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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
NASA NTRS2017

Surface Monitoring of CFRP Structures for Adhesive Bonding

Adhesive bonding of composite materials requires reliable monitoring and detection of surface contaminants to assure robust and durable bonded structures. Surface treatment and effective monitoring prior to bonding is essential in order to obtain a surface free from contaminants that may degrade structural performance. Two techniques which monitor the effectiveness of the laser surface treatment of carbon fiber reinforced polymer (CFRP) materials are being investigated: laser induced breakdown spectroscopy (LIBS) and optically stimulated electron emission (OSEE). The applicability of LIBS to detect silicone contaminants on CFRP composites is studied using ~35 ns Nd:YAG laser pulses at 355 nm with a pulse energy of 45 mJ. The LIBS regime in which pulse energies are < 100 mJ is referred to as mLIBS. CFRP surfaces were contaminated with polydimethylsiloxane (PDMS), a major component of silicone based mold release agents. The presence of PDMS is found by inspecting the Si I emission line at 288.2 nm. Untreated CFRP samples and CFRP contaminated with PDMS were tested. The PDMS areal density ranged from 0.36 Â+/- 0.04 to 0.51 Â+/- 0.16 mg/cm2. The results demonstrate the successful detection of PDMS on CFRP using mLIBS. In addition, OSEE was used to measure CFRP surface cleanliness pre- and post-treatment by laser ablation on specimens contaminated with PDMS coatings from 8 nm to 1311 nm in thickness. The results showed a significant increase in the OSEE photocurrent after laser surface treatment.

Ledesma, Rodolfo↗
NASA NTRS2017

Surface Characterization of Carbon Fiber Reinforced Polymers by Picosecond Laser Induced Breakdown Spectroscopy

Adhesive bonding of composite materials requires reliable monitoring and detection of surface contaminants as part of a vigorous quality control process to assure robust and durable bonded structures. Surface treatment and effective monitoring prior to bonding are essential in order to obtain a surface which is free from contaminants that may lead to inferior bond quality. In this study, the focus is to advance the laser induced breakdown spectroscopy (LIBS) technique by using pulse energies below 100 μJ (μLIBS) for the detection of low levels of silicone contaminants in carbon fiber reinforced polymer (CFRP) composites. Various CFRP surface conditions were investigated by LIBS using ∼10 ps, 355 nm laser pulses with pulse energies below 30 μJ. Time-resolved analysis was conducted to optimize the gate delay and gate width for the detection of the C I emission line at 247.9 nm to monitor the epoxy resin matrix of CFRP composites and the Si I emission line at 288.2 nm for detection of silicone contaminants in CFRP. To study the surface sensitivity to silicone contamination, CFRP surfaces were coated with polydimethylsiloxane (PDMS), the active ingredient in many mold release agents. The presence of PDMS was studied by inspecting the Si I emission lines at 251.6 nm and 288.2 nm. The measured PDMS areal densities ranged from 0.15 to 2 μg/cm(sup 2). LIBS measurements were performed before and after laser surface ablation. The results demonstrate the successful detection of PDMS thin layers on CFRP using picosecond μLIBS.

Rodolfo Ledesma↗
NASA NTRSDate not supplied

A Mars 2020 Perseverance SuperCam Perspective on the Igneous Nature of the Máaz Formation at Jezero Crater, Mars

The Mars2020 Perseverance rover landed in Jezero crater in February 2020,and first encountered the Máaz formation (or Crater floor-fractured rough(Cf-fr) unit previously mapped based on orbital data[1]).In this study, we use data from the SuperCam instrument(SCAM) to show that the Máaz formation has an igneous origin. SuperCam is a remote-sensing instrument onboard Perseverance, and investigates the texture, mineralogy, and chemistry of rocks and soils, as well as atmospheric features [2,3]. SuperCam comprises the Remote Micro Imager (RMI) to provide high-resolution images, laser-induced breakdown spectroscopy (LIBS)to investigate the major and minor element chemistry of materials, Raman, and passive visible-near infrared (VISIR) spectroscopy to analyze the mineralogy of targets, and time-resolved luminescence spectroscopy (TRLS)to measure organic fluorescence and inorganic luminescence. In addition, the microphone (MIC) can constrain the rock hardness through measurements of the shockwave of LIBS shots. In this study, we use LIBS-based major-oxide compositions (MOC),quantified using the calibration in [2].

Mars 2020↗
NASA NTRSDate not supplied

Material Property Estimation in Thin Battery Components Using Guided Wave Measurement, Experimental Dispersion Curve Extraction and Finite Element Modeling

At NASA, we are investigating nondestructive evaluation (NDE) and structural health monitoring (SHM) techniques to detect precursors of thermal runaway failure in lithium metal based lithium ion batteries (LIB). The approach is centered on computational simulation models to guide inspection and aid in interpretation of results. Since lithium metal LIBs have combinations of solid and fluid-filled porous materials, obtaining accurate material properties is both challenging and critical for successful simulation of battery inspection. To this end, we investigated a multi-verification approach for material characterization of thin battery components. First, a laser Doppler vibrometer (LDV) was used to measure guided wave fields in thin (microns-thick) battery components subject to broadband excitation. The time-space wavefield data was converted to frequency-wave number data to extract guided wave dispersion curves. A data visualization and post processing graphics user interface (GUI) was developed at NASA to aid the data exploration and analysis. Due to the thinness of the samples, low frequency-thickness-product plate wave approximations allowed for the calculation of closed-form solutions for material elastic property estimation. These approximations were then verified by calculating the Lamb wave solutions using the previously obtained material properties. Finally, the estimated elastic material properties were implemented in a COMSOL simulation model, and dispersion curves were extracted from simulation results. The dispersion curves and derived material properties were then compared to the analysis results from the experimental data. These comparisons informed on the accuracy of the measured material properties and helped demonstrate the accuracy of the finite element analysis (FEA) computational models. This assessment will prove vital when we start simulating more complex multi-layer components and poroelastic media. This paper gives a brief background of the problem space, outlines the workflow for data analysis and verification, shows results from the workflow, and gives an overview of future plans for simulation of lithium metal LIB inspection.

Peter Juarez↗
NASA NTRS2024

High Precision and Spatial Resolution Chemical Interrogation of Planetary Materials Using fs-LA/LIBS in Tandem With Multi-Collector ICP-MS

Combining femtosecond laser ablation (fs-LA) with laser-induced breakdown spectroscopy (LIBS), together with multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS), can provide remarkable insights into the composition, structure, and therefore geologic history of planetary materials and their terrestrial analogs. Using the Applied Spectra iX-fs-Tandem LA-LIBS Instrument and the Nu SP1700 MC-ICP-MS housed within the Center for Isotope Cosmochemistry and Geochronology at NASA Johnson Space Center, we present preliminary tandem fs-LA-(MC)-ICP-MS/LIBS measurements of planetary analog materials. The synergistic integration of fs-LA-LIBS offers high spatial resolution elemental mapping, enabling the identification of microscale variations within samples. Simultaneously, the MC-ICP-MS can deliver precise isotopic analyses, and integrating the two datasets yields a wealth of geochemical information for a given sample. LA-based chemical mapping experiment designs are contingent on the information sought (i.e., quantitative, or semi-quantitative) and the preferred or available volume of material removed for the analysis. For example, occasionally, there are significant limitations in the depth of ablation due to the sample value, the amount of material available, or simply the need to coordinate with other in-situ techniques. In these limited sample scenarios, the “depth-controlled” chemical maps allow for precise post-mapping ion-polishing of the sample, while the isotopic and elemental maps can be used for targeting future analyses (e.g., conventional LA analyses, SIMS analyses, and micro milling for solution ICP-MS/TIMS). The emerging methodology will establish a powerful tool for investigation of astromaterials and materials returned by future planetary sample science missions.

Jacob B Setera↗
DOE OSTI2023

MATBOX, an Open-Source Microstructure Analysis Toolbox for Meshing, Generation, Segmentation, and Characterization of 3D Heterogenous Volumes

Battery performance is strongly correlated with electrode microstructural properties. To account for its impact, lithium-ion battery (LIB) models either abstract the microstructural heterogeneity of composite electrodes using effective macroscopic properties (macro- or meso- scale models) or directly solve the system of equations on the microstructure geometry or mesh (microstructure-scale models). Therefore, to be adequate, both families of models require information from the microstructure geometry, which can be provided by the numerical tool presented in this work. MATBOX is a MATLAB open-source application [1] developed by NREL for performing various microstructure-related tasks including microstructure numerical generation, image filtering and microstructure segmentation, microstructure characterization and correlation, visualization, and microstructure meshing. MATBOX was originally developed for the analysis of LIB electrode microstructures; however, the algorithms provided by the toolbox are widely applicable to other heterogeneous materials. The toolbox provides a user-friendly experience thanks to a Graphical-User Interface, requires no coding by the user, and is well documented. This presentation will illustrate various MATBOX features for the characterization of a LIB electrode, including a fully automated Representative Volume Element (RVE) analysis, the numerical generation of complex 'virtual' microstructure, including dual-layer electrodes and carbon-binder additive phase, and the meshing of a complex NMC/graphite full cell microstructure suitable for 3D finite-element modeling. Other modules (segmentation, visualization, and correlation) will be briefly presented. Thanks to its modular, open-source approach, MATBOX can easily incorporate third-party algorithms to eventually build a standard in the field that will benefit the whole scientific community. Effective diffusion coefficient [2], additive phase numerical generation [3], and meshing [4] third-party algorithms have been already integrated in the toolbox with more to come.

DIRECT ENERGY CONVERSION,MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Dual Protective Mechanism of AlPO 4 Coating on High-Nickel Cathode Material for High Energy Density and Long Cycle Life Lithium-Ion Batteries

Cathode material with high nickel content is a promising candidate for the future generation of Li-ion batteries (LIBs). However, severe structural degradation during cycling limits its practical use, especially for electric vehicles. Herein, AlPO 4 nanoparticles were synthesized and then coated onto the surface of a high-nickel layer-structured cathode via a dry coating method. The AlPO 4 nanoparticles coating significantly improved the cycling stability from 69.2% to over 80% capacity retention after 140 cycles. Furthermore, the structure and chemical composition of the AlPO 4 -coated cathode was investigated by XRD, SEM, XPS, and STEM. Compared with the non-coated cathode, we revealed a dual protective mechanism for enhanced cycling stability, where Al doping and Li 3 PO 4 coating play synergistic roles in protecting cathode material through long-term cycling. This work demonstrates a facile and environmentally friendly approach toward improving the performance of high-nickel LIB cathodes, which can be easily scaled up for industrial applications.

25 ENERGY STORAGE↗
DOE OSTI2026

Design of a Molten Salt Flow Cell for Combined Absorbance and Laser-Induced Breakdown Spectroscopy for Online Measurements

A novel flow cell allowing for multiple optical spectroscopy measurements on flowing molten salts was designed, and demonstrative calibrations of impurities in aqueous samples were performed. Online compositional measurements of molten salts are of high interest to monitor the state of relevant solar and nuclear systems. Here, the Spectroscopic Configuration for Optical Real-Time Characterization of High-Temperature (SCORCH) fluids cell was designed to meet this need by providing optical access to a high-temperature molten salt sample stream without physical contact between the sample and window materials. Laser-induced breakdown spectroscopy (LIBS) was utilized to quantify Li, Cr, Fe, Ni, Sr, and Pr at concentrations ranging nominally from 0 to 315 mmol L −1 . Laser power, frequency, and plasma position were optimized to mitigate challenges associated with sample splashing. Univariate calibration models were built with R 2 > 0.98, percent root mean square error of cross-validation (%RMSECV) as low as 2.7%, and limits of quantification (LOQs) down to 4.1 mmol L −1 . Simultaneously, absorbance calibrations were developed for the applicable analytes (Cr, Ni, and Pr) using Beer’s law with a pathlength of 4.41 ± 0.10 mm. These models provide excellent quantification performance with R 2 > 0.999, %RMSECV as low as 0.6%, and LODs down to 0.08 mmol L −1 . Although these calibrations were performed for each spectroscopic technique separately, the two methods may be combined in the future through multivariate modeling and sensor fusion to provide more robust models with the benefits of both techniques (e.g., absorbance: oxidation state concentrations, LIBS: elemental concentration). Additionally, optimized spectrometers may be deployed to enhance sensitivity.

absorbance spectroscopy↗
DOE OSTI2023

Biopolymer‐assisted Synthesis of P‐doped TiO 2 Nanoparticles for High‐performance Lithium‐ion Batteries: A Comprehensive Study

Abstract TiO 2 material has gained significant attention for large‐scale energy storage due to its abundant, low‐cost, and environmentally friendly properties, as well as the availability of various nanostructures. Phosphorus doping has been established as an effective technique for improving electronic conductivity and managing the slow ionic diffusion kinetics of TiO 2 . In this study, non‐doped and phosphorus doped TiO 2 materials were synthesized using sodium alginate biopolymer as chelating agent. The prepared materials were evaluated as anode materials for lithium‐ion batteries (LIBs). The electrodes exhibit remarkable electrochemical performance, including a high reversible capacity of 235 mAh g −1 at 0.1 C and excellent first coulombic efficiency of 99 %. An integrated approach, combining operando XRD and ex‐situ XAS, comprehensively investigates the relationship between phosphorus doping, material structure, and electrochemical performance, reinforced by analytical tools and first principles calculations. Furthermore, a full cell was designed using 2 %P‐doped TiO 2 anode and LiFePO 4 cathode. The output voltage was about 1.6 V with high initial specific capacity of 148 mAh g −1 , high rate‐capability of 120 mAh g −1 at 1 C, and high‐capacity retention of 96 % after 1000 cycles at 1 C.

El Halya, Nabil↗
DOE OSTI2025

Single particle trace element analysis of uranium oxide standards with laser-induced breakdown spectroscopy

Femtosecond Laser-Induced Breakdown Spectroscopy (LIBS) was used to analyze over 1000 individual particles of uranium oxide trace element standard CRM124. Intra-granular analysis showed elemental concentrations were consistent across different surface locations on each uranium grain. However, inter-granular comparison revealed large heterogeneity between different grains of the same sample. By comparing the distribution of elemental concentrations across the particle populations, we were able to correctly identify a manufacturing process involving wet chemistry, rather than a dry mixing of two powders to give an overall chemical average. In conclusion, this demonstrates the utility of LIBS as a large-scale single particle analysis tool for nuclear forensics.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

The SuperCam Instrument Suite on the NASA Mars 2020 Rover: Body Unit and Combined System Tests

The SuperCam instrument suite provides the Mars 2020 rover, Perseverance, with a number of versatile remote-sensing techniques that can be used at long distance as well as within the robotic-arm workspace. These include laser-induced breakdown spectroscopy (LIBS), remote time-resolved Raman and luminescence spectroscopies, and visible and infrared (VISIR; separately referred to as VIS and IR) reflectance spectroscopy. A remote micro-imager (RMI) provides high-resolution color context imaging, and a microphone can be used as a stand-alone tool for environmental studies or to determine physical properties of rocks and soils from shock waves of laser-produced plasmas. SuperCam is built in three parts: The mast unit (MU), consisting of the laser, telescope, RMI, IR spectrometer, and associated electronics, is described in a companion paper. The on-board calibration targets are described in another companion paper. Here we describe SuperCam’s body unit (BU) and testing of the integrated instrument. The BU, mounted inside the rover body, receives light from the MU via a 5.8 m optical fiber. The light is split into three wavelength bands by a demultiplexer, and is routed via fiber bundles to three optical spectrometers, two of which (UV and violet; 245–340 and 385–465 nm) are crossed Czerny-Turner reflection spectrometers, nearly identical to their counterparts on ChemCam. The third is a high-efficiency transmission spectrometer containing an optical intensifier capable of gating exposures to 100 ns or longer, with variable delay times relative to the laser pulse. This spectrometer covers 535–853 nm ( $105\text{--}7070~\text{cm}^{-1}$ Raman shift relative to the 532 nm green laser beam) with $12~\text{cm}^{-1}$ full-width at half-maximum peak resolution in the Raman fingerprint region. The BU electronics boards interface with the rover and control the instrument, returning data to the rover. Thermal systems maintain a warm temperature during cruise to Mars to avoid contamination on the optics, and cool the detectors during operations on Mars.Results obtained with the integrated instrument demonstrate its capabilities for LIBS, for which a library of 332 standards was developed. Examples of Raman and VISIR spectroscopy are shown, demonstrating clear mineral identification with both techniques. Luminescence spectra demonstrate the utility of having both spectral and temporal dimensions. Finally, RMI and microphone tests on the rover demonstrate the capabilities of these subsystems as well.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Molten salt electrochemical upcycling of CO 2 to graphite for high performance battery anodes

The efficient transformation of CO 2 into a value-added material is a potential strategy to help mitigate climate effects caused by CO 2 emissions. One potential CO 2 conversion product is graphite which is an important and versatile material extensively used in many applications including as an anode for lithium-ion batteries (LIBs). Commercial graphite, however, is traditionally synthesized via the energy intensive Acheson process (>3000 °C) and the performance of such graphite can be limited under fast charging conditions which is important for vehicle electrification. We report the electrochemical transformation of CO 2 to highly crystalline nano-graphite with a controlled microstructure in a carbonate molten salt at 780 °C. The use of a nickel foam electrode and controlled electrochemical parameters during the molten salt conversion process yielded pure graphite at a lower temperature compared to the Acheson process. Moreover, when investigated as an anode material for LIBs, the CO 2 -converted graphite exhibited high reversible capacity, long cycle life, and excellent rate capability even under fast charging conditions. This process provides a way to potentially reduce carbon emissions through the utilization of waste CO 2 by converting it into value-added graphite suitable for fast charging, high-energy-density batteries for vehicle electrification.

25 ENERGY STORAGE↗
DOE OSTI2023

Radiative transition probabilities of neutral and singly ionized rare earth elements (La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) estimated by laser-induced breakdown spectroscopy

Rare earth elements (REEs) are essential to society given their prevalence in many modern technologies. Quantitative elemental analysis of REEs is therefore a critical capability. Calibration free–laser-induced breakdown spectroscopy (CF-LIBS) is a rapidly maturing and promising approach to quantitative elemental analysis with many attractive qualities. The application of CF-LIBS to analyzing samples containing the REEs is hindered by a lack of fundamental data, specifically transition probabilities (TPs). As such, this study seeks to help address this knowledge deficiency by reporting 967 previously unreported TPs for 13 REEs (lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium). The method developed in this study to estimate the TPs requires small amounts of material (a few nanograms) compared with other approaches (~ milligrams), uses non-specialized equipment, and does not involve complicated sample preparations.

(LIBS)↗
DOE OSTI2021

Electrospun Separator Based on Sulfonated Polyoxadiazole with Outstanding Thermal Stability and Electrochemical Properties for Lithium-Ion Batteries

Traditional polyolefin separators used in lithium-ion batteries (LIBs) are seriously limited by the issues of inferior security and poor electrolyte wettability. Most of the very promising candidate separators based on heat-resistant polymers are, however, inherently difficult to process. Herein, a unique sulfonated aromatic heterocyclic polymer, lithiated poly(diphenyl ether oxadiazole) sulfonate (Li-SPEOD), was synthesized through a simple one-pot method and further electrospun to act as a novel separator (es-Li-SPEOD) for LIBs. In this work, the prepared Li-SPEOD possesses a high degree of sulfonation with a high molecular weight (M w = 4.31 × 10 5 ). The es-Li-SPEOD separator exhibits excellent mechanical and fire-resistance properties and is able to maintain dimensional stability at a temperature of even up to 400 °C in air. The ionic conductivity (3.57 mS cm –1 ) and lithium-ion transference number (0.37) of the es-Li-SPEOD with an electrochemical stability window of 4.5 V vs Li + /Li can be improved by 382.4 and 32.1%, respectively, compared to those of Celgard-2500 in the LiPF 6 electrolyte. The enhanced rate capability and cycle performance of the LiFePO 4 –Li half-cell are therefore obtained. Moreover, the es-Li-SPEOD displays an outstanding dendrite-suppressing effect for the lithium metal anode. This research proves that the Li-SPEOD-based separator has a broad application perspective in next-generation lithium batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Valence Effects of Fe Impurity for Recovered LiNi 0.6 Co 0.2 Mn 0.2 O 2 Cathode Materials

Iron impurities are generally included in the obtained leaching liquor solution during the hydrometallurgical recycling method of spent lithium-ion batteries (LIBs) due to the usage of iron in battery casings and machinery parts of recycling equipment, which would definitely affect the physical and electrochemical features of the recovered active materials. In this paper, the effects of iron impurity with different valence states (Fe 2+ and Fe 3+ ) and gradient concentrations (0.2, 1.0, and 5.0 at. %) for the obtained LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathodes are fully studied. It is found that Fe3+ impurity could easily lower the tap density and average size of NCM622 particles and even introduce some impurity phases in the NCM622 structure at high concentration (5.0 at. %), leading to much lower specific capacity, worse rate capability, and cycling performance of the Fe 3+ -based NCM622 cathode. On contrast, with certain concentrations of Fe 2+ impurity (0.2 and 1.0 at. %), the NCM622 cathode material exhibits comparable and much better electrochemical properties compared with the virgin NCM622 materials. Based on these results, the valence of Fe impurity should be considered and controlled as well as its concentration during the recycling process design for spent LIBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Dynamic deuterium retention properties of tungsten measured using laser-induced breakdown spectroscopy

Dynamic deuterium (D) retention properties of tungsten (W) are investigated under steady-state D plasma exposure in the PISCES-A linear plasma device. In contrast to static retention, dynamic retention is quickly released from the material at the termination of the incident plasma flux, and thus in-operando laser-induced breakdown spectroscopy (LIBS) measurements have been conducted during steady-state D plasma exposure. A procedure is, first, established to extract the dynamic retention component from the in-operando LIBS D I 656.1 nm line intensity, which can contain contributions from dynamic and static retention as well as background D/D 2 gas, excited by both steady-state and laser-induced plasmas. Using the developed procedure, the dynamic D retention in W is systematically examined while scanning the following plasma exposure parameters: incident ion energy, E i , sample temperature, T s , incident ion flux, Γ i . No clear E i dependence is seen in the range of E i ~ 45–175 eV, as expected from a small variation in the average implantation depth (~3-6 nm) of D in W. The dynamic retention is found to monotonously decrease with increasing T s from 348 to 573 K, while the total static retention is reported to peak at T s ~ 500–600 K. It is revealed that the dynamic retention linearly increases with increasing Γ i , and then saturates at Γ i ≥ 0.75 × 10 21 m –2 s –1 . Possible physical mechanisms for the observed dependence of the dynamic retention on T s and Γ i are discussed. Furthermore, sequential pure He, followed by pure D, plasma exposures show that the dynamic D retention is not strongly affected by He bubbles in the near-surface region.

super-saturated surface layer↗
DOE OSTI2022

Determination of fluorine distribution in shark teeth by laser-induced breakdown spectroscopy

Quantifying the chemical composition of fast-growing hard tissues in the environment can shed valuable information in terms of understanding ecosystems both prehistoric and current. Changes in chemical composition can be correlated with environmental conditions and can provide information about the organism's life. Sharks can lose 0.1 to 1.1 teeth/day, depending on species, which offers a unique opportunity to record environmental changes over a short duration of time. Shark teeth contain a biomineral phase that is made up of fluorapatite [Ca 5 (PO 4 ) 3 F], and the F distribution within the tooth can be correlated to tooth hardness. Typically, this is determined by bulk acid digestion, energy-dispersive X-ray spectroscopy (EDS), or wavelength-dispersive spectroscopy. Here we present laser-induced breakdown spectroscopy (LIBS) as an alternative and faster approach for determining F distribution within shark teeth. Using a two-volume laser ablation chamber (TwoVol3) with innovative embedded collection optics for LIBS, shark teeth were investigated from sand tiger (Carcharias Taurus), tiger (Galeocerdo Cuvier), and hammerhead sharks (Sphyrnidae). Fluorine distribution was mapped using the CaF 603 nm band (CaF, Β 2 Σ + → X 2 Σ + ) and quantified using apatite reference materials. In addition, F measurements were cross referenced with EDS analyses to validate the findings. Distributions of F (603 nm), Na (589 nm), and H (656 nm) within the tooth correlate well with the expected biomineral composition and expected tooth hardness. This rapid methodology could transform the current means of determining F distribution, particularly when large sample specimens (350 mm 2 , presented here) and large quantities of specimens are of interest.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Quantification of Lanthanides in a Molten Salt Reactor Surrogate Off-Gas Stream Using Laser-Induced Breakdown Spectroscopy

To enable the deployment of molten salt reactor technology, the development of off-gas treatment systems and advanced monitoring tools capable of operating with high temperatures and radiation fields while delivering near real-time information is necessary. Here, we aim to fulfill this requirement and proposes laser-induced breakdown spectroscopy (LIBS) for monitoring molten salt aerosol streams. A sheath gas measuring method was developed to protect optical elements from aerosol particles and to ensure a relatively constant aerosol stream for measurement. An aqueous system was studied to demonstrate the utility of LIBS for monitoring possible fission products in an aerosol stream: Gd, Nd, and Sm up to 2000 parts per million (ppm). A calibration model was built using partial least squares (PLS) regression with five, six, and nine latent variables for Gd, Nd, and Sm, respectively. This calibration model successfully estimated the concentrations of three test samples, which were validated with inductively charged plasma optical emission spectroscopy measurements at a 99.9% confidence interval. To enhance these models, a genetic algorithm was used to filter the spectra before entering the PLS model, thereby limiting the spectral features being regressed to those with greater correlations to concentration. This allowed for the number of latent variables used in the PLS models to be reduced to four, three, and three for Gd, Nd, and Sm, respectively. Finally, the genetic algorithm-filtered PLS models were used to predict the concentrations of the aerosol stream on a real-time dataset and resulted in a 73%, 18%, and 25% improvement in root mean squared error of prediction compared to the original PLS models developed.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗