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Results for “RAMAN SPECTROSCOPY”

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.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Operando Raman spectroscopy uncovers hydroxide and CO species enhance ethanol selectivity during pulsed CO 2 electroreduction

Pulsed CO 2 electroreduction (CO 2 RR) has recently emerged as a facile way to in situ tune the product selectivity, in particular toward ethanol, without re-designing the catalytic system. However, in-depth mechanistic understanding requires comprehensive operando time-resolved studies to identify the kinetics and dynamics of the electrocatalytic interface. Here, we track the adsorbates and the catalyst state of pre-reduced Cu 2 O nanocubes (~30 nm) during pulsed CO 2 RR using sub-second time-resolved operando Raman spectroscopy. By screening a variety of product-steering pulse length conditions, we unravel the critical role of co-adsorbed OH and CO on the Cu surface next to the oxidative formation of Cu-O ad or CuO x /(OH) y species, impacting the kinetics of CO adsorption and boosting the ethanol selectivity. However, a too low OH ad coverage following the formation of bulk-like Cu 2 O induces a significant increase in the C 1 selectivity, while a too high OH ad coverage poisons the surface for C-C coupling. Thus, we unveil the importance of co-adsorbed OH on the alcohol formation under CO 2 RR conditions and thereby, pave the way for improved catalyst design and operating conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

High-pressure behavior of 3.65 Å phase: Insights from Raman spectroscopy

Abstract The 3.65 Å phase [MgSi(OH)6] is a hydrous phase that is predicted to be stable in a simplified MgO-SiO2-H2O (MSH) ternary system at pressures exceeding 9 GPa. Along cold subduction zones, it is likely to transport water, bound in its crystalline lattice, into the Earth’s interior. The 3.65 Å phase consists of Mg and Si octahedral sites attached to the hydroxyl group that forms a hydrogen bond and is predicted to undergo pressure-induced symmetrization of the hydrogen bond. Therefore, in this study, we investigate the high-pressure behavior of the 3.65 Å phase using Raman spectroscopy. We have conducted five distinct compressions up to ~60 GPa using two different pressure-transmitting media—alcohol mixture and neon. At ambient conditions, we identified vibrational modes using complementary first-principles simulations based on density functional perturbation theory. Upon compression, we note that the first derivative of the vibrational modes in the lattice region stiffens, i.e., b1lattice > 0. In contrast, the hydroxyl region softens, i.e., b1OH > 0. This is indicative of the strengthening of hydrogen bonding upon compression. We noticed a significant broadening of vibrational modes related to hydroxyl groups that are indicative of proton disorder. However, within the maximum pressures explored in this study, we did not find evidence for pressure-induced symmetrization of the hydrogen bonds. We used the pressure derivative of the vibrational modes to determine the ratio of the bulk moduli and their pressure derivative. We note that the smaller bulk moduli of hydrous phases compared to the major mantle phases are compensated by significantly larger pressure derivatives of the bulk moduli for the hydrous phases. This leads to a significant reduction in the elasticity contrast between hydrous and major mantle phases. Consequently, the detection of the degree of mantle hydration is likely to be challenging at greater depths.

Geochemistry & Geophysics↗
DOE OSTI2025

Characterization of the degradation of gamma-irradiated elastomers using Raman spectroscopy

This report presents key findings from Raman spectroscopic analysis of gamma-irradiated rubber samples extracted from a laminated lead-damped rubber (LDR) seismic isolation device. The samples were exposed to gamma radiation from a 60Co source in a Foss Therapy Services gamma irradiator, reaching absorbed doses up to 1600 kGy. A distinct threshold near 400 kGy was identified, beyond which significant spectral changes were observed. Two Raman peaks - at approximately 425 cm-1 and 2440 cm-1 - were tracked as a function of dose using Gaussian fitting. The 425 cm-1 peak, attributed to sulfur–sulfur (S–S) bond stretching (resulting from vulcanization of the rubber), exhibited a dose-dependent upshift, indicating radiation-induced crosslinking within the sulfur-based polymer network. Conversely, the 2440 cm-1 peak, likely associated with vibrational modes of additives or impurities, showed a downward shift with increasing dose, suggesting chain scission and degradation of non-rubber constituents. These results provide first-of-a-kind insights into the microstructural evolution of elastomers under high-dose gamma irradiation and establish a preliminary dose threshold for significant degradation. Future work will incorporate multi-modal characterization—including Fourier Transform Infrared (FTIR) spectroscopy, scanning electrom microscopy (SEM) of the rubber surface morphology, thermogravimetric analysis (TGA) to determine changes in thermal stability, and mechanical testing—to correlate molecular-level changes with macroscopic performance of these elastomers as damping media in seismic isolation devices. These findings are expected to provide regulatory guidance and design criteria for qualifying low-damping rubber seismic isolators in advanced nuclear reactor applications.

36 - MATERIALS SCIENCE↗
DOE OSTI2025

Rapid and Ultrasensitive Short-Chain PFAS (GenX) Detection in Water via Surface-Enhanced Raman Spectroscopy with a Hierarchical Nanofibrous Substrate

GenX, the trade name of hexafluoropropylene oxide dimer acid (HFPO-DA) and its ammonium salt, is a short-chain PFAS that has emerged as a substitute for the legacy PFAS perfluorooctanoic acid (PFOA). However, GenX has turned out to be more toxic than people originally thought. In order to monitor and regulate water quality according to recently issued drinking water standards for GenX, rapid and ultrasensitive detection of GenX is urgently needed. For the first time, this study reports ultrasensitive (as low as 1 part per billion (ppb)) and fast detection (in minutes) of GenX in water via surface-enhanced Raman spectroscopy (SERS) using a hierarchical nanofibrous SERS substrate, which was prepared by assembling ~60 nm Ag nanoparticles on electrospun nylon-6 nanofibers through a “hot start” method. The findings in this research highlight the potential of the engineered hierarchical nanofibrous SERS substrate for enhanced detection of short-chain PFASs in water, contributing to the improvement of environmental monitoring and management strategies for PFASs.

Ismail, Ali K. (ORCID:0009000005987973)↗
DOE OSTI2024

Quantification of Hydrogen Isotopes Utilizing Raman Spectroscopy Paired with Chemometric Analysis for Application across Multiple Systems

On-line and real-time analysis of a chemical process is a major analytical challenge that can drastically change the way the chemical industry or chemical research operates. With in situ analyses, new and powerful understanding of chemistry can be gained; however, building robust tools for long-term monitoring faces many challenges that include compensating for instrument drift, instrument replacement, and sensor or probe replacement. Accounting for these changes by recollecting calibration data and rebuilding quantification models can be costly and time consuming. Here, in this study, methods to overcome these challenges are demonstrated with an application of Raman spectroscopy to monitoring hydrogen isotopes with varied speciation within dynamic gas streams. Specifically, chemical data science tools such as chemometric modeling are leveraged along with several examples of calibration transfer approaches. Furthermore, the optimization of instrument and sensors cell parameters for targeted gas phase analyses is discussed. While the particular focus on hydrogen is highly beneficial within the nuclear energy sector, mechanisms built and demonstrated here are widely applicable to optical spectroscopy monitoring in numerous other chemical systems that can be leveraged in other hazardous processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Raman Spectroscopy to Detect and Measure NOW Pheromones ("Orchard in a box")

Insect sex pheromones are chemical compounds that insects release to attract mates over distances of hundreds of meters or even kilometers, in complete darkness and without any audible signals. Use of synthetic forms of key compounds have in some cases become an essential component of monitoring and/or managing key pests of agricultural crops, including navel orangeworm (Amyelois transitella) (NOW) in California tree nuts. There are currently multiple commercially available mating disruption products available for NOW and recent studies have demonstrated that they can be effectively used to reduce crop damage. How mating disruption works is not fully established and likely varies across products and target species. For instance, it is not well understood how synthetic pheromones compete with natural pheromones and, in the case of monitoring, how efficaciously the insect follows the diffusing plumes, especially across large blocks and at plot borders. Whether an aerosol puffer is used for mating disruption or lure for monitoring population development, we currently lack the ability to fully understand how these synthetic pheromone compounds diffuse away from their point-source of emission – and subsequently how this might affect the efficacy of mating disruption and/or the accuracy of monitoring efforts. In response to these unknowns, Raman spectroscopy may offer a way to detect synthetic pheromone because of its analytical properties and recent technological advancements. In combination with nanostructured probes, RS has demonstrated the capability to detect volatiles at extremely low concentrations. We proposed to evaluate the use of Raman for the detection of synthetic and natural NOW pheromones and, were that to be successful, use this tool in subsequent years to measure pheromone diffusion in orchards.

47 OTHER INSTRUMENTATION↗
NASA NTRS2007

Effects of Short-Term Thermal Alteration on Organic Matter in Experimentally-Heated Tagish Lake Observed by Raman Spectroscopy

Carbonaceous chondrites exhibit a wide range of aqueous and thermal alteration characteristics. Examples of the thermally metamorphosed carbonaceous chondrites (TMCCs) include the C2-ung/CM2TIVs Belgica (B)-7904 and Yamato (Y) 86720. The alteration extent is the most complete in these meteorites and thus they are considered typical end-members of TMCCs exhibiting complete dehydration of matrix phyllosilicates [1, 2]. The estimated heating conditions are 10 to 10(sup 3) days at 700 C to 1 to 100 hours at 890 C, i.e. short-term heating induced by impact and/or solar radiation [3]. The chemical and bulk oxygen isotopic compositions of the matrix of the carbonate (CO3)-poor lithology of the Tagish Lake (hereafter Tag) meteorite bears similarities to these TMCCs [4]. We investigated the experimentally-heated Tag with the use of Raman spectroscopy to understand how short-term heating affects the maturity of insoluble organic matter (IOM) in aqueously altered meteorites.

Chan, Q. H. S.↗
DOE OSTI2021

Raman Spectroscopy to Detect and Measure NOW Pheromones. Annual Report [2021]

Insect sex pheromones are chemical compounds that insects release to attract mates over distances of hundreds of meters or even kilometers, in complete darkness and without any audible signals. Use of synthetic forms of key compounds have in some cases become an essential component of monitoring and/or managing key pests of agricultural crops, including navel orangeworm (Amyelois transitella) (NOW) in California tree nuts There are currently multiple commercially available mating disruption products available for NOW and recent studies have demonstrated that they can be effectively used to reduce crop damage. How mating disruption works is not fully established and likely varies across products and target species. For instance, it is not well understood how synthetic pheromones compete with natural pheromones and, in the case of monitoring, how efficaciously the insect follows the diffusing plumes and how those evolve from emission points, especially across large blocks and at plot borders. We proposed to evaluate the use of enhanced Raman spectroscopy for the detection of synthetic and natural NOW pheromones and, were that to be successful, use it in subsequent years to measure pheromone diffusion in orchards.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Raman Spectroscopy to Detect and Measure NOW Pheromones. Annual Report [Dec 2021]

Insect sex pheromones are chemical compounds that insects release to attract mates over distances of hundreds of meters or even kilometers, in complete darkness and without any audible signals. Use of synthetic forms of key compounds have in some cases become an essential component of monitoring and/or managing key pests of agricultural crops, including navel orangeworm (Amyelois transitella) (NOW) in California tree nuts There are currently multiple commercially available mating disruption products available for NOW and recent studies have demonstrated that they can be effectively used to reduce crop damage. How mating disruption works is not fully established and likely varies across products and target species. For instance, it is not well understood how synthetic pheromones compete with natural pheromones and, in the case of monitoring, how efficaciously the insect follows the diffusing plumes and how those evolve from emission points, especially across large blocks and at plot borders. We proposed to evaluate the use of enhanced Raman spectroscopy for the detection of synthetic and natural NOW pheromones and, were that to be successful, use it in subsequent years to measure pheromone diffusion in orchards.

47 OTHER INSTRUMENTATION↗
NASA NTRS2016

Characterization of Shock Effects in Calcite by Raman Spectroscopy: Results of Experiments

Carbonates comprise approx. 20% by volume of present day Earth's sedimentary rocks and store most of the terrestrial CO2 inventory. Some of the oldest meta-sedimentary rocks found on Earth contain abundant carbonate from which impact-induced release of CO2 could have played a role in the formation and evolution of the atmosphere. Carbonates are also present in the target materials for approx. 30% of all terrestrial impact structures including large impacts such as Chicxulub which happened to occur at a location with extraordinarily thick platform carbonate 3-6 km deep. The impact release of CO2 from carbonates can cause global warming as a result of the well-known greenhouse effect and have subsequent effects on climate and biota. Therefore, the shock behavior of calcite is important in understanding the Cretaceous-Paleogene event and other impacts with carbonate-bearing sediments in their target(s) such as Mars and some asteroids. A comprehensive survey utilizing a variety of techniques to characterize the effects manifest in Calcite (Iceland Spar) experimentally shocked to 60.8 GPa has been completed. Results of analysis by Raman Spectroscopy are reported here.

Bell, M. S.↗
NASA NTRS2017

Effects of Short-Term Thermal Alteration on Organic Matter in Experimentally-Heated Tagish Lake Observed by Raman Spectroscopy

Carbonaceous chondrites exhibit a wide range of aqueous and thermal alteration characteristics, while some are known to demonstrate mineralogical and petrologic evidence of having been thermally metamorphosed after aqueous alteration. This group of meteorites are commonly referred as thermally met-amorphosed carbonaceous chondrites (TMCCs), and their reflectance spectra show resemblances to that of C-type asteroids which typically have low albedos. This suggests that the surfaces of the C-type asteroids are also composed of both hydrous and dehydrated minerals, and thus TMCCs are among the best samples that can be studied in laboratory to reveal the true nature of the C-type asteroids. Although TMCCs are usually meteorites that were previously categorized as CI and CM chondrites, they are not strictly CI/CM because they exhibit isotopic and petrographic characteristics that significantly deviate from typical CI/CM. More appropriately, they are called CI-like and/or CM-like chondrites. Typical examples of TMCCs include the C2-ung/CM2TIV Belgica (B)-7904 and Yamato (Y) 86720. Thermal alteration is virtually complete in these meteorites and thus they are considered typical end-members of TMCCs exhibiting complete dehydration of matrix phyllosilicates. The estimated heating conditions are 10 to 103 days at 700 C to 1 to 100 hours at 890 C, i.e. short-term heating induced by impact and/or solar radiation. While the petrology and chemistry of TMCCs have only recently been extensively characterized, we have just begun to study in detail their organic contents. In order to understand how short-term heating affects the maturity of insoluble organic matter (IOM) in hydrous chondrites, we investigated experimentally-heated Tagish Lake meteorite using Raman spectroscopy, as the chemical and bulk oxygen isotopic compositions of the matrix of the carbonate (CO3)-poor lithology of the Tagish Lake (hereafter Tag) meteorite bears similarities to the TMCCs.

Chan, Q. H. S.↗
NASA NTRS2009

Use of Raman Spectroscopy and Delta Volume Growth from Void Collapse to Assess Overwrap Stress Gradients Compromising the Reliability of Large Kevlar/Epoxy COPVs

Composite Overwrapped Pressure Vessels (COPVs) are frequently used for storing pressurized gases aboard spacecraft and aircraft when weight saving is desirable compared to all-metal versions. Failure mechanisms in fibrous COPVs and variability in lifetime can be very different from their metallic counterparts; in the former, catastrophic stress-rupture can occur with virtually no warning, whereas in latter, a leak before burst design philosophy can be implemented. Qualification and certification typically requires only one burst test on a production sample (possibly after several pressure cycles) and the vessel need only meet a design burst strength (the maximum operating pressure divided by a knockdown factor). Typically there is no requirement to assess variability in burst strength or lifetime, much less determine production and materials processing parameters important to control of such variability. Characterizing such variability and its source is crucial to models for calculating required reliability over a given lifetime (e.g. R = 0.9999 for 15 years). In this paper we present a case study of how lack of control of certain process parameters in COPV manufacturing can result in variations among vessels and between production runs that can greatly increase uncertainty and reduce reliability. The vessels considered are 40-inch ( NASA Glenn Research center, Cleveland, OH, 44135 29,500 in3 ) spherical COPVs with a 0.74 in. thick Kevlar49/epoxy overwrap and with a titanium liner of which 34 were originally produced. Two burst tests were eventually performed that unexpectedly differed by almost 5%, and were 10% lower than anticipated from burst tests on 26-inch sister vessels similar in every detail. A major observation from measurements made during proof testing (autofrettage) of the 40-inch vessels was that permanent volume growth from liner yielding varied by a factor of more than two (150 in3 to 360 in3 ), which suggests large differences in the residual stress gradient through their overwraps. This resulted in large uncertainty in true fiber stress ratio (fiber stress at operating pressure divided by fiber stress at burst) which governs lifetime. The vessels were originally designed with tight safety margins, so it became crucial to develop a non-destructive evaluation (NDE) technique to directly measure the overwrap residual stress state of each vessel, and to identify those vessels at highest risk of having poor reliability. This paper describes a Raman Spectroscopy technique for measuring certain patterns of fluctuation in fiber elastic strains over the outside vessel surface (where all but one wrap is exposed at certain locations) that are shown to directly correlate to increased fiber stress ratios and reduced reliability.

Kezirian, Michael T.↗
DOE OSTI2024

Carbon fiber classification using raman spectroscopy

Carbon fiber characterization processes are described that include multi-condition Raman spectroscopy-based examination combined with multivariate data analyses. Methods are a nondestructive material characterization approach that can provide predictions as to carbon fiber bulk physical properties, as well as identification of unknown carbon fiber materials for quality control purposes. The framework of the multivariate analysis methods includes a principal component-based identification protocol including comparison of Raman spectral data from an unknown carbon fiber with a data library of multiple principal component spaces.

Houk, Amanda L.↗
DOE OSTI2025

Evidence for Ga clusters in β-Ga 2 O 3 from Raman spectroscopy and density functional theory

Monoclinic gallium oxide (β-Ga 2 O 3 ) single crystals have a Raman mode at ∼250 cm −1 that is strongly correlated with free-electron density. Prior work attributed this peak to an electronic excitation of a shallow donor impurity band. However, heavily n-type thin films grown by metalorganic chemical vapor deposition or molecular beam epitaxy do not have the peak. In the present work, an alternate model is proposed: the 250 cm −1 Raman peak arises from Ga clusters, defined as two or more Ga atoms that form Ga–Ga bonds. Raman mapping reveals variations in the frequency that are consistent with a distribution of cluster sizes. The intensity of the peak decreases as the temperature is raised, attributed to melting of the Ga clusters. First-principles calculations indicate that the 250 cm −1 mode is due to Ga–Ga bond-stretching vibrations. As the Fermi energy is raised, the formation of Ga–Ga dimers becomes energetically favorable, explaining the correlation between n-type conductivity and the appearance of the Raman peak.

36 MATERIALS SCIENCE↗
DOE OSTI2024

High-temperature Raman spectroscopy of K 2 Ca(CO 3 ) 2 bütschliite and Na 2 Ca 2 (CO 3 ) 3 shortite

Raman spectra of Na 2 Ca 2 (CO 3 ) 3 shortite and K 2 Ca(CO 3 ) 2 bütschliite were measured to 715°C and 740°C respectively, under vacuum. The vibrational spectra demonstrate that shortite converts to nyerereite (Na 2 Ca(CO 3 ) 2 ) and calcite at 535°C. This assemblage is stable to ~700°C, where nyerereite begins to decompose. Bütschliite converts to the isochemical phase fairchildite at 570°C, which is stable to 665°C, where it decomposes to an assemblage of K 2 CO 3 and CaO. The variation of anharmonicity between different vibrational modes of each of the low temperature phases is assessed, and these yield insights into inter-carbonate group couplings. In conclusion, both fairchildite and nyerereite exhibit spectral features consistent with extensive disordering.

58 GEOSCIENCES↗