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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 55 records · Page 3

A Spatially Resolved Evaluation of Accelerated Environmental Aging on Emerging Polypropylene-Based Photovoltaic Backsheets Using Raman Spectroscopy

For this work, accelerated aging was used to assess environmental degradation in emerging co-extruded polypropylene (PP)-based backsheets under three different environmental conditions (65°C/20% relative humidity (RH), 75°C/20% RH, and 75°C/50% RH). Although differential scanning calorimetry did not measure crystallinity changes with exposure, spatially resolved Raman spectroscopy identified crystallinity increases in the core layer of aged samples, indicating a heterogeneous postcrystallization process. The Raman results were in agreement with synchrotron-based microfocused wide-angle X-ray scattering measurements. Cross-sectional nanoindentation was used to correlate localized crystallinity shifts with changes in Young's modulus. A similar trend was found where increased modulus was measured in the core layer, supporting the relationship between modulus and crystallinity. Finally, dielectric characterization was used to assess the impact of these material property changes on performance. While changes in the backsheet material properties and dielectric performance were observed with accelerated aging, these shifts generally equilibrated with time, indicating overall stability in response to environmental stressors. Additionally, the identified heterogeneous material property changes indicate that spatially resolved crystallinity measurements may be a valuable early failure indicator to be used in the assessment of PV backsheet long-term durability.

36 MATERIALS SCIENCE↗

Thermal processing of omicron-terphenyl - A Raman study

Raman spectra from omicron-terphenyl sealed in glass capillary tubes were acquired over temperatures ranging from 233 to 343 K. Over this temperature range, omicron-terphenyl can exist in the solid-crystalline, molten, supercooled-liquid, and amorphous-glassy states. Representative structure-sensitive spectra are presented along with a qualitative description. The lattice spectral feature occurring at a Raman shift of 123/cm displays abrupt changes in profile and intensity as melting and glass transition occur. The intensity ratio of the C-C stretching 996/cm line and C-H stretching line at 1008/cm displays a change related to the transformation of the ordered-crystalline phase to the disordered-liquid or glassy state. At a Raman shift of 1162/cm the solid-crystalline state shows a splitting due to the effect of the crystal field. The possibility of using these structure-sensitive Raman characteristics for in situ diagnostics during materials processing is discussed.

Biswas, A.↗

Confocal Raman Microscopy as a Probe of Material Deconstruction in Processed Low-Density Polyethylene Particles

Confocal Raman microscopy was applied to detect structural change within individual particles of low-density polyethylene (LDPE) following chemical and electrochemical processing steps that aimed to facilitate material decomposition. A high numerical aperture (NA) oil-immersion objective enabled depth-profiling through the near surface region (20 μm–40 μm) of irregularly shaped particles with an axial spatial resolution < 2 μm estimated from measurements of instrument detection efficiency profiles. Changes in vibrational bands sensitive to polyethylene crystallinity were evident following treatments and linked to the release of low molecular weight compounds present as additives and products of processing. Effects of processing were probed by monitoring the rise of Raman scattering intensity in vibrational modes associated with polyethylene chains in a zig-zag (trans) conformation near 1128 cm –1 , 1294 cm –1 , and 1418 cm –1 , signaling chain clustering and development of organized, crystalline-like assemblies. Pristine LDPE particles displayed a uniform structure across the near surface region, while particles treated initially with chemical extractant and then further processed displayed increasingly enhanced crystallinity up to the maximum depth probed (40 μm). As a step toward measurements on ensembles of particles, least squares modeling was adapted to derive pure component spectra reflecting crystallinity change within spectral datasets. The work demonstrates high spatial resolution Raman depth-profiling for the characterization of processed polymers using a high NA immersion objective to overcome the limitations of air-objectives often used for confocal Raman microscopy.

Wahiduzzaman, Md. [Department of Chemistry and Bio↗

Online Monitoring of Catalytic Processes by Fiber-Enhanced Raman Spectroscopy

An innovative solution for real-time monitoring of reactions within confined spaces, optimized for Raman spectroscopy applications, is presented. This approach involves the utilization of a hollow-core waveguide configured as a compact flow cell, serving both as a conduit for Raman excitation and scattering and seamlessly integrating into the effluent stream of a cracking catalytic reactor. The analytical technique, encompassing device and optical design, ensures robustness, compactness, and cost-effectiveness for implementation into process facilities. Notably, the modularity of the approach empowers customization for diverse gas monitoring needs, as it readily adapts to the specific requirements of various sensing scenarios. As a proof of concept, the efficacy of a spectroscopic approach is shown by monitoring two catalytic processes: CO 2 methanation (CO 2 + 4H 2 → CH 4 + 2H 2 O) and ammonia cracking (2NH 3 → N 2 + 3H 2 ). Leveraging chemometric data processing techniques, spectral signatures of the individual components involved in these reactions are effectively disentangled and the results are compared to mass spectrometry data. This robust methodology underscores the versatility and reliability of this monitoring system in complex chemical environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Beyond the Charge Transfer Mechanism for 2D Materials-Assisted Surface Enhanced Raman Scattering

Two-dimensional (2D) materials have been extensively implemented as surface-enhanced Raman scattering (SERS) substrates, enabling trace-molecule detection for broad applications. However, the accurate understanding of the mechanism remains elusive because most theoretical explanations are still phenomenological or qualitative based on simplified models and rough assumptions. To advance the development of 2D material-assisted SERS, it is vital to attain a comprehensive understanding of the enhancement mechanism and a quantitative assessment of the enhancement performance. Here, the microscopic chemical mechanism of 2D material-assisted SERS is quantitatively investigated. The frequency-dependent Raman scattering cross sections suggest that the 2D materials’ SERS performance is strongly dependent on the excitation wavelengths and the molecule types. By analysis of the microscopic Raman scattering processes, the comprehensive contributions of SERS can be revealed. Beyond the widely postulated charge transfer mechanisms, the quantitative results conclusively demonstrate that the resonant transitions within 2D materials alone are also capable of enhancing the molecular Raman scattering through the diffusive scattering of phonons. Furthermore, all of these scattering routines will interfere with each other and determine the final SERS performance. Our results not only provide a complete picture of the SERS mechanisms but also demonstrate a systematic and quantitative approach to theoretically understand, predict, and promote the 2D materials SERS toward analytical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Non-intrusive measurements in a rocket engine combustor

In recent years analytical tools to characterize combustor flow have been developed in order to support design. To facilitate anchoring of combustion related physical models and the CFD codes in which they are incorporated, considerable development and application of non-intrusive combustion diagnostic capabilities has occurred. Raman spectroscopy can be used to simultaneously detect all polyatomic molecules present in significant concentrations and to determine gas temperature. This is because all molecules possess a distinct temperature dependent Raman spectrum. A multi-point diagnostic system for non-intrusive temperature and species profiling in rocket engines has been developed at Rocketdyne. In the present effort, the system has been undergoing validation for application to rocket engine component testing. A 4 inch diameter windowed combustor with a coaxial gas-gas injector was chosen for this series of validation experiments. Initially an excimer-pumped tunable dye laser and later a solid state Nd-Yag laser served as excitation sources. The Raman signal was dispersed by a monochromator and detected by a gated, intensified Charged Coupled Device (CCD) array. Experiments were carried out prior to each series of hot fire tests to ensure that the Raman signal detected was due to a spontaneous rather than a stimulated Raman emission process. Over sixty hot fire tests were conducted during the first series of tests with the excimer/dye laser. All hot fire testing was at a mixture ratio of 0.5 and chamber pressures of approximately 100 and approximately 300 psia. The Raman spectra of hydrogen, water vapor and oxygen recorded during single element hot fire tests were reduced and analyzed. A significant achievement was the attainment of single shot Raman spectra in cold flow tests. Unfortunately, the single shot signal-to-noise ratio deteriorated to an unacceptable level during the hot fire testing. Attempts to obtain temperature data from the hydrogen Q1-branch profiles obtained in hot fire tests suggest that potentially complicating factors may render the approach of averaging data on the photodiode array invalid. A second series of hot fire tests was conducted with a 4 element coaxial injector using the Nd-Yag laser. A very compact and portable diagnostics set up was assembled for ease of alignment, relocation and flexibility. Measurements were made at several regions in the chamber in order to map concentration profiles. High spatial resolution and improved signal to noise characteristics were demonstrated.

Farhangi, S.↗

Monitoring the Caustic Dissolution of Aluminum Alloy in a Radiochemical Hot Cell Using Raman Spectroscopy

Chemical processing of highly radioactive materials commonly takes place in heavily shielded hot cells. The remote, real-time monitoring of chemical processing streams via optical spectroscopic techniques in hot cells may be particularly useful. Here in this paper, we describe the implementation of Raman spectroscopy and chemometric analysis to monitor the dissolution of aluminum-clad targets containing irradiated aluminum–neptunium oxide cermet pellets in caustic solutions in a hot cell environment. Partial least squares regression analysis was used to generate calibration models to quantify the concentration of dissolved aluminum, nitrate, and hydroxide in solutions within the radiochemical hot cell. This work explored a systematic approach to optimize a matrix of calibration standards using a D-optimal experimental design. The Design of Experiments-based regression model, in comparison to more traditional analytical approaches, was found to be the more practical method for building calibration models, with fewer samples, to obtain informative analytical data from Raman spectra.

36 MATERIALS SCIENCE↗

Spontaneous Raman Scattering Diagnostics: Applications in Practical Combustion Systems

In this chapter, the recent advancements and practical aspects of laser SRS diagnostics have been reviewed wi til regards to applications in practical combustion systems. Clearly, SRS represents a theoretically and experimentally mature diagnostic technology that has become an essential tool for multiscalar measurements in turbulent combustion at elevated pressures. Today, time-, space-, spectrally, and even polarization-resolved S RS diagnostics is at hand, with aid from recent innovations in theoretical and technological developments on electro-optical or electromechanical devices. Whilst a linear increase in SRS signals can be expected in high-pressure systems (this is perhaps one of the most important advantages for using SRS in high-pressure systems), there are practical (often severe) restrictions associated with pressurized vessels, due mainly to the limited degree of optical access. This narrows ti,e available choice of diagnostics that can be employed at any given time. Point-wise SRS diagnostics provides the highest accuracy on the chemical species and temperature measurements, and will continue to remain a vital approach for the study in such harsh environments. The practical design considerations and hands-on set-up guide for SRS diagnostics provided in this chapter are rarely presented elsewhere. Although the second-harmonic Nd:YAG pulsed laser (532 nm), combined with pulse-stretching optics or the recently introduced White Cell-based laser, seems to be the most favored excitation source of choice by the research community, UV excitation will undoubtedly continue to be used on many occasions, and especially in sooting flames. Detection methods may be divided into ICCD-based nanosecond-gate detection or a rotary-chopper electromechanical shutter-based CCD array detection, and the levels of background flame emission in individual cases would determine this critical design choice. Here, a process of Raman signal calibration based on ti,e crosstalk matrix formalism was explained step-by-step. As tI,is process may be very time-consuming and expensive, a well-planned experimental approach (01' building a transferable calibration database or library (at least with in a user's own facility over a series of different testing and runs) is vitally important. Hands on advice on the design and construction of flow control systems for high pressure burner facilities were also presented.

Kojima, Jun↗

Evidence for Trapping-Induced Nonlinear Frequency Shifts in Langmuir Waves Driven via Stimulated Raman Scattering

Thomson scattering is used to detect the spectra of Langmuir waves driven through the backward stimulated Raman scattering process in a diffraction limited laser focal spot. Measured Langmuir wave spectral frequencies are found to vary in time and have broadened spectral power, consistent with a nonlinear frequency shift of the driven Langmuir wave due to electron-trapping. Broadening of the Langmuir wave spectral power is observed to decrease in time, consistent with measured variations in the frequency shift of the driven Langmuir waves. Furthermore, the observed spectral broadening is consistent with the temporally short (ps), bursty nature of backward stimulated Raman scattered light observed in simulations that cannot be resolved by the Thomson scattering diagnostic. Comparison of the broadened spectrum with time integrated spectra from two-dimensional particle-in-cell simulations shows favorable comparison in the broadened spectral widths, supporting the supposition of electron-trapping induced, nonlinear shifting of daughter Langmuir wave frequencies.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Examination of Lunar Regolith Simulants By SEM-EDS and Imaging Raman Spectroscopy

The Artemis series lunar missions will include sample returns from the lunar south pole. Lunar regolith simulants (RS) generated in the lab provide opportunities to compare two surface science techniques: scanning electron microscopy (SEM-EDS) and Raman induced surface spectroscopy. The results will also be applicable for supporting future commercial lunar payload services (CLPS) and Artemis surface. Surface characterization contributes to continued development of lunar regolith studies and adds to various regolith databases. In characterizing various lunar regolith simulants, part of the aim should be to standardize techniques and utilize anticipated methods available for astromaterials studied during, or returned from, upcoming missions, particularly samples collected from the Moon’s south pole and permanently shadowed regions (PSRs).. An initial survey of available simulants has been started with Raman scanning process for particle counting the results of which will enrich the NASA-JSC Simulant Development Lab (SDL) simulant properties database and the Colorado School of Mines Planetary Simulant Data Base. An SEM-EDS dataset of raw regolith simulant materials are collected.

Raman Microscopy↗

Theory of stimulated and spontaneous axion scattering.

We present a theory for nonlinear, resonant excitation of dynamical axions by counterpropagating electromagnetic waves in materials that break both 𝒫 and 𝒯 symmetries. We show that dynamical axions can mediate an exponential growth in the amplitude of the lower frequency (Stokes) beam. We also discuss spontaneous generation of a counterpropagating Stokes mode, enabled by resonant amplification of quantum and thermal fluctuations in the presence of a single pump laser. Remarkably, the amplification can be orders of magnitude larger than that obtained via stimulated Brillouin and Raman scattering processes, and can be modulated with the application of external magnetic fields, making stimulated axion scattering promising for optoelectronics applications.

Smith, M.↗

Navigating the complexities of solvent and binder selection for solution processing of sulfide solid-state electrolytes

We introduce a paradigm of solvent and binder selection for solution-processing Li 6 PS 5 Cl solid-state electrolyte particles based on Hansen solubility parameters. Treatment of the Li 6 PS 5 Cl in selected solvents results in particle morphological change, but crystallographic structure remains intact. Although solution processing reduced the Li 6 PS 5 Cl ionic conductivity, it promotes interfacial stability by alleviating reduction of the solid electrolyte in contact with Li metal. In conclusion, these findings have the potential to enhance the stability, structural integrity, and performance of sulfide solid-state electrolytes in practical applications.

25 ENERGY STORAGE↗

Fabricating Graphene Oxide/h-BN Metal Insulator Semiconductor Diodes by Nanosecond Laser Irradiation

To employ graphene’s rapid conduction in 2D devices, a heterostructure with a broad bandgap dielectric that is free of traps is required. Within this paradigm, h-BN is a good candidate because of its graphene-like structure and ultrawide bandgap. We show how to make such a heterostructure by irradiating alternating layers of a-C and a-BN film with a nanosecond excimer laser, melting and zone-refining constituent layers in the process. With Raman spectroscopy and ToF-SIMS analyses, we demonstrate this localized zone-refining into phase-pure h-BN and rGO films with distinct Raman vibrational modes and SIMS profile flattening after laser irradiation. Furthermore, in comparing laser-irradiated rGO-Si MS and rGO/h-BN/Si MIS diodes, the MIS diodes exhibit an increased turn-on voltage (4.4 V) and low leakage current. The MIS diode I-V characteristics reveal direct tunneling conduction under low bias and Fowler-Nordheim tunneling in the high-voltage regime, turning the MIS diode ON with improved rectification and current flow. This study sheds light on the nonequilibrium approaches to engineering h-BN and graphene heterostructures for ultrathin field effect transistor device development.

2D materials↗

Stationary and non-stationary nonlinear optical spectroscopy on surface polaritons

A phenomenological theory is given for non-stationary electromagnetic surface waves propagating along the boundary plane between two homogeneous isotropic media. The description of nonlinear optical effects using shortened wave equations is demonstrated for spontaneous and simulated Raman scattering processes on surface polaritons.

Ponath, H. E.↗

Verification measurement of a polarization Raman elastic-backscatter lidar

By measuring the depolarization of light Raman scattered from a gas of known number density (nitrogen), it is possible to determine the influence of multiple scattering on lidar signals. In order to realize such measurements, linearly polarized laser light is emitted and two components of the nitrogen Raman signals, with E vectors parallel (parallel P sub lambda R) and perpendicular (perpendicular P sub lambda R) to the plane of polarization of the laser light, are measured. The depolarization ratio, delta sub lambda R = perpendicular P sub lambda R/parallel P sub lambda R, is constant if only the Raman scattering process contributes to the signal. Any variation of the depolarization is caused by additional elastic, and, thus, multiple scattering. If the contribution of multiple scattered light to the lidar signals is known, other parameters determined with the systems such as extinction, backscattering, and the depolarization of elastically scattered light, can be corrected for this influence. The lidar system used for the polarization measurements, especially the receiver setup, is described. The calibration of the apparatus and a clear air measurement are discussed.

Schulze, Christoph↗

Laser Raman sensor for measurement of trace-hydrogen gas

A new optical hydrogen sensor based on spontaneous Raman scattering of laser light has been designed and constructed for rugged field use. It provides good sensitivity, rapid response, and the inherent Raman characteristics of linearity and background gas independence of the signal. Efficient light collection and discrimination by using fast optics and a bandpass interference filter compensate for the inefficiency of the Raman-scattering process. A multipass optical cavity with a Herriott-type configuration provides intense illumination from an air-cooled CW gas laser. The observed performance is in good agreement with the theoretical signal and noise level predictions.

Adler-Golden, Steven M.↗

Sensor Fusion: Comprehensive Real-Time, On-Line Monitoring for Process Control via Visible, Near-Infrared, and Raman Spectroscopy

On-line monitoring based on optical spectroscopy provides unprecedented insight into the chemical composition of process streams or batches. Amplifying this approach through utilizing multiple forms of optical spectroscopy in sensor fusion can greatly expand the number and type of chemical species that can be identified and quantified. This is demonstrated herein, on the analysis of used nuclear fuel recycling streams: highly complex processes with multiple target and interfering analytes. The optical techniques of visible absorbance, near infrared absorbance, and Raman spectroscopy were combined to quantify plutonium (III, IV, VI), uranium (IV, VI), neptunium (IV, V, VI), and nitric acid. Chemometric modeling was used to quantify analytes in process streams in real-time and results were successfully used to enable immediate process control and generation of a product stream at a set composition ratio. This represents a significant step forward in the ability to monitor and control complex chemical processes occurring in harsh chemical environments.

47 OTHER INSTRUMENTATION↗

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.↗