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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Raman-shifting an ArF excimer laser to generate new lines for obtaining optical diagnostic based information in flow fields

The application of tunable excimer lasers in combustion and flow diagnostics is almost routine nowadays. The properties of this laser system that enable density and temperature measurements in supersonic and hypersonic flow fields to be conducted are its high power, high repetition rate, and high spectral brightness. The limitation imposed by this system on these measurements is the paucity of lines in the wavelength region, the vacuum-ultraviolet, where species of interest, such as OH, N2, O2, H2, H2O, CO, NO, etc., are susceptible to electronic excitation to high-lying states. To circumvent this problem one normally resorts to nonlinear optical techniques such as frequency conversion via stimulated Raman scattering (SRS), more commonly known as Raman shifting or Raman mixing, to extend these nonintrusive and nonperturbing techniques to the shorter wavelengths in the VUV region and, for that matter, to longer wavelengths in the infrared region, if the need arises. The theoretical basis of SRS and its application are well documented in the literature. In essence, the Raman shift is a consequence of the inelastic scattering of the incident radiation by the sample. Most of the scattered radiation from the molecules of the sample is unchanged in frequency. However, a small fraction of the incident radiation is changed in frequency. This shift is a result of the fact that some of the incident photons on colliding with the molecules of the sample give up some of their energy and emerge with a lower energy resulting in the lower-frequency Stokes radiation. Other incident photons may increase their energy by colliding with the vibrationally excited molecules of the medium and emerge as higher-frequency antistokes radiation. The generation of the latter is the main objective of this project. The process, however, depends on several factors, including the beam quality of the pump laser, the cross-section of the gaseous medium, the gas pressure, and the ambient temperature of the gas near the focal region. Furthermore, since the Raman shifting process is polarization sensitive, it is necessary to have all of the laser energy in a single polarization. These factors were taken into consideration in the execution of the project. The implementation of the Raman shift was accomplished by focusing the 193 nm output of an ArF excimer laser (Lamda-Physik LPX 150) into a 1-meter long high pressure recirculating Raman cell filled with H2 gas. The laser system was modified in order to improve the mode quality of the pump beam to enhance the Raman shifting. To accomplish this feat, a prism beam expander and grating on the oscillator discharge provided wavelength tuning over the excimer gain profile. Furthermore, a triple-pass configuration, as opposed to unstable resonator optics, was employed in the operation of the amplifier cavity so that when the oscillator output radiation, focused by a 51-cm focal length fused silica lens through a 50 micron pinhole (serving as a spatial filter) and recollimated with a 25-cm focal length lens, was fed into the amplifier, it was injection locked, thereby providing tunable radiation with relatively low divergence. The forward scattered radiation emanating from the impingement of the modified pump beam on the Raman cell was detected using an energy meter after the latter had been separated from it using a dispersing prism.

Koker, Edmond B.↗
DOE OSTI2022

Combined Raman and Turbidity Probe for Real-Time Analysis of Variable Turbidity Streams

We know that real-time and in situ process monitoring is a powerful tool that can empower operators of hazardous processes to better understand and control their chemical systems without increased risk to themselves. However, applying monitoring techniques to complex chemical processes can face challenges. An example of this is the application of optical spectroscopy, otherwise capable of providing detailed chemical composition information, to processes exhibiting variable turbidity. Here, details on a novel combined Raman spectroscopy and turbidimetry probe are discussed. Furthermore, the analytical approach to accurately account for both Raman signal and turbidity while quantifying chemical targets is detailed. Through leveraging Raman and turbidity data simultaneously collected from the combined probe within chemometric models, accurate quantification of multiple chemical targets can be achieved under conditions of variable concentrations and turbidity.

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

Crowd-Sourced Data and Analysis Tools for Advancing the Chemical Vapor Deposition of Graphene: Implications for Manufacturing

Industrial production of graphene by chemical vapor deposition (CVD) requires more than the ability to synthesize large domain, high-quality graphene in a lab reactor. The integration of graphene in the fabrication process of electronic devices requires the cost-effective and environmentally friendly production of graphene on dielectric substrates, but current approaches can only produce graphene on metal catalysts. Sustainable manufacturing of graphene should also conserve the catalyst and reaction gases, but today the metal catalysts are typically dissolved after synthesis. Progress toward these objectives is hindered by the hundreds of coupled synthesis parameters that can strongly affect CVD of low-dimensional materials and poor communication in the published literature of the rich experimental data that exists in individual laboratories. We report here on a platform, "graphene recipes for synthesis of high quality material" (Gr-ResQ: pronounced graphene rescue), which includes powerful new tools for data-driven graphene synthesis. At the core of Gr-ResQ is a crowd-sourced database of CVD synthesis recipes and associated experimental results. The database captures similar to 300 parameters ranging from synthesis conditions such as a catalyst material and preparation steps, to ambient lab temperature and reactor details, as well as resulting Raman spectra and microscopy images. These parameters are carefully selected to unlock the potential of machine-learning models to advance synthesis. A suite of associated tools enable fast, automated, and standardized processing of Raman spectra and scanning electron microscopy images. To facilitate community-based efforts, Gr-ResQ provides tools for cyber-physical collaborations among research groups, allowing experiments to be designed, executed, and analyzed by different teams. Gr-ResQ also allows publication and discovery of recipes via the Materials Data Facility, which assigns each recipe a unique identifier when published and collects parameters in a search index. We envision that this holistic approach to data-driven synthesis can accelerate CVD recipe discovery and production control and open opportunities for advancing not only graphene but also many other 1D and 2D materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Raman Digital Twin of Monolayer Janus Transition Metal Dichalcogenides

Monolayer transition metal dichalcogenides (TMDs) are a key class of two-dimensional (2D) materials with broad technological potential. Their Janus counterparts exhibit unique properties due to broken out-of-plane symmetry and further enrich the functionalities of TMDs. However, experimental synthesis and identification of Janus TMDs remain challenging. It is thus highly desirable to have a rapid, simple, and in situ characterization technique to monitor, in real time, the conversion process from the parent to Janus structure. Raman spectroscopy stands out for such a task as it is a powerful, nondestructive, and very commonly used tool to characterize 2D materials both in situ and ex situ. To realize the full potential of Raman spectroscopy on rapid characterization of Janus TMDs, we present a computational “Raman digital twin” library for various monolayer Janus TMDs in both 2H and Td phases. We focus on group-6 TMDs: MoS 2 , WS 2 , MoSe 2 , WSe 2 , MoTe 2 , WTe 2 and their Janus variants: MoSSe, MoSTe, MoSeTe, WSSe, WSTe, and WSeTe. Using first-principles density functional theory (DFT), we calculate their vibrational properties and predict distinct Raman fingerprints. These phonon and Raman signatures reflect each material’s structural symmetry and atomic composition, enabling clear identification via Raman spectroscopy. Our theoretical work supports experimental efforts by providing benchmarks for material identification, structural analysis, and quality control. In conclusion, the computational library expedites the discovery and development of Janus 2D materials, facilitating tighter integration between theoretical predictions and experimental validation.

Chalcogenides↗
DOE OSTI2020

Overcoming Oxidation State-Dependent Spectral Interferences: Online Monitoring of U(VI) Reduction to U(IV) via Raman and UV–vis Spectroscopy

Analytical characterization of chemical processes is an essential component of both industrial processes and fundamental studies. Applicable techniques abound, but optical spectroscopy has the unique combination of being easily incorporated into on-line (in-situ) monitoring probes and can also provide abundant chemical information (concentration, oxidation state, speciation). However, this abundance of chemical information can make applying optical spectroscopy to complex chemical processes challenging. This is particularly evident in the bulk electrolysis of U(VI) to U(IV), an essential preparatory step in some nuclear fuel recycling schemes. Starting and product materials have interfering spectral signatures in both electronic and vibrational spectroscopies, making accurate and real-time analysis difficult to achieve. In this paper, we discuss the application of optical spectroscopy to the on-line monitoring of a bulk electrolysis process and the methods utilized to analyze data as well as characterize the efficiency and mechanism of U(IV) generation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1987

In situ process diagnostics of silane plasma for device-quality a-Si:H deposition

Coherent anti-Stokes Raman spectroscopy (CARS) and mass spectrometry (MS) have been applied to in situ process diagnostics of a silane plasma for device-quality a-Si:H film deposition. Silane depletion was directly measured by CARS and is linearly dependent on RF power in the region of 4-12 W with a slope of 0.5 percent/mW-sq cm. The depletion is also dependent on SiH4 flow rate starting with a 50 percent depletion at a low flow rate of 5.6 sccm and asymptotically approaching an 8 percent depletion at a flow rate of 80 sccm. The mass spectral line signal intensity of disilane increases with RF power and shows an apparent transition at 6 W. Disilane formation in silane plasma, film deposition rate, and silane depletion ratio as a function of the RF power indicate that the film growth mechanism in the low-power region of 3.5-6.5 W is substantially different from that in the high-power region of 6.5-12 W.

Shing, Y. H.↗
DOE OSTI2023

In-situ Synthesis of PuCl 3 and Corresponding Raman and Density Functional Theory Vibrational Modes

The experimental and calculated Raman spectrum of PuCl 3 has been reported for the first time. PuCl 3 is a primary species found in plutonium metal refinement, specifically in pyrochemical salt processes including multicycle direct oxide reduction, metal chlorination, and electrorefining. As such, Raman signatures of PuCl 3 could serve as potential forensic indicators of material process history. A novel technique for synthesizing PuCl 3 from the in situ chlorination of plutonium metal with HCl was developed to establish these signatures. Cerium metal surrogates were utilized to ensure optimization of the plutonium experiments and to minimize personnel exposure, and all experiments were carried out in a Raman reaction chamber designed for air-tight, high vacuum environments. In situ Raman spectroscopy was employed in conjunction with density functional theory (DFT) to investigate the vibrational modes of PuCl 3 . Associated mixed oxy and hydroxyl phases are also reported. The combined Raman and DFT results have eliminated inconsistencies in Raman mode assignments for the MX 3 family of metal chlorides having P6 3 /m symmetry, and IR modes derived from the DFT calculations are additionally presented. The data observed in this study are of potential interest to nuclear forensic analyses, nuclear sample aging, nuclear energy, plutonium processing, and stockpile stewardship.

36 MATERIALS SCIENCE↗
DOE OSTI2023

In-situ Synthesis of PuCl 3 and Corresponding Raman and Density Functional Theory Vibrational Modes

The experimental and calculated Raman spectrum of PuCl 3 has been reported for the first time. PuCl 3 is a primary species found in plutonium metal refinement, specifically in pyrochemical salt processes including multicycle direct oxide reduction, metal chlorination, and electrorefining. As such, Raman signatures of PuCl 3 could serve as potential forensic indicators of material process history. A novel technique for synthesizing PuCl 3 from the in-situ chlorination of plutonium metal with HCl was developed to establish these signatures. Cerium metal surrogates were utilized to ensure optimization of the plutonium experiments and to minimize personnel exposure, and all experiments were carried out in a Raman reaction chamber designed for air-tight, high vacuum environments. In-situ Raman spectroscopy was employed in conjunction with Density Functional Theory (DFT) to investigate the vibrational modes of PuCl 3 . Associated mixed oxy and hydroxyl phases are also reported. The combined Raman and DFT results have eliminated inconsistencies in Raman mode assignments for the MX 3 family of metal chlorides having P6 3 /m symmetry, and IR modes derived from the DFT calculations are additionally presented. The data observed in this study is of potential interest to nuclear forensic analyses, nuclear sample aging, nuclear energy, plutonium processing, and stockpile stewardship.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Improved cycle stability and high-rate capability of LiNbO 3 -coated Li 3 VO 4 as anode material for lithium-ion battery

Lithium vanadate (Li 3 VO 4 ) has garnered considerable attention as an alternative negative electrode material for non-aqueous lithium-ion batteries due to its high capacity, energy efficiency, and stable discharge voltage. Nonetheless, the Li 3 VO 4 material displays a low rate capability, attributed mainly to its poor intrinsic electronic conductivity. Here, in this study, we report the synthesis of lithium niobate LiNbO 3 -coated Li 3 VO 4 (LVO@LNO) using a one-pot sol-gel method. The resulting LVO@LNO demonstrates a high reversible capacity of approximately 530 mAh/g, which is more than double that of free Li 3 VO 4 . To explore the effect of the LNO coating process on the morphological and structural properties, Raman, XRD, operando XRD, XPS, SEM and HTEM analyses were conducted. To explain the enhancement of electronic conductivity in our modified material after a LiNbO 3 coating, we conducted an Ex-Situ electrochemical impedance (EIS) and Density Functional Theory (DFT) computational study. Additionally, we designed a full cell utilizing a 1 wt% LNO-coated LVO anode and NMC-811 cathode. The cell yielded an output voltage of approximately 2.8 V with a high initial specific capacity of 350 mAh/g versus to the anode, at 1C with a capacity retention of 85 % after 100 cycles.

25 ENERGY STORAGE↗
DOE OSTI2022

Recovery of release cloud from laser shock-loaded graphite and hydrocarbon targets: in search of diamonds

Abstract This work presents first insights into the dynamics of free-surface release clouds from dynamically compressed polystyrene and pyrolytic graphite at pressures up to 200 GPa, where they transform into diamond or lonsdaleite, respectively. These ejecta clouds are released into either vacuum or various types of catcher systems, and are monitored with high-speed recordings (frame rates up to 10 MHz). Molecular dynamics simulations are used to give insights to the rate of diamond preservation throughout the free expansion and the catcher impact process, highlighting the challenges of diamond retrieval. Raman spectroscopy data show graphitic signatures on a catcher plate confirming that the shock-compressed PS is transformed. First electron microscopy analyses of solid catcher plates yield an outstanding number of different spherical-like objects in the size range between ten(s) up to hundreds of nanometres, which are one type of two potential diamond candidates identified. The origin of some objects can unambiguously be assigned, while the history of others remains speculative.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1973

A new effect in the depolarization of resonant light scattering from molecules in the vapor phase: I2

Theoretical discussions of the depolarization ratios in two types of resonance processes are given. These processes are discrete state resonance fluorescence, and Raman scattering when the resonance is between a bound state and evanescent-dissociative states. Theory predicts a dramatic difference for these two cases due to a quantum mechanical phase cancellation in the case of virtual dissociative states. The predictions have been verified experimentally.

Silverstein, S. D.↗
NASA NTRS1990

On diamond, graphitic and amorphous carbons in primitive extraterrestrial solar system materials

Carbon is among the most abundant elements in the universe and carbon chemistry in meteorites and comets is an important key to understanding many Solar System and interstellar processes. Yet, the mineralogical properties and interrelations between various structural forms of elemental carbon remain ambiguous. Crystalline elemental carbons include rhombohedral graphite, hexagonal graphite, cubic diamond, hexagonal diamond (i.e., lonsdaleite or carbon-2H) and chaoite. Elemental carbon also occurs as amorphous carbon and poorly graphitized (or turbostratic) carbon but of all the forms of elemental carbon only graphite is stable under physical conditions that prevail in small Solar System bodies and in the interstellar medium. The recent discovery of cubic diamond in carbonaceous chondrites and hexagonal diamond in chondritic interplanetary dust particles (IDPs) have created a renewed interest in the crystalline elemental carbons that were not formed by shock processes on a parent body. Another technique, Raman spectroscopy, confirms a widespread occurrence of disordered graphite in the Allende carbonaceous chondrite and in chondritic IDPs. Elemental carbons have also been identified by their characteristic K-edge features in electron energy loss spectra (EELS). However, the spectroscopic data do not necessarily coincide with those obtained by selected area electron diffraction (SAED). In order to interpret these data in terms of rational crystalline structures, it may be useful to consider the principles underlying electron diffraction and spectroscopic analyses. Electron diffraction depends on electron scattering, on the type of atom and the distance between atoms in a crystal lattice. Spectroscopic data are a function of the type of atom and the energy of bonds between atoms. Also, SAED is a bulk sampling technique when compared to techniques such as Raman spectroscopy or EELS. Thus, it appears that combined analyses provide contradictory results and that amorphous, or short-range ordered, carbon identified by conventional TEM imaging and SAED may show evidence for sp(3) bonds in EELS spectra. It is suggested that complex, nanometer-scale, mineralogical interrelations are common to all elemental carbons irrespective of their origin. The subsequent thermal history, or energy balance, will determine the ultimate microstructure.

Rietmeijer, Frans J. M.↗
NASA NTRS1995

Thermal Line Shift and Broadening of Ho(3+) in Y3AI5O12 and Lu3AIO12

The interaction between the active ion and the host lattice manifests itself in two distinct ways: the static interaction with the crystal field that causes the splitting of the free ion energy levels and the active interaction through the surrounding phonon system that produces temperature dependent characteristics in the optical spectrum of the ion (e.g. line broadening and line shift). The strength of the splitting depends heavily on the electronic configuration of the atom. The model give by McCumber and Sturge describes the thermal effects on line width and position above 77 K with Raman scattering of Debye model phonons. These processes predict a Lorentzian line shape. However, below 77 K the principal contributions are from crystal inhomogeneities that result in a Gaussian line shape. We have investigated the experimental Stark levels as well as the thermal effects on the line width and the position of trivalent holmium ions in both yttrium aluminum garnet, Y3Al5O12 (YAG) and lutetium aluminum garnet, Lu3Al5O12 (LuAG) crystals. We have compared the Stark levels of the (5)I(6) state, and the thermal line shift and broadening of an isolated transition (Z2 to X13) between the (5)I(8) and (5)I(6) stark levels in these crystals. This transition occurs in the near infrared region at approximately 1117 nm.

Snoke, Elizabeth R.↗
DOE OSTI2022

Raman Interferometry between Autoionizing States to Probe Ultrafast Wave-Packet Dynamics with High Spectral Resolution

Photoelectron interferometry with femtosecond and attosecond light pulses is a powerful probe of the fast electron wave-packet dynamics, albeit it has practical limitations on the energy resolution. We show that one can simultaneously obtain both high temporal and spectral resolution by stimulating Raman interferences with one light pulse and monitoring the modification of the electron yield in a separate step. Applying this spectroscopic approach to the autoionizing states of argon, we experimentally resolved its electronic composition and time evolution in exquisite detail. Theoretical calculations show remarkable agreement with the observations and shed light on the light-matter interaction parameters. Using appropriate Raman probing and delayed detection steps, this technique enables highly sensitive probing and control of electron dynamics in complex systems.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Radiation Effects on the Performance of Advanced Sulfur Monochloride Chlorination Processes

Advanced sulfur chloride-based chlorination technologies are being developed to enable efficient recycling of aluminum and zirconium-based materials used in the nuclear industry. However, the impacts of ionizing radiation on the performance of these sulfur chloride compounds are not well established, despite this being critical knowledge for assessing their feasibility and longevity under envisioned process conditions. Here, in the present article, we report on the effects of cobalt-60 gamma irradiation (≤ 5 MGy) on the aluminum alloy 6061 (AA6061-T6) chlorination yield in sulfur monochloride (S 2 Cl 2 ). Our findings indicate that, compared to nonirradiated solvent, radiation-induced changes in the chemical composition of S 2 Cl 2 —identified using Raman spectroscopy—afford an additional, dose-dependent exothermic process prior to the chlorination reaction’s typical thermodynamic behavior. We attribute this new process to reactions involving aluminum species (metal, oxide, or [oxy]hydroxides) and sulfur dichloride (SCl 2 ), an S 2 Cl 2 radiolysis product that accumulates with absorbed gamma dose, but is absent following an AA6061-T6 chlorination study. Despite the exothermicity of this new process, the overall yield of chlorination decreased with increasing preirradiation dose. Consequently, the chemical reactivity, specificity (aluminum metal vs aluminum passivation and corrosion layer constituents), and byproducts of SCl 2 must be more thoroughly evaluated to support the continued development of advanced S 2 Cl 2 chlorination technologies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

High Throughput Data-Driven Design of Laser-Crystallized 2D MoS 2 Chemical Sensors: A Demonstration for NO 2 Detection

High throughput characterization and processing techniques are becoming increasingly necessary to navigate multivariable, data-driven design challenges for sensors and electronic devices. For two-dimensional materials, device performance is highly dependent upon a vast array of material properties including the number of layers, lattice strain, carrier concentration, defect density, and grain structure. In this work, laser crystallization was used to locally pattern and transform hundreds of regions of amorphous MoS 2 thin films into 2D 2H-MoS 2 . Here a high throughput Raman spectroscopy approach was subsequently used to assess the process-dependent structural and compositional variations for each illuminated region, yielding over 6000 distinct nonresonant, resonant, and polarized Raman spectra. The rapid generation of a comprehensive library of structural and compositional data elucidated important trends between structure–property processing relationships involving laser-crystallized MoS 2 , including the relationships between grain size, grain orientation, and intrinsic strain. Moreover, extensive analysis of structure/property relationships allowed for intelligent design and evaluation of major contributions to device performance in MoS 2 chemical sensors. In particular, it is found that NO 2 sensor performance is strongly dependent on the orientation of the MoS 2 grains relative to the crystal plane.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Confocal Raman Microscopy for Measuring In Situ Temperature-Dependent Structural Changes in Poly(Ethylene Oxide) Thin Films

Crystallization from the melt is a critical process governing the properties of semi-crystalline polymeric materials. While structural analyses of melting and crystallization transitions in bulk polymers have been widely reported, in contrast, those in thin polymer films on solid supports have been underexplored. Herein, in situ Raman microscopy and self-modeling curve resolution (SMCR) analysis are applied to investigate the temperature-dependent structural changes in poly(ethylene oxide) (PEO) films during melting and crystallization phase transitions. By resolving complex overlapping sets of spectra, SMCR analysis reveals that the thermal transitions of 50 µm thick PEO films comprise two structural phases: an ordered crystalline phase and a disordered amorphous phase. The ordered structure of the crystalline PEO film entirely disappears as the polymer is heated; conversely, the disordered structure of the amorphous PEO film reverts to the ordered structure as the polymer is cooled. Broadening of the Raman bands was observed in PEO films above the melting temperature (67 °C), while sharpening of bands was observed below the crystallization temperature (45 °C). The temperatures at which these spectral changes occurred were in good agreement with differential scanning calorimetry (DSC) measurements, especially during the melting transition. The results illustrate that in situ Raman microscopy coupled with SMCR analysis is a powerful approach for unraveling complex structural changes in thin polymer films during melting and crystallization processes. Furthermore, we show that confocal Raman microscopy opens opportunities to apply the methodology to interrogate the structural features of PEO or other surface-supported polymer films as thin as 2 µm, a thickness regime beyond the reach of conventional thermal analysis techniques.

Koh, Miharu [Department of Chemistry, University o↗