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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 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

New Material for Surface-Enhanced Raman Spectroscopy

A chemical method of synthesis and application of coating materials that are especially suitable for surface-enhanced Raman spectroscopy (SERS) has been developed. The purpose of this development is to facilitate the utilization of the inherently high sensitivity of SERS to detect chemicals of interest (analytes) in trace amounts, without need for lengthy sample preparation. Up to now, the use of SERS has not become routine because the methods available have not been able to reproduce sampling conditions and provide quantitative measurements. In contrast, the coating materials of the present method enable analysis with minimum preparation of samples, and SERS measurements made using these materials are reproducible and reversible. Moreover, unlike in methods investigated in prior efforts to implement SERS, sampling is not restricted to such specific environments as electrolytes or specific solvents. The coating materials of this method are porous glasses, formed in sol-gel processes, that contain small particles of gold or silver metal. Materials of this type can be applied to the sample-contact surfaces of a variety of sampling and sensing devices, including glass slides, glass vials, fiber-optic probes, and glass tubes. Glass vials with their insides coated according to this method are particularly convenient for SERS to detect trace chemicals in solutions: One simply puts a sample solution containing the analyte(s) into a vial, then puts the vial into a Raman spectrometer for analysis. The chemical ingredients and the physical conditions of the sol-gel process have been selected so that the porous glass formed incorporates particles of the desired metal with size(s) to match the wavelength(s) of the SERS excitation laser in order to optimize the generation of surface plasmons. The ingredients and processing conditions have further been chosen to tailor the porosity and polarity of the glass to optimize the sample flow and the interaction between the analyte(s) and the plasmon field that generates Raman photons. The porous silica network of a sol-gel glass creates a unique environment for stabilizing SERS-active metal particles. Relative to other material structures that could be considered for SERS, the porous silica network offers higher specific surface area and thus greater interaction between analyte molecules and metal particles. Efforts to perform SERS measurements with the help of sampling devices coated by this method have been successful. In tests, numerous organic and inorganic chemicals were analyzed in several solvents, including water. The results of the tests indicate that the SERS measurements were reproducible within 10 percent and linear over five orders of magnitude. One measure of the limits of detectability of chemicals in these tests was found to be a concentration of 300 parts per billion. Further development may eventually make it possible to realize the full potential sensitivity of SERS for detecting some analytes in quantities as small as a single molecule.

Farquharson, Stuart↗
NASA NTRS2007

Single-Shot Rotational Raman Thermometry for Turbulent Flames Using a Low-Resolution Bandwidth Technique

An alternative optical thermometry technique that utilizes the low-resolution (order 10(exp 1)/cm) pure-rotational spontaneous Raman scattering of air is developed to aid single-shot multiscalar measurements in turbulent combustion studies. Temperature measurements are realized by correlating the measured envelope bandwidth of the pure-rotational manifold of the N2/O2 spectrum with a theoretical prediction of a species-weighted bandwidth. By coupling this thermometry technique with conventional vibrational Raman scattering for species determination, we demonstrate quantitative spatially resolved, single-shot measurements of the temperature and fuel/oxidizer concentrations in a high-pressure turbulent Cf4-air flame. Our technique provides not only an effective means of validating other temperature measurement methods, but also serves as a secondary thermometry technique in cases where the anti-Stokes vibrational N2 Raman signals are too low for a conventional vibrational temperature analysis.

Kojima, Jun↗
NASA NTRS2013

Surface-Enhanced Raman Scattering Using Silica Whispering-Gallery Mode Resonators

The motivation of this work was to have robust spectroscopic sensors for sensitive detection and chemical analysis of organic and molecular compounds. The solution is to use silica sphere optical resonators to provide surface-enhanced spectroscopic signal. Whispering-gallery mode (WGM) resonators made from silica microspheres were used for surface-enhanced Raman scattering (SERS) without coupling to a plasmonic mechanism. Large Raman signal enhancement is observed by exclusively using 5.08-micron silica spheres with 785-nm laser excitation. The advantage of this non-plasmonic approach is that the active substrate is chemically inert silica, thermally stable, and relatively simple to fabricate. The Raman signal enhancement is broadly applicable to a wide range of molecular functional groups including aliphatic hydrocarbons, siloxanes, and esters. Applications include trace organic analysis, particularly for in situ planetary instruments that require robust sensors with consistent response.

Anderson, Mark S.↗
NASA NTRS2016

Electride Mediated Surface Enhanced Raman Scattering (SERS)

An electride may provide surface enhanced Raman scattering (SERS). The electride, a compound where the electrons serve as anions, may be a ceramic electride, such as a conductive ceramic derived from mayenite, or an organic electride, for example. The textured electride surface or electride particles may strongly enhance the Raman scattering of organic or other Raman active analytes. This may also provide a sensitive method for monitoring the chemistry and electronic environment at the electride surface. The results are evidence of a new class of polariton (i.e., a surface electride-polariton resonance mechanism) that is analogous to the surface plasmon-polariton resonance that mediates conventional SERS.

Anderson, Mark S.↗
NASA NTRS2020

PIV and Rotational Raman-Based Temperature Measurements for CFD Validation of a Perforated Plate Cooling Flow: Part I

Film cooling is used in a wide variety of engineering applications for protection of surfaces from hot or combusting gases. The design of more efficient film cooling geometries/configurations could be facilitated by an ability to accurately model and predict the effectiveness of current designs using computational fluid dynamics (CFD) code predictions. Hence, a benchmark set of flow field property data was obtained to assess current CFD capabilities and develop better modeling approaches for these turbulent flow fields where accurate calculation of turbulent heat flux is important. Both Particle Image Velocimetry (PIV) and spontaneous rotational Raman scattering (SRS) spectroscopy were used to acquire high quality, spatially-resolved measurements of the mean and root mean square (rms) velocities as well as the mean and rms temperatures in a film cooling flow field. In addition to off-body flow field measurements, infrared thermography (IR) and thermocouple measurements on the plate surface enabled estimates of the film effectiveness. Raman spectra in air were obtained across a matrix of axial locations downstream from a 68.07 mm square nozzle blowing heated air over a range of temperatures (up to TR = 2.7) and Mach numbers (up to Mach 0.9), across a 30.48 cm long plate equipped with three patches of 45 small (~1 mm) diameter cooling holes arranged in a staggered configuration. In addition, both streamwise 2-component PIV (on the plate centerline) and cross-stream 3-component Stereo PIV data at 14 axial stations were collected in the same flows. Only a subset of the data collected in the test program is included in this Part I report. The rest of the data will be published in a future report, Part II, along with planned CFD predictions of the complex cooling film flow. The entire data set of Raman temperature data, PIV velocity data and IR camera data covering the Set Points 23 and 49 in the test matrix in Table 1 is available in an accompanying DVD (available online from www.sti.nasa.gov) for those interested in further analysis.

Nozzle↗
NASA NTRS2020

PIV and Rotational Raman-Based Temperature Measurements for CFD Validation of a Perforated Plate Cooling Flow Part I

Film cooling is used in a wide variety of engineering applications for protection of surfaces from hotor combusting gases. The design of more efficient film cooling geometries/configurations could be facilitated by an ability to accurately model and predict the effectiveness of current designs using computational fluid dynamics (CFD) code predictions. Hence, a benchmark set of flow field property data were obtained to assess current CFD capabilities and develop better modeling approaches for these turbulent flow fields where accurate calculation of turbulent heat flux is important. Both Particle Image Velocimetry (PIV) and spontaneous rotational Raman scattering (SRS) spectroscopy were used to acquire high quality, spatially-resolved measurements of the mean and root mean square (rms) velocities as well as the mean and rms temperatures in a film cooling flow field. In addition to off-body flow field measurements, infrared thermography (IR) and thermocouple measurements on the plate surface enabled estimates of the film effectiveness. Raman spectra in air were obtained across a matrix of axial locations downstream from a 68.07 mm square nozzle blowing heated air over a range of temperatures (up to TR =2.7) and Mach numbers (up to Mach 0.9), across a 30.48 cm long plate equipped with three patches of 45 small (~1 mm) diameter cooling holes arranged in a staggered configuration. In addition, both streamwise 2-component PIV (along the plate centerline) and cross-stream 3-component Stereo PIV data at 14 axial stations were collected in the same flows. Only a subset of the data collected in the test program is included in this Part 1 report. The rest of the data will be published in a future report, Part 2, along with planned CFD predictions of the complex cooling film flow.The entire data set of Raman temperature data, PIV velocity data and IR camera data covering the Set Points 23 and 49 in the test matrix in Table 1 is available in an accompanying DVD (available online from www.sti.nasa.gov) for those interested in further analysis.

Mark P Wernet↗
NASA NTRS2023

Constructing a Raman Spectroscopy System

The project aims to understand how Raman spectroscopy works by constructing a system based on existing concepts of the technique and utilizing NASA’s available tools and software to analyze the collected data. Once the data is successfully interpreted and proven, other improvements to the assembled system will then be explored. Part of the paper goes through several phases of construction of the system and improvements made. Nevertheless, the data obtained and the results were unsatisfactory as they need to be further analyzed for accuracy. The ultimate ambition was to be able to assist NASA with its objective of implementing a remote and compact Raman spectroscopy system on a rover for future planetary surface characterization such as Mars and lunar surfaces via a Raman spectroscopy system that the agency’s Senior Engineer, Dr. M. Nurul Abedin, has been working on since the early 2000s [2,3,4].

Jake Nguyen↗
NASA NTRSDate not supplied

An Overview of SHERLOC Raman and Fluorescence Spectroscopy Results Obtained During Perseverance’s Green Zone Campaign at Jezero Crater, Mars

The Perseverance rover landed in Jezero crater, Mars, in February 2021. The field site was chosen because orbiter data provided evidence that the crater hosted an ancient (>2.7 Ga) fluvio-lacustrine environment. The Octavia E. Butler landing site is located ~1.9 km east of the erosional remnant of the Jezero river delta. Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) is an arm-mounted instrument that combines fluorescence and Raman spectroscopy with microscopic imaging to analyze geological materials in order to better understand the history of the environments recorded in the rocks within Jezero crater and to search for potential biosignatures. SHERLOC has two microscopic cameras, the Autofocus and Context Imager (ACI) and the Wide-Angle Topographic Sensor for Operations and eNgineering, (WATSON). These subsystems obtain high spatial resolution (10.1–100 µm/pixel) images to identify grain-scale structure and texture. SHERLOC spectroscopy enables high-sensitivity detection, characterization, and spatially-resolved correlation of trace organic materials. SHERLOC’s 248.6 nm deep UV laser generates a 100 µm-diameter spot. Photons generated by Raman scattering and fluorescence emission are collected and the spectra are downlinked to Earth for analysis. Knowledge of where the laser is pointed allows for mineral and compositional maps to be generated and overlain in ACI and WATSON images. Early spectroscopy observations focused on natural rock surfaces at targets named Nataani (sol 83), Bi_la_sana (sol 98) and Foux (sol 141). These surfaces included patches of aeolian dust that had settled upon the rocks. Perseverance’s abrasion tool is expected to become available in August 2021; it will grind to depths of 14 mm to remove dust and penetrate coatings and weathering rinds. This presentation will summarize major results from analysis of the rocks examined by SHERLOC during Perseverance’s first science and sample coring campaign (Green Zone Campaign).

Luther W Beegle↗
NASA NTRSDate not supplied

Classifying Agnostic Biosignatures using Raman, VNIR, and Elemental Data

How can we use our current wealth of terrestrial data, encompassing biogenic and abiogenic systems, to determine the distinguishing properties of life? SCOBI (Statistical Classification of Biosignature Information) uses machine learning techniques to algorithmically identify combinations of measurements that are “indicative of life”. A set of ~1000 observations, comprising elemental abundance, isotopic fractionation, VNIR reflectance, and (in progress) Raman spectra, have been assembled from existing literature and databases. The observations cover systems classified as “indicative alive” (e.g., cells, vegetation), “indicative non-alive” (e.g., fossils, teeth), “mixed indicative” (e.g., soil, pond water), or “non-indicative” (e.g., rocks, meteorites). VNIR data was preprocessed by linear interpolation from 400-2100 nm and smoothed with a Savitzky-Golay filter. To limit the amount of Earth-biochemistry-specific (non-agnostic) information included, the first five spectral features extracted were number of peaks, number of troughs, mean reflectance, mean peak width, and broadest peak width. To help further emphasize agnostic biosignatures, Earth-specific features such as chlorophylls have been manually flagged so that feature importance with and without them can be compared. Classifiers including k-nearest neighbors (KNN), Gaussian Naïve Bayes (GNB), logistic regression (LR), random forest (RF), and support vector machine (SVM) were implemented, as was a combination voting classifier. Performance metrics included false positive rates, false negative rates, and AUC with 50-50 test/train splits (Monte Carlo simulations). Key takeaways from this stage, prior to the inclusion of Raman spectra, are (1) the overall success rate of 0.933 AUC was most heavily influenced by the elemental abundance data; and (2) VNIR reflectance had the lowest classification performance with 0.52 AUC (58% of objects correctly classified). The next steps are to complete integration of Raman spectral data and to improve the approach to pre-processing and feature extraction for both types of spectral data, such as automated baseline removal, whole spectrum matching, and dimensionality reduction.

Biosignatures↗
NASA NTRSDate not supplied

Effects of Mars Analogue Dust Deposition on DUV Raman Spectra: Implications for the Mars2020 Perserverance Rover SHERLOC Instrument

The Scanning Habitable Environments with Raman & Luminescence for Organics & Chemicals (SHERLOC) instrument suite includes a deep ultraviolet (DUV) Raman and fluorescence instrument on the robotic arm of the Mars2020 (M2020) Perseverance rover [1]. When sufficiently thick dust coatings are present, substrate surfaces are not detected, and mineralogical information not obtained. For example, the effect of palagonitic dust coatings as a function of depth to various substrates on thermal emission, VNIR, and Mössbauer spectra are reported by [2, 3]. In this study, we use the same palagonitic dust to study the effect of dust coating thickness on DUV Raman spectra.

N. C. Haney↗
DOE OSTI2021

Raman Microscopy Analysis of Wyoming CarbonSAFE Pilot Well Thin Sections for Mineralogy and Organic Matter Characterization

Scanning confocal Raman microspectroscopy (RMS) was used to analyze thin sections for inorganic mineral content and for evaluation of organic material (OM). Thin sections were selected from a stratigraphic test well core in the Powder River Basin, Wyoming under the Wyoming CarbonSAFE project. The well was analyzed with a variety of rock and fluid characterization techniques to determine the feasibility of a commercial-scale CO2 storage site. RMS complements other analyses, including traditional petrography, SEM, porosity and permeability, and XRD For this aspect of the study, RMS is especially important in the evaluation of OM in sealing lithologies. At prospective geologic CO2 storage sites, it is imperative to assess the unconventional oil and gas potential of seals to ensure that any future development would not compromise the integrity of the seals. Whole-slide mineralogical surveys were performed on thin sections from various shale and sandstone formations. Surveys were analyzed with Direct Classical Least Squares to identify and quantify minerals. The location and concentration of minerals was color-coded and overlaid on optical images for visualization of the distribution of minerals. Dense hyperspectral Raman mapping of OM was performed on five thin sections. Eleven spectral parameters diagnostic of organic type and thermal maturity were used to train a Partial Least Squares (PLS) calibration against a set of artificially matured samples spanning the pre- to mid-oil window. The PLS was applied to the study set and a post-mature set. Additionally, the PLS was applied to each point in hyperspectral maps for visualization of trends in maturity across sample sets and discrimination of organic matter types within a given map. In inorganic surveys on thin sections, a total of 14 unique inorganic minerals were identified in Raman spectra including quartz, dolomite, calcite, hematite and anhydrite. Shale thin sections tended to be dominated by organic material. OM was often observed mixed with inorganic minerals. Sand- and mudstones were dominated by inorganic minerals. The PLS extrapolated the post-mature set to reflectances >1.2%. The study set ranged from very immature to postmature in the median of map fit-peak parameters. However, point maturity maps indicate that matrix OM in all study samples is immature and that discreet organic particles selected for mapping, which may be inertinites, bias medians towards more-mature. The work demonstrates the capabilities of RMS to perform both whole-slide mineralogy and OM analysis with applications to formation evaluation in oil & gas, carbon sequestration and mining. Here, analysis of sealing formations in the well indicates high levels of immature organic matter that would not be a viable target for future oil production that could compromise the CO2 storage site. The work brings together diverse disciplines from geology and petrography to analytical chemistry, big data and microscopy.

Myers, Grant↗
DOE OSTI2022

The electronic Raman scattering spectrum of PuO 2

Here the Raman spectrum of PuO 2 was measured up to 13,000 cm –1 with three different laser excitation wavelengths spanning the resonance (405 nm), near-resonance (457 nm), and preresonance (514 nm) energy range. Approximately 26 never-before-seen bands were observed between 3500 and 13,000 cm –1 . Given the very high energy of the Raman shifts of these bands and the relative insensitivity of their spectral position to the interrogating laser wavelength, they are believed to arise from an electronic origin. These bands are present in both freshly calcined and radiolytically aged PuO 2 , although a broad luminescence is observed in the aged material, which obscures many of the high frequency features. In situ laser annealing of the material attenuated this luminescence and allowed for clear observation of these never-before-seen spectral features. Discovery of these high-energy bands presents a new way of identifying PuO 2 for nuclear nonproliferation and forensics purposes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

A Closer Look at Tip-Enhanced Raman Chemical Reaction Nanoimages

Tip-enhanced Raman spectroscopy (TERS) is a powerful technique that enables ultrahigh spatial resolution and ultrasensitive chemical imaging. This technique’s ability to track plasmon-induced/enhanced chemical reactions in real space has gained increasing popularity in recent years. Here, in this study, we expose inherent difficulties associated with assigning TERS signatures that accompany chemical transformations. Namely, distinct selection rules as well as the possibility of multiple physical processes/chemical reaction pathways complicate spectral assignments and necessitate caution in assigning the experimental observables. We illustrate the latter using 4,4'-dimercaptostilbene-functionalized plasmonic silver nanocubes, wherein we identify the TERS signatures of product formation, molecular charging, multipolar Raman scattering, and preferred molecular orientations that all lead to distinct and assignable spectral patterns.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Multipolar Raman Scattering vs Interfacial Nanochemistry: Case of 4-Mercaptopyridine on Gold

Caution needs to be exercised in associating changes in plasmon-enhanced Raman spectra with chemical transformations. This is demonstrated through a detailed analysis of tip-enhanced Raman (TER) scattering from 4-mercaptopyridine (MPY) on gold. The substrate used consists of gold nanoplates atop a gold surface featuring heterogeneous grooves, all coated with a monolayer of MPY. The brightest spectra across the substrate exhibit features that can only be recovered by considering the generalized polarizability of oriented MPY molecules. Finally, the complex TER spectra we observe do not mark interfacial chemistry, but rather, multipolar TER scattering driven by local field gradients.

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

High-pressure response of vibrational properties of b-As x P 1– x : in situ Raman studies

The structural evolution of black arsenic-phosphorous (b-As x P 1–x ) alloys with varying arsenic concentrations was investigated under hydrostatic pressure using in situ Raman spectroscopy. High-pressure experiments were conducted using a diamond anvil cell, which revealed pressure-induced shifts in vibrational modes associated with P–P bonds (A 1 g , A 2 g , ${B}_{2g}$), As–As bonds (A 1 g , A 2 g , ${{B}}_{2g}$), and As–P bonds in b-As x P 1–x alloys. Two distinct pressure regimes were observed. In the first regime (region I), all vibrational modes exhibited a monotonic upshift, indicating phonon hardening due to hydrostatic pressure. In the second regime (region II), As 0.4 P 0.6 and As 0.6 P 0.4 alloys displayed a linear blueshift (or negligible change in some modes) at a reduced rate, suggesting local structural reorganization with less compression on the bonds. Notably, the alloy with the highest As concentration, As 0.8 P 0.2 , exhibited anomalous behavior in the second pressure regime, with a downward shift observed in all As–As and As–P Raman modes (and some P–P modes). Interestingly, the emergence of new peaks corresponding to the E g mode and A 1g mode of the gray-As phase was observed in this pressure range, indicating compressive strain-induced structural changes. The anomalous change in region II confirms the formation of a new local structure, characterized by elongation of the P–P, As–As, and As–P bonds along the zigzag direction within the b-As x P 1–x phase, possibly near the grain boundary. Additionally, a gray-As phase undergoes compressive structural changes. This study underscores the significance of pressure in inducing structural transformations and exploring novel phases in two-dimensional materials, including b-As x P 1–x alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Electrolyte Solvation and Ionic Association. VII. Correlating Raman Spectroscopic Data with Solvate Species

Raman spectroscopy is a widely utilized method for determining information about the solvate species present in electrolyte solutions. Difficulties arise, however, when interpreting the Raman data in terms of correlating the spectroscopic vibrational bands with specific solvate species. Examples are provided to demonstrate how erroneous conclusions may be drawn with regard to the identity and population (distribution) of the solvent-separated ion pair (SSIP), contact ion pair (CIP) and aggregate (AGG) solvate species frequently mentioned in the scientific literature.

contact ion pairs↗
DOE OSTI2025

An Optothermal Raman Model Accounting for Convection, Radiation, and Substrate Effects for Evaluation of the Thermal Conductivity of Two‐Dimensional Coatings

Thermal conductivity of two‐dimensional (2D) materials is important to characterize as this will govern thermal transport physics in the various thermal and energy applications benefitting from the unique properties of these materials. Here, analytical and numerical techniques are presented to determine the thermal conductivity and interfacial conductance of a 2D material coating using confocal micro‐Raman spectroscopy as a noncontact diagnostic. While several methods have been proposed for calculating the values of thermal conductivity, interfacial conductance, and spatial temperature profile, these models often do not consider effects of radiation, convection, and substrate resistance on the temperature and heat flux profiles. We present a model to calculate the thermal conductivity and interfacial conductance which accounts for convection, radiation, and substrate effects to characterize a variety of 2D material coatings, which is demonstrated using large area graphene transferred onto copper and nickel substrates. Convection and radiation effects are found to have a negligible effect on the temperature profile of supported coatings, while the substrate effects have a considerable effect and therefore impact the quantification of thermal conductivity and interfacial conductance in addition to limiting the spatial resolution of the technique. These findings will allow for more accurate and reproducible extraction of the thermal conductivity of graphene and other 2D material coatings when employing noncontact optothermal Raman spectroscopy methods.

2D coatings↗
DOE OSTI2022

Raman signatures of detonation soot

Soot generated from the detonation of nine explosives was investigated with Raman microspectroscopy and high-resolution transmission electron microscopy (HRTEM). The first order bands, located at approximately 1,580 (G), 1,350 (D1), 1,620 cm –1 (D2), 1,500 (D3), and 1,200 (D4), are used to provide information on the carbon allotropes and defects. The intensity ratios and the full-width at half-maximum provide an indication of the disorder in the material. The Raman spectra of soot acquired from the detonation of nine explosives showed differences which can be used to identify the precursor explosive. Overall, most differences in the spectra were correlated with the presence of amorphous carbon in the soot. In additional to identification of distinct bands in the spectra via deconvolution, principal component analysis was also used to differentiate the different types of soot. HRTEM performed on soot samples with different explosive precursors identified several distinct allotropes of carbon such as nanodiamonds, carbon onions, graphite fibers, and amorphous carbon.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗