High-Pressure Raman and Infrared Spectroscopic Study of Prehnite
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99 GENERAL AND MISCELLANEOUS↗
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Use of an Internal Mercury-Argon Lamp for the Calibration of Raman Frequency in Large Raman Images of Astromaterials
Raman imaging is an emerging tool for the analysis of meteorites, as it is capable of describing mineralogy, carbon composition/speciation, and crystal orientation all within a petrographic context. Adequately examining the heterogeneous composition of a meteorite, while maintaining low laser powers needed to prevent damage to meteorite mineralogy and organics, often requires the collection of large Raman images with long collection times on the timescale of days. However, the frequency calibration of the Raman instrument/spectrometer drifts on long timescales resulting in low frequency precision for the Raman spectra comprising a large Raman image. This decrease in frequency precision can compromise the analysis of geological markers that can provide important information on a meteorite sample. We examine, in detail, the change in bandwidth and frequency of the Raman bands and Hg-Ar emission lines in our Raman images as a function of time and laboratory temperature. To overcome the drift in calibration, we utilize a commercial WITec Raman instrument with an internal Hg-Ar calibration lamp to individually calibrate each spectrum in the Raman image. Our instrument, known as “Ratatoskr”, uses a beam splitter in place of the customary mirror to facilitate collection of Hg-Ar calibration lines concurrent with Raman spectra. We show that using the internal calibration we can improve the frequency precision for the spectra in our Raman images from ~±0.15 cm(exp -1) to ~±0.05 cm(exp -1) for Raman spectra collected over multiple days. This is important as it improves measurements of mineral chemistry, latent strain, and other features that are dependent upon accurate peak position determination. We also examine the spectral signal-to-noise ratio needed to minimize the frequency error when fitting bands to Gaussian/Lorentzian profiles. We then use our results to suggest a general method for calibrating the frequency of Raman spectra in large Raman images.
Jakubek, Ryan S.↗
Development of an immersion fiber optic Raman probe for real-time analysis of molten materials
This study presents an advancement in high-temperature Raman spectroscopy, specifically for analyzing molten materials. It introduces an approach by integrating a fiber-optic Raman probe with a copper block protection system designed to endure extreme thermal conditions. The copper block features an open port designed to accommodate an external telescope with a 3 cm focal length, enabling Raman spectra collection in challenging high-temperature environments. A built-in gas channel ensures a continuous flow of argon gas to prevent flux intrusion. The robust copper block acts as a reliable shield, safeguarding the fiber-optic Raman probe within molten materials. This enhancement maintains the probe's integrity and significantly improves its resilience, making it ideal for rigorous investigations of molten substances. This advancement is particularly relevant in metallurgy, where flux materials impact production quality and efficiency. The ability to acquire Raman signals under elevated thermal conditions offers opportunities for studying molecular dynamics, compositional changes, and chemical interactions within molten substances. This introduced direct immersion probing technique has implications, benefiting both scientific and industrial fields. It holds promise for advancing research and exploration in various contexts, from fundamental scientific inquiries to practical applications in metallurgical processes, where flux materials are critical for optimizing production quality and efficiency. Furthermore, this approach enhances the capabilities of high-temperature Raman spectroscopy, making it a valuable tool for investigating molten materials and their properties in diverse settings.
Argon↗
Use of an Internal Mercury-Argon Lamp for the Calibration of Raman Frequency in Large Raman Images of Astromaterials
Raman imaging is an emerging tool for the analysis of meteorites, as it is capable of describing the mineralogy and organics within a petrographic context. Adequately examining the heterogeneous composition of a meteorite often requires the collection of large Raman images with long collection times on the time-scale of days. However, the frequency calibration of the Raman instrument/spectrometer drifts on long timescales resulting in low frequency precision for the Raman spectra comprising a large Raman image. Here we utilize a Hg-Ar calibration lamp integrated into our Raman microscope to calibrate the Raman spectra within a Raman image. We characterize this method of calibration in detail.
Ryan S. Jakubek↗
Enabling phase quantification of anhydrous cements via Raman imaging
The phase composition of Portland cements is typically determined using conventional techniques like X-ray Diffraction (XRD) Rietveld analysis, optical microscopy point counting, and electron microscopy. However, these techniques have several limitations that may affect their accuracy in certain sample-specific scenarios. Here, we report a highly accurate phase quantification of 11 different types of commercial, anhydrous cements using a new and complementary technique: Raman imaging. Specifically, for the 4 principal phases, composition from our extensive data (250,000 Raman spectra per sample, error < 0.71%) and those obtained from XRD Rietveld and supplier data have high coefficients of determination (R{sup 2} > 0.98, mean deviation <2%). Additionally, we also quantify 8 secondary phases present in cement clinkers (gypsum, anhydrite, bassanite, syngenite, dolomite, calcite, quartz, and portlandite) with a high degree of confidence, thereby demonstrating that Raman imaging is a highly versatile tool for anhydrous phase quantification in a broad variety of cements.
36 MATERIALS SCIENCE↗
Raman Spectroscopy Based On-Line, Real-Time Monitoring to Reduce Composition Uncertainties: Enhanced sensitivity through optimization of Raman Parameters
Optical spectroscopy-based on-line monitoring of Hanford processing streams can enable real-time characterization of chemical composition of process streams and batches, ultimately enabling and enhancing process control. It can provide immediate feedback on process conditions and has the potential to reduce the needed number of grab sample collections, thereby reducing times and costs associated with laboratory processing. Here we discuss the utilization of Raman spectroscopy to quantify multiple target analytes that are common within Hanford tanks and waste processing streams. Analytes include: nitrate, nitrite, carbonate, chromate, sulfate, phosphate, hydroxide, oxalate, ammonia, and aluminate. Most notably in this work, Raman applications to low-concentration streams are explored and optimized. Raman instrument specifications are compared; specifically, the impact of utilizing three different Raman excitation wavelengths, 405, 532, and 671 nm, is discussed. Also, Raman data collection parameters such as collection time and spectral averaging are measured and discussed. Finally, optical libraries of chemical targets were collected using optimized collection parameters and chemometric models were built to automate quantification of chemical targets. These models were validated through application to simulants and real Hanford process samples. Chemometric models performed well on both training and validation sets, suggesting these approaches can be successfully applied to on-line and real-time monitoring of low concentration Hanford processing streams. The use of the combine Raman wave lengths with the enhanced chemometric models for the low concentration streams significantly improved the chemical detection levels and significantly reduced uncertainties of those measurements.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Plastic deformation mechanism of calcium-silicate hydrates determined by deviatoric-stress Raman spectroscopy
Highlights: • C-(A-)S-H samples under stress were characterized at the bond and grain level. • Small angle scattering showed that 720 MPa reduced grain thickness by 30%. • In-situ Raman showed that cross-linked C-A-S-H slips along its intralayer. • However, in-situ Raman showed that C-S-H slips along the interlayer. • In-situ Raman also showed a growth in CaCO{sub 3}, indicating fracture in both samples. Creep of the cement matrix affects the structural stability of concrete. In Portland cements, the creep is largely controlled by the binding phase calcium-(aluminum-)silicate-hydrate, or C-(A-)S-H. This phase has a lamellar structure and under deviatoric stress aligns its c-axis with the principal stress. However, the limiting resistance to this reorientation is unknown at the nanocrystalline level. Small-angle X-ray scattering shows that the lamellae thickness decreases under 100's MPa deviatoric stress. Deviatoric stress Raman spectroscopy shows that there are two ways that this break-up can occur. If the material's silicate chains are cross-linked, then strain in SiO bonds does not increase above certain stresses, indicating a relaxation adjacent to the SiO bond. If the chains are not cross-linked, then the silicate chains are broken up by rastering against each other, introducing defects. These results show that the plastic deformation of C-(A-)S-H is relevant for Portland cement creep.
36 MATERIALS SCIENCE↗
A New Way to Measure Cirrus Ice Water Content by Using Ice Raman Scatter with Raman Lidar
High and cold cirrus clouds mainly contain irregular ice crystals, such as, columns, hexagonal plates, bullet rosettes, and dendrites, and have different impacts on the climate system than low-level clouds, such as stratus, stratocumulus, and cumulus. The radiative effects of cirrus clouds on the current and future climate depend strongly on cirrus cloud microphysical properties including ice water content (IWC) and ice crystal sizes, which are mostly an unknown aspect of cinus clouds. Because of the natural complexity of cirrus clouds and their high locations, it is a challenging task to get them accurately by both remote sensing and in situ sampling. This study presents a new method to remotely sense cirrus microphysical properties by using ice Raman scatter with a Raman lidar. The intensity of Raman scattering is fundamentally proportional to the number of molecules involved. Therefore, ice Raman scattering signal provides a more direct way to measure IWC than other remote sensing methods. Case studies show that this method has the potential to provide essential information of cirrus microphysical properties to study cloud physical processes in cirrus clouds.
Wang, Zhien↗
Raman Microscopy Investigation of GLP-1 Peptide Association with Supported Phospholipid Bilayers
A wide range of important biological processes occur at phospholipid membranes including cell signaling, where a peptide or small molecule targets a membrane-localized receptor protein. In this work, we report the adaptation of confocal-Raman microscopy to quantify populations of unlabeled glucagon-like peptide-1 (GLP-1), a membrane-active 30-residue incretin peptide, in supported phospholipid bilayers deposited on the interior surfaces of wide-pore porous silica particles. Quantification of lipid bilayer-associated peptide is achieved by measuring the Raman scattering intensity of the peptide relative to that of the supported-lipid bilayer, which serves as an internal standard. The dependence of the bilayer-associated GLP-1 population on the solution-concentration of GLP-1 produces an isotherm used to determine the equilibrium constant for peptide-bilayer association and the maximum peptide surface coverage. The maximum coverage of GLP-1 in the lipid bilayer was found to be only 1/5th of a full monolayer based on its hydrodynamic radius. The saturation coverage, therefore, is not limited by the size of GLP-1 but by the ability of the bilayer to accommodate the peptide at high concentrations within the bilayer. Raman spectra show that GLP-1 association with the supported bilayer is accompanied by structural changes consistent with the intercalation of the peptide into bilayer, where the observed increase in acyl-chain order would increase the lipid density and provide free volume needed to accommodate the peptide. Furthermore, these results were compared with previous measurements of the association of fluorescently-labeled GLP-1 with a planar-supported bilayer; the unlabeled peptide exhibits a 3-fold greater affinity for the lipid-bilayer on the porous-silica support suggesting that the fluorescent label alters GLP-1 lipid-bilayer association.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Measurement of Residual Stress in Silicon Carbide Fibers of Tubular Composites Using Raman Spectroscopy
Not provided.
Materials Science↗
Raman Shifting a Tunable ArF Excimer Laser to Wavelengths of 190 to 240 nm With a Forced Convection Raman Cell
Tunable radiation, at ultraviolet wavelengths, is produced by Raman shifting a modified 285-mJ ArF excimer laser. Multiple Stokes outputs are observed in H2, CH4, D2, N2, SF6, and CF4 (20, 22, 53, 21, 2.1, and 0.35 percent, respectively). Numbers in parentheses are the first Stokes energy conversion efficiencies. We can access 70 percent of the frequency range 42000-52000 cm (exp -1) (190-240 nm) with Stokes energies that vary from 0.2 microJoule to 58 mJ inside the Raman cell. By using 110 mJ of pump energy and D 2 , the tunable first Stokes energy varies over the 29-58 mJ range as the wavelength is tuned over the 204-206 nm range. Dependence on input energy, gas pressure, He mixture fraction, and circulation of the gas in the forced convection Raman cell is discussed; Stokes conversion is also discussed for laser repetition rates from 1 to 100 Hz. An empirical equation is given to determine whether forced convection can improve outputs for a given repetition rate.
Balla, R. Jeffrey↗
Spatially Offset Femtosecond Stimulated Raman Spectroscopy: Observing Exciton Transport through a Vibrational Lens
To design better molecular electronic devices, we need a strong understanding of how charges or excitons propagate, as many efficiency losses arise during transport. Exciton transport has been difficult to study because excitons tend to be short-lived, have short diffusion lengths, and can easily recombine. Here, we debut spatially offset femtosecond stimulated Raman spectroscopy (SO-FSRS), a three-pulse ultrafast microscopy technique. By offsetting the photoexcitation beam, we can monitor Raman spectral changes as a function of both time and position. We used SO-FSRS on 6,13-bis(triisopropylsilylethynyl) pentacene, a well-studied organic semiconductor used in photovoltaics and field-effect transistors. Furthermore, we demonstrated that the fast exciton and free charge carrier transport axes are identical and observed that exciton transport is less anisotropic by a factor of ~3. SO-FSRS is the first technique that directly tracks molecular structural evolution during exciton transport, which can provide roadmaps for tailor-making molecules for specific electronic devices.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Nanoindentation-Enhanced Tip-Enhanced Raman Spectroscopy
We combine nanoindentation, herein achieved using atomic force microscopy (AFM)-based pulsed-force lithography, with tip-enhanced Raman spectroscopy (TERS) and imaging. Our approach entails indentation and multimodal characterization of otherwise flat Au substrates, followed by chemical functionalization and TERS spectral imaging of the indented nanostructures. We find that the resulting structures, which vary in shape and size depending on the tip used to produce them, may sustain nano-confined and significantly enhanced local fields. We take advantage of the latter and illustrate TERS-based ultrasensitive detection/chemical fingerprinting as well as chemical reaction imaging – all using a single platform for nano-lithography, topographic imaging, hyperspectral dark field optical microscopy, and TERS.
Wang, Chih-Feng↗
Simultaneous observation of rotational coherent Stokes Raman scattering and coherent anti-Stokes Raman scattering in air and nitrogen
Rotational coherent Stokes Raman scattering (CSRS) and coherent anti-Stokes Raman scattering (CARS) in air and in nitrogen were observed simultaneously by using broadband generation and detection. In the broadband technique used, the entire CARS and CSRS spectrum was generated in a single laser pulse; the CSRS and CARS signals were dispersed by a spectrograph and detected simultaneously by an optical multichannel analyzer. A three-dimensional phase-matching geometry was used to achieve spatial resolution of the CSRS and CARS beams from the input beams. Under resonant conditions, similar experiments may provide a means of investigating the possible interaction between the CSRS and CARS processes in driving the rotational levels.
Snow, J. B.↗
Remote-Raman and Micro-Raman Studies of Solid CO2, CH4, Gas Hydrates and Ice
It is well known that on Mars CO2 is the principal constituent of the thin atmosphere and on a seasonal basis CO2 snow and frost coats the polar caps. Also over 25% of the Martian atmosphere freezes out and sublimes again each year. The Mars Odyssey Emission Imaging system (THEMIS) has discovered water ice exposed near the edge of Mars southern perennials cap. In recent years, it has been suggested that in Martian subsurface CO2 may exist as gas hydrate (8CO2 + 44 H2O) with melting temperature of 10C. Since the crust of Mars has been stable for enough time there is also a possibility that methane formed by magmatic processes and/or as a byproduct of anaerobic deep biosphere activity to have raised toward the planet s surface. This methane would have been captured and stored as methane hydrate, which concentrates methane and water. Determination of abundance and distribution of these ices on the surface and in the near surface are of fundamental importance for understanding Martian atmosphere, and for future exploration of Mars. In this work, we have evaluated feasibility of using remote Raman and micro-Raman spectroscopy as potential nondestructive and non-contact techniques for detecting solid CO2, CH4 gas, and gas hydrates as well as water-ice on planetary surfaces.
Sharma, S. K.↗
Tip-enhanced Raman imaging of photocatalytic reactions on thermally-reshaped gold and gold–palladium microplates
The plasmonic/photocatalytic properties of thermally-reshaped walled gold–palladium microplates (WAu@PdMPs) have been explored by TERS.
Li, Zhandong↗
Resonant Raman scattering by Raman-active infrared-inactive phonons in II-IV semiconductors
Mg compounds family of antifluorite structured small-gap semiconductors, investigating surface light scattering properties by Raman scattering techniques
Anastassakis, E.↗
Comparison of measurements by the NASA/GSFC scanning raman lidar and the DOE/ARM CART raman lidar
Latent heat transfer through evaporation and condensation of water vapor is the most important energy transport mechanism in the atmosphere. In addition, water vapor is the most active greenhouse gas. Any global warming scenario must take accurate account of the spatial and temporal variation of water vapor in order to account for both of these effects. Due to the great importance of water vapor in atmospheric radiation studies, specific intensive operations periods (IOPs) have been hosted by the Department of Energy's Atmospheric Radiation Measurements (ARM) program. One of the goals of these IOPs has been to determine the quality of and explain any discrepancies among a wide variety of water vapor measuring instruments. Raman lidar systems developed by NASA/Goddard Space Flight Center and DOE/Sandia National Laboratories have participated in the two Water Vapor IOPs (WVIOPs) held at the Southern Great Plains (SGP) Cloud and Radiation Testbed Site (CART) site during 1996 (WVIOP1) and 1997 (WVIOP2). Detailed comparisons of these two systems is ongoing but this effort has already resulted in numerous improvements in design and data analysis for both lidar systems.
Whiteman, David↗