Raman signal. Conclusion: The three instruments discussed can be used collaboratively to establish the presence of potential biosignatures in samples. These high-priority samples may then be returned to Earth for detailed laboratory analysis.

S. Sharma↗

Time evolution studies of laser induced chemical changes in InAs nanowire using Raman spectroscopy

We report the study of time evolution of chemical changes on the surface of an InAs nanowire (NW) on laser irradiation in different power density regime, using Raman spectroscopy for a time span of 8–16 min. Mixture of metastable oxides like InAsO{sub 4,} As{sub 2}O{sub 3} are formed upon oxidation, which are reflected as sharp Raman peaks at ∼240–254 and 180–200 cm{sup −1}. Evidence of removal of arsenic layer by layer is also observed at higher power density. Position controlled laser induced chemical modification on a nanometer scale, without changing the core of the NW, can be useful for NW based device fabrication.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Electronically induced surface reactions: Evolution, concepts, and perspectives

This is a personal account of the development of the title subject which is the broader field encompassing surface photochemistry. It describes the early times when the main interest centered on desorption induced by slow electrons, follows its evolution in experiment (use of synchrotron radiation and connections to electron spectroscopies; use of lasers) and mechanisms, and briefly mentions the many different subfields that have evolved. It discusses some practically important aspects and applications and ends with an account of an evolving new subfield, the application to photochemistry on nanoparticles.

36 MATERIALS SCIENCE↗

Femtosecond time-resolved photoelectron spectroscopy with a vacuum-ultraviolet photon source based on laser high-order harmonic generation

A laser-based tabletop approach to femtosecond time-resolved photoelectron spectroscopy with photons in the vacuum-ultraviolet (VUV) energy range is described. The femtosecond VUV pulses are produced by high-order harmonic generation (HHG) of an amplified femtosecond Ti:sapphire laser system. Two generations of the same setup and results from photoelectron spectroscopy in the gas phase are discussed. In both generations, a toroidal grating monochromator was used to select one harmonic in the photon energy range of 20-30 eV. The first generation of the setup was used to perform photoelectron spectroscopy in the gas phase to determine the bandwidth of the source. We find that our HHG source has a bandwidth of 140 {+-} 40 meV. The second and current generation is optimized for femtosecond pump-probe photoelectron spectroscopy with high flux and a small spot size at the sample of the femtosecond probe pulses. The VUV radiation is focused into the interaction region with a toroidal mirror to a spot smaller than 100 x 100 {mu}m{sup 2} and the flux amounts to 10{sup 10} photons/s at the sample at a repetition rate of 1 kHz. The duration of the monochromatized VUV pulses is determined to be 120 fs resulting in an overall pump-probe time resolution of 135 {+-} 5 fs. We show how this setup can be used to map the transient valence electronic structure in molecular dissociation.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Optimization of LIBS Acquisition Parameters for Chemical Analysis on HLW Liquid Solution - 18291

Research programs are currently underway in the Joint CEA-AREVA Vitrification Laboratory (LCV) to develop and optimize Laser Induced Breakdown Spectroscopy (LIBS) for nuclear waste streams analyses. The laboratory has full scale prototypes with the advantage of working on simulated inactive solutions of fission products. LIBS is an elemental chemical analysis technology that uses a short laser pulse to create a micro-plasma on the sample surface. This analytical technique offers many advantages compared to other techniques. It includes a sample preparation-free measurement and an extremely fast measurement time, from a few seconds to a few minutes. This paper presents the LIBS technique available in the laboratory. The first LIBS analyzes results of liquid samples from the off-gas treatment unit integrated on the full scale vitrification process are also presented and discussed. These complex solutions contain suspended particles and up to 30 chemical elements. A vision of an online LIBS analysis cell is also proposed with the development and associated research steps. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of Robotic Multisensor Inspection System for Used Nuclear Fuel Canisters

Dry storage of used nuclear fuel is an integral part of the fuel cycle and methods to inspect the canisters that confine the used fuel rods are being established. The challenges for inspection systems include geometric constraints, elevated temperature, and radiation. A novel robotic inspection system focusing on stress corrosion cracking capable of in-situ surface composition characterization and crack detection is under development. The delivery system, laser induced breakdown spectroscopy for surface composition, and ultrasonic guided waves for crack detection are summarized herein. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Frequency stabilization of a 1083 nm fiber laser to {sup 4}He transition lines with optical heterodyne saturation spectroscopies

Two kinds of optical heterodyne saturation spectroscopies, namely, frequency modulation spectroscopy (FMS) and modulation transfer spectroscopy (MTS), are demonstrated for locking a fiber laser to the transition lines of metastable {sup 4}He atoms around 1083 nm. The servo-loop error signals of FMS and MTS for stabilizing laser frequency are optimized by studying the dependence of the peak-to-peak amplitude and slope on the optical power of pump and probe beams. A comparison of the stabilization performances of FMS/MTS and polarization spectroscopy (PS) is presented, which shows that MTS exhibits relatively superior performance with the least laser frequency fluctuation due to its flat-background dispersive signal, originated from the four-wave mixing process. The Allan deviation of the stabilized laser frequency is 5.4 × 10{sup −12}@100 s with MTS for data acquired in 1000 s, which is sufficiently applicable for fields like laser cooling, optical pumping, and optical magnetometry.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗