SEARCH · Engineering Papers

Results for “raman”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,207 records · Page 67

All sources NASA NTRS DOE OSTI

DOE OSTI2021

Spectroscopic evidence for the Fe3+ spin transition in iron-bearing δ-AlOOH at high pressure

δ-AlOOH has emerged as a promising candidate for water storage in the lower mantle and could have delivered water into the bottom of the mantle. To date, it still remains unclear how the presence of iron affects its elastic, rheological, vibrational, and transport properties, especially across the spin crossover. In this study, we conducted high-pressure X-ray emission spectroscopy experiments on a δ-(Al 0.85 Fe 0.15 ) OOH sample up to 53 GPa using silicone oil as the pressure transmitting medium in a diamond-anvil cell. We also carried out laser Raman measurements on δ-(Al 0.85 Fe 0.15 )OOH and δ-(Al 0.52 Fe 0.48 )OOH up to 57 and 62 GPa, respectively, using neon as the pressure-transmitting medium. Evolution of Raman spectra of δ-(Al 0.85 Fe 0.15 )OOH with pressure shows two new bands at 226 and 632 cm –1 at 6.0 GPa, in agreement with the transition from an ordered ( P 2 1 nm ) to a disordered hydrogen bonding structure ( Pnnm ) for δ-AlOOH. Similarly, the two new Raman bands at 155 and 539 cm –1 appear in δ-(Al 0.52 Fe 0.48 )OOH between 8.5 and 15.8 GPa, indicating that the incorporation of 48 mol% FeOOH could postpone the order-disorder transition upon compression. On the other hand, the satellite peak ( K β') intensity of δ-(Al 0.85 Fe 0.15 )OOH starts to decrease at ~30 GPa and it disappears completely at 42 GPa. That is, δ-(Al 0.85 Fe 0.15 )OOH undergoes a gradual electronic spin-pairing transition at 30–42 GPa. Furthermore, the pressure dependence of Raman shifts of δ-(Al 0.85 Fe 0.15 )OOH discontinuously decreases at 32–37 GPa, suggesting that the improved hydrostaticity by the use of neon pressure medium could lead to a relatively narrow spin crossover. Notably, the pressure dependence of Raman shifts and optical color of δ-(Al 0.52 Fe 0.48 )OOH dramatically change at 41–45 GPa, suggesting that it probably undergoes a relatively sharp spin transition in the neon pressure medium. Together with literature data on the solid solutions between δ-AlOOH and ε-FeOOH, we found that the onset pressure of the spin transition in δ-(Al,Fe)OOH increases with increasing FeOOH content. These results shed new insights into the effects of iron on the structural evolution and vibrational properties of δ-AlOOH. The presence of FeOOH in δ-AlOOH can substantially influence its high-pressure behavior and stability at the deep mantle conditions and play an important role in the deep-water cycle

58 GEOSCIENCES↗

DOE OSTI2022

High-Pressure Investigation of 2,4,6-Trinitro-3-bromoanisole (TNBA): Structural Determination and Piezochromism

Understanding phase transitions in energetic materials is crucial for developing predictive models of detonation. 2,4,6-Trinitro-3-bromoanisole (TNBA), an energetic material, was studied in its single-crystal form up to pressures of 45 GPa in a diamond anvil cell. The material was characterized by using X-ray, Raman, and optical transmission measurements. From single-crystal X-ray diffraction, the ambient structure of TNBA was determined which crystallizes in the P2 1 /c space group having four molecular units per unit cell. The X-ray data up to 9.2 GPa were fitted to a third-order Birch–Murnaghan equation of state by using the parameters K o = 13.2(2.4) GPa and K p = 5.1(1.4). Between 6.8 and 7.3 GPa, a phase transition was inferred in TNBA from concurrent fading of X-ray diffraction, disappearance of Raman peaks, increase in sample fluorescence, and discontinuous color change. The new phase was consistent with an amorphous state of at least partially intact molecules judging from the presence of higher-order Raman modes and irreversibility of the Raman spectra upon release. Piezochromism was observed with the translucent yellow TNBA gradually darkening and becoming opaque black at ~25 GPa. This correlated to the absorption edge gradually shifting to the red in the visible spectrum. Signs of two possible additional structural transitions were detected in the 32.4–41.0 GPa range as suggested by a jump in the absorption edge, the irreversible changes in the absorption spectrum upon release to ambient pressure, and by the lack of Raman modes in recovered samples. Here, the crystal and electronic structures of TNBA were also investigated up to 10 GPa by using DFT calculations and crystal structure prediction (CSP) simulations. In agreement with the experimentally observed transition at 7 GPa, the simulations at 10 GPa found a bevy of polymorphs lower in enthalpy and higher in density than P2 1 /c. The lowest calculated enthalpy structure was determined to be P2 1 2 1 2 1 , being in a different space group than the ambient experimental result.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Investigating Hydrogen Isotope Exchange Reactions on Lithium Aluminate Pellets in TPBAR (FY22 Report)

We developed a novel operando Raman spectroscopy method for investigation of hydrogen (H) isotope exchange reactions in the lithium aluminate (γ-LiAlO 2 ) that allows modeling of tritium behaviors in high temperature and in an irradiated environment. The lithium aluminate pellet is a main component in the Tritium-Producing Burnable Absorber Rod (TPBAR). We used deuterium ( 2 H or D) as a surrogate to simulate tritium ( 3 H or T). We used a surface analysis tools in situ/operando Raman spectroscopy to observe the transformation OH and OD compositional changes. We also used ToF-SIMS to analyze the lithium aluminate pellet control sample to build the base line for future in situ/operando analysis. To conduct operando Raman spectroscopy, we developed a custom reaction cell with a detachable micro heater using microelectromechanical systems (MEMS) and 3D printing techniques. Multiple versions were developed and tested. Using the new reaction cell, we demonstrated operando Raman spectroscopy of water (H 2 O) and deuterated water (D 2 O) with nitrogen (N 2 ) exposure onto the lithium aluminate (LiAlO2) pellet specimen, respectively, using a wet gas injection setup. We also successfully developed a detachable microheater that can heat up to ~250°C for ~90 mins. The Raman spectra did not show clear H 2 O and D 2 O characteristic peaks, which indicates that introducing H 2 O and D 2 O onto the surface of the pellet is challenging due to its dense structure nature. Our efforts suggest that various improvements are needed, such as increasing reaction cell operating gas pressure and thinning pellet sample thickness, to obtain meaningful measurements.

07 ISOTOPE AND RADIATION SOURCES↗

NASA NTRS1989

Structural comparison of nickel electrodes and precursor phases

A summary of previous Raman spectroscopic results and a discussion of important structural differences in the various phases of active mass and active mass precurors are presented. Raman spectra provide unique signatures for these phases, and allow one to distinguish each phase, even when the compound is amorphous to X-rays (i.e., does not scatter X-rays because of a lack of order and/or small particle size). The structural changes incurred during formation, charge and discharge, cobalt addition, and aging will be discussed and related to electrode properties. Important structural differences include NiO2 layer stacking, nonstoichiometry (especially cation-deficit nonstoichiometry), disorder, dopant content, and water content. The results indicate that optimal nickel active mass is non-close packed and nonstoichiometric. The formation process transforms precursor phases into this structure. Therefore, the precursor disorder, or lack thereof, influences this final active mass structure and the rate of formation. Aging processes induce structural change which is believed to be detrimental. The role of cobalt addition can be appreciated in terms of structures favored or stabilized by the dopant. In recent work, the in situ Raman technique to characterize the critical structural parameters was developed. An in situ method relates structure, electrochemistry, and preparation. In situ Raman spectra of cells during charge and discharge, either during cyclic voltammetry or under constant current conditions were collected. With the structure-preparation knowledge and the in situ Raman tool, it will be possible to define the structure-property-preparation relations in more detail. This instrumentation has application to a variety of electrode systems.

Cornilsen, Bahne C.↗

NASA NTRS2002

Characterization of Upper Troposphere Water Vapor Measurements during AFWEX using LASE

Water vapor profiles from NASA's Lidar Atmospheric Sensing Experiment (LASE) system acquired during the ARM/FIRE Water Vapor Experiment (AFWEX) are used to characterize upper troposphere water vapor (UTWV) measured by ground-based Raman lidars, radiosondes, and in situ aircraft sensors. Initial comparisons showed the average Vaisala radiosonde measurements to be 5-15% drier than the average LASE, Raman lidar, and DC-8 in situ diode laser hygrometer measurements. We show that corrections to the Raman lidar and Vaisala measurements significantly reduce these differences. Precipitable water vapor (PWV) derived from the LASE water vapor profiles agrees within 3% on average with PWV derived from the ARM ground-based microwave radiometer (MWR). The agreement among the LASE, Raman lidar, and MWR measurements demonstrates how the LASE measurements can be used to characterize both profile and column water vapor measurements and that ARM Raman lidar, when calibrated using the MWR PWV, can provide accurate UTWV measurements.

Ferrare, R. A.↗

NASA NTRS2005

Local Intensity Enhancements in Spherical Microcavities: Implications for Photonic Chemical and Biological Sensors

In this report, we summarize recent findings regarding the use spherical microcavities in the amplification of light that is inelastically scattered by either fluorescent or Raman-active molecules. This discussion will focus on Raman scattering, with the understanding that analogous processes apply to fluorescence. Raman spectra can be generated through the use of a very strong light source that stimulates inelastic light scattering by molecules, with the scattering occurring at wavelengths shifted from that of the source and being most prominent at shifts associated with the molecules natural vibrational frequencies. The Raman signal can be greatly enhanced by exposing a molecule to the intense electric fields that arise near surfaces (typically of gold or silver) exhibiting nanoscale roughness. This is known as surface-enhanced Raman scattering (SERS). SERS typically produces gain factors of 103 - 106, but under special conditions, factors of 1010 - 1014 have been achieved.

Fuller, Kirk A.↗

NASA NTRS2012

Real-Time, Non-Intrusive Detection of Liquid Nitrogen in Liquid Oxygen at High Pressure and High Flow

An integrated fiber-optic Raman sensor has been designed for real-time, nonintrusive detection of liquid nitrogen in liquid oxygen (LOX) at high pressures and high flow rates in order to monitor the quality of LOX used during rocket engine ground testing. The integrated sensor employs a high-power (3-W) Melles Griot diode-pumped, solid-state (DPSS), frequency-doubled Nd:YAG 532- nm laser; a modified Raman probe that has built-in Raman signal filter optics; two high-resolution spectrometers; and photomultiplier tubes (PMTs) with selected bandpass filters to collect both N2 and O2 Raman signals. The PMT detection units are interfaced with National Instruments Lab- VIEW for fast data acquisition. Studies of sensor performance with different detection systems (i.e., spectrometer and PMT) were carried out. The concentration ratio of N2 and O2 can be inferred by comparing the intensities of the N2 and O2 Raman signals. The final system was fabricated to measure N2 and O2 gas mixtures as well as mixtures of liquid N2 and LOX

Singh, Jagdish P.↗

NASA NTRS2015

Mineralogy and Astrobiology Detection Using Laser Remote Sensing Instrument

A multispectral instrument based on Raman, laser-induced fluorescence (LIF), laser-induced breakdown spectroscopy (LIBS), and a lidar system provides high-fidelity scientific investigations, scientific input, and science operation constraints in the context of planetary field campaigns with the Jupiter Europa Robotic Lander and Mars Sample Return mission opportunities. This instrument conducts scientific investigations analogous to investigations anticipated for missions to Mars and Jupiter's icy moons. This combined multispectral instrument is capable of performing Raman and fluorescence spectroscopy out to a >100 m target distance from the rover system and provides single-wavelength atmospheric profiling over long ranges (>20 km). In this article, we will reveal integrated remote Raman, LIF, and lidar technologies for use in robotic and lander-based planetary remote sensing applications. Discussions are focused on recently developed Raman, LIF, and lidar systems in addition to emphasizing surface water ice, surface and subsurface minerals, organics, biogenic, biomarker identification, atmospheric aerosols and clouds distributions, i.e., near-field atmospheric thin layers detection for next robotic-lander based instruments to measure all the above-mentioned parameters. OCIS codes: (120.0280) Remote sensing and sensors; (130.0250) Optoelectronics; (280.3640) Lidar; (300.2530) Fluorescence, laser-induced; (300.6450) Spectroscopy, Raman; (300.6365) Spectroscopy, laser induced breakdown

Abedin, M. Nurul↗

NASA NTRS2019

TPSAS-NF1676L-32345-DND

Interest in the use of Raman spectrometers has seen an increase in the fields of geology and planetary sciences due to the non-destructive insight Raman spectra may provide into the molecular makeup of a given sample. Advancements in Raman spectrometer hardware have allowed for compact instruments to have deployment capabilities directly on interplanetary missions, flexible usage conditions requiring no sample collection/preparation, and no need for daylight radiation shielding. As the amount of science which can be collected from a Raman spectrometer in a given amount of time increases, a bottleneck will be created in data analysis which leaves a need for a faster method of spectral data classification. Recent studies have shown that machine learning models are able to solve this problem by achieving high-accuracy classification. Liu et al4 found the convolutional neural network (CNN) held the highest classification accuracy (96% top 5) for single sample Raman data.

A Atkinson↗

NASA NTRS2012

TPSAS-NF1676L-14292-DND

NASA Langley Research Center (LaRC) initiated the development of the miniature Raman-Fluorescence spectrograph and Lidar system with Langley investment funds. Later, a proposal called “Combined Raman, Fluorescence, and Lidar Multi-Sensor (RFLMS) Instrument Development Program” under NASA Mars Instrument Development Project (MIDP) was jointly proposed by University of Hawaii and NASA LaRC in 2008 and was selected for funding. Finally, Raman, Fluorescence, and Lidar prototype instrument has been integrated onto a rover system and demonstrated at NASA LaRC. Surface and atmospheric characterizations are performed with this prototype instrument from a robotic platform to investigate and identify the water, ice, and dry-ice at a 15 meter distance as well as conducting atmospheric aerosol and cloud distributions profiling. Recently acquired Raman spectra from water, ice, and dry-ice as well as atmospheric characterization results [refs. 1-2] are discussed in this study. The objective of this study is to develop a remote Raman-Fluorescence spectroscopy and Lidar multi-sensor instrument capable for investigation and identification of minerals, organics, and biogenic materials as well as conducting atmospheric studies of Mars, Moon, Asteroids/Comets, Europa, Titan, Venus, and other planets from rovers and landers.

M Nurul Abedin↗

NASA NTRSDate not supplied

Calibration and Validation of the SHERLOC Instrument Operating in Jezero Crater, Mars

The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemistry (SHERLOC) is an instrument onboard the Mars 2020 Perseverance rover. It consists of a spectrometer that measures deep ultraviolet (DUV) resonance Raman and native fluorescence photons generated through surface interactions with a 248.6 nm pulsed laser. Two microscopic imagers, the Autofocus Context Imager (ACI) and the Wide-Angle Topographic Sensor for Operations and eNgineering (WATSON), provide high-resolution context images of SHERLOC targets. The ACI is co-boresighted with the spectrometer. To ensure proper calibration, the SHERLOC calibration target (SCT) is mounted on the front of the rover and consists of ten different materials. The SCT was designed, fabricated, assembled, and tested by Jacobs Technology, Inc., and NASA Johnson Space Center. The dimensions of the calibration target housing are 150 x 89 x 33 mm and it weighs ~437 g. The ten targets are arranged in two rows; the first six are hard targets (AlGaN for Raman and fluorescence, diffuse transmission target, a slice of the SaU008 Mars meteorite, an intensity maze, and polycarbonate over geocache coin) and the remaining four are soft-goods targets (Vectran, Ortho-Fabric, Teflon, and nGimat-coated Teflon). The hard targets calibrate the spectrometer’s Raman and fluorescence spectral accuracy, ambient light reflection, and Raman response curve, while the soft-goods targets are spacesuit materials that function as human exploration targets, some of which are also used for spectral calibration. SHERLOC also has an internal calibration target consisting of AlGaN on sapphire (275 nm) located inside the ACI opaque dust cover to ensure proper instrument functioning between calibration target analyses. Initial SHERLOC, ACI, and WATSON calibration and validation on Mars was performed using the internal calibration target on sols 59, 83, 98, and 141; WATSON imaging of the SCT on sols 26 and 62, and SHERLOC spectroscopy and ACI imaging of the SCT on sol 59. These early data provide initial insights into instrument performance and the stability and degradation of the calibration target materials relative to the Martian surface and dust environment. Early observations also have implications for future astronaut spacesuit materials.

Trevor G Graff↗

NASA NTRS2024

Structural Differences Between Insoluble Organic Matter in Matrix and Chondrules: Potential Insights into Pre-Parent Body Thermal Alteration

Carbon is a major molecular constituent of primitive chondrites of low petrologic grade. A majority of the carbon (>70%) is in the insoluble organic matter (IOM) fraction that cannot be extracted from the meteorite sample using polar or nonpolar solvents. The IOM is comprised of a kerogen-like macromolecular carbon (MMC) structure that consists of aromatic rings connected by highly branching aliphatic chains. Raman spectroscopy is highly sensitive to IOM due to a strong resonance enhancement that occurs for all visible excitation wavelengths, making Raman a powerful in-situ probe of IOM. The Raman spectrum of IOM consists of two primary bands, the G band originates from all carbon-carbon bonds in the MMC structure and the D band that originates from carbon 6-member ring breathing motions. The peak position and width of the G and D bands probe the structure of the IOM. Using Raman spectroscopy, the IOM structure has been shown to correlate with the thermal alteration history of the meteorite, allowing for petrologic grade classification to the tenths place in the 3.0-3.9 range. Here, we have collected Raman images of GRA 06100,41 (CR2) for the examination of the IOM spatial distribution and observe significant differences between the IOM in the matrix and chondrules.

R S Jakubek↗

DOE OSTI2022

Gate-tunable modulation of the optical properties of multilayer graphene by the reversible intercalation of ionic liquid anions

We demonstrate a substantial modulation of the optical properties of multilayer graphene (~100 layers) using a simple device consisting of a multilayer graphene/polymer electrolyte membrane/gold film stack. Applying a voltage of 3–4 V drives the intercalation of anion [TFSI] - [ion liquid diethylmethyl(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide [DEME][TFSI]] resulting in the reversible modulation of the properties of this optically dense material. Upon intercalation, we observe an abrupt shift of 35 cm -1 in the G band Raman mode, an abrupt increase in FTIR reflectance over the wavelength range from 1.67 to 5 $μ$m (2000–6000 cm -1 ), and an abrupt increase in luminescent background observed in the Raman spectra of graphene. Furthermore, all of these abrupt changes in the optical properties of this material arise from the intercalation of the TFSI - ion and the associated change in the free carrier density (Δ$n$ = 10 20 cm -3 ). Suppression of the 2D band Raman mode observed around 3 V corresponds to Pauli blocking of the double resonance Raman process and indicates a modulation of the Fermi energy of Δ$E$ F = 1.1 eV.

42 ENGINEERING↗

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 OSTI2026

Sub-melt nanosecond pulsed-laser induced densification and strain-field relaxation in single-crystal diamond

Dislocations and polishing-induced defect networks in synthetic diamond introduce local strain fields and broaden Raman features, limiting performance in optical, thermal, and electronic applications. Laser annealing is emerging as a promising approach to repair surface and near-surface defects in diamond without entering the melt regime, yet surface densification, defect-state modification, and associated structural changes have not been well quantified. In this work, we show that sub-melt nanosecond pulsed-laser annealing (PLA) induces near-surface densification and defect-mediated strain relaxation in single-crystal Chemical Vapor Deposition (CVD) diamond. Single- and two-pulse PLA were applied, and structural evolution was quantified using co-registered ISO 25,178 white-light interferometry, depth-resolved Raman spectroscopy, and cross-sectional STEM with geometric phase analysis (GPA). Across a 5 × 6 grid (n = 30), responsive regions exhibit large reductions in local slope (Sdq 45–65%), developed area (Sdr 60–90%), height spread (Sp, Sz 30–65%), void volume (Vv 57–60%), and roughness amplitude (Sa, Sq 48–57%), consistent with densification of ∼4–6.5 nm. Raman profiling shows narrowing of the diamond line and improved spectral uniformity to depths of ∼2–3 μm. Given that the Raman probing depth significantly exceeds the densified layer thickness, this response is interpreted as consistent with long-range strain-field redistribution originating from the near-surface region. STEM-GPA strain maps further support this interpretation, showing smoother strain fields, suppressed hotspots, and redistribution of localized strain concentrations following PLA. These results are consistent with defect-mediated strain relaxation and densification-driven modification of the near-surface energy state. The approach provides a scalable pathway for improving near-surface structural quality in diamond relevant to electronic, photonic, and quantum applications.

Areal surface metrology (ISO 25,178)↗

DOE OSTI2019

Oxidation and anion lattice defect signatures of hypostoichiometric lanthanide-doped UO 2

A series of sintered UO 2 pellets doped with lanthanide (Ce, Nd, Yb) elements were investigated using powder X-ray diffraction, Raman spectroscopy, thermogravimetric analyses and differential scanning calorimetry. A combination of electron microprobe and thermogravimetric analyses, for oxygen content, enabled precise determination of the hypostoichiometry for lanthanide-doped samples at 1 and 5 atom percent. Two Raman laser wavelengths (785 and 455 nm) have afforded greater sensitivity to spectroscopic signatures of the phonon bands (1LO and 2LO) associated with oxidation of (U 1-y M y )O 2-x and the anion defects introduced by lanthanide substitution. Oxygen hypostoichiometry forces a reduction in the average coordination number surrounding (U,M) sites, which is compensated by a decrease in U-O bond length, and concomitantly the lattice parameter, consistent with the obtained Raman spectra. The evolution of O/M ratio up to (U 1-y M y )O 2 after oxidation was also examined using Raman spectroscopy, revealing that the ‘defect band’, including a component attributed to oxygen vacancies (~540 cm -1 ) and the 1LO phonon (~575 cm -1 ) increased in intensity with increasing dopant concentration and upon oxidation. Here, the lanthanide dopants inhibited oxidation to U 3 O 8 , most prominently for Yb 5 at%, having been delayed by ~180 °C. Thermogravimetric analyses reveal an early oxidation feature that may be related to influx of O to satisfy hypostoichiometry up to (U 1-y M y )O 2 , possibly stabilizing a U 4 O 9 or U 3 O 7 intermediate, delaying oxidation to U 3 O 8 .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2022

Radiolytic evaluation of select sulfur chlorides (S 2 Cl 2 and SOCl 2 ) for advanced low temperature chlorination of zirconium-based used nuclear fuel cladding

New sulfur chloride compounds—sulfur monochloride (S 2 Cl 2 ) and thionyl chloride (SOCl 2 )—have been proposed as alternative chlorinating agents for the chemical decladding of zirconium-based used nuclear fuel cladding materials. However, the radiation stability of these compounds has not been thoroughly evaluated, despite envisioned process conditions involving intense, multi-component radiation fields. Knowledge of the radiation chemistry of these sulfur chlorides is essential for the development and optimization of alternative chlorination technologies. To this end, we present preliminary findings on the gamma radiolysis of neat S 2 Cl 2 and SOCl 2 at ambient temperature up to ~ 34 MGy. In this study, Raman spectroscopy and density functional theory calculations were used to identify the Raman-active degradation products from S 2 Cl 2 and SOCl 2 radiolysis. Both sulfur chloride compounds exhibited significant radiation resistance, with respect to changes in the Raman signatures of the parent compounds and the ingrowth of Raman-active degradation products. For S 2 Cl 2 , molecular chlorine (Cl 2 ) was directly identified as the predominant degradation product, which was completely consumed at higher absorbed doses (> 9 MGy). Similarly, the main degradation product from SOCl 2 radiolysis was also Cl 2 , although in this system it continued to grow in with dose over the entire dose range. Further, an “S=O” containing degradation product(s) was also identified as a compliment to Cl 2 . Overall, the perceived radiation resistance of these sulfur chloride compounds makes them suitable for inclusion in a used nuclear fuel chemical decladding process, especially as radiolytically formed Cl 2 can be used to reform the parent compounds, thereby increasing the longevity of the solvents used.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2025

Overcoming Variability: A Reproducible Approach to SERS Detection of Nanodiamonds

Detonation nanodiamonds (DNDs) are formed at specific pressures and temperatures during explosions. Different explosives produce varied yields of DNDs within their detonation soot, with Composition B producing the highest yield. Raman spectroscopy (RS) is often used for the characterization of sp 2 - and sp 3 -hybridized carbon allotropes in carbonaceous materials because of distinct disorder and graphitic bands. Bulk diamond also gives a distinct Raman peak at 1332 cm –1 . Furthermore, as bulk diamond decreases in size to nanometer-sized species, the peak red-shifts and broadens, becoming increasingly difficult to detect with RS using visible excitations. Therefore, surface-enhanced Raman spectroscopy (SERS) was used to enhance the diamond peak of DNDs, enabling better detection and faster examination of DNDs within detonation soot. Previous literature of the SERS of DNDs delivered inconsistent results in spectral signatures and SERS substrates. Herein, refining of the methodology for the acquisition of SERS spectra of DNDs was achieved. Before any SERS experiments, the DNDs were first characterized with normal Raman (NR) and scanning electron microscopy. Two routes for SERS enhancement were evaluated: colloidal noble metal nanoparticles and evaporated silver films. Silver films produced the best signal enhancement of DNDs with the best signal-to-noise and peak enhancements observed at 20–30 nm thick silver films at 5% (∼300 μW) laser power. Consistent, reproducible SERS spectra were acquired of small aggregates of DNDs down to ∼500 nm. NR and SERS mapping analysis of DNDs before and after evaporation of silver films revealed the improvements in the detection capabilities of SERS compared with NR.

Carbon↗