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At least 181 records · Page 10

Aging of microstructural compartments in human compact bone

Composition of microstructural compartments in compact bone of aging male subjects was assessed using Raman microscopy. Secondary mineralization of unremodeled fragments persisted for two decades. Replacement of these tissue fragments with secondary osteons kept mean composition constant over age, but at a fully mineralized limit. Slowing of remodeling may increase fracture susceptibility through an increase in proportion of highly mineralized tissue. In this study, the aging process in the microstructural compartments of human femoral cortical bone was investigated and related to changes in the overall tissue composition within the age range of 17-73 years. Raman microprobe analysis was used to assess the mineral content, mineral crystallinity, and carbonate substitution in fragments of primary lamellar bone that survived remodeling for decades. Tissue composition of the secondary osteonal population was investigated to determine the composition of turned over tissue volume. Finally, Raman spectral analysis of homogenized tissue was performed to evaluate the effects of unremodeled and newly formed tissue on the overall tissue composition. The chemical composition of the primary lamellar bone exhibited two chronological stages. Organic matrix became more mineralized and the crystallinity of the mineral improved during the first stage, which lasted for two decades. The mineral content and the mineral crystallinity did not vary during the second stage. The results for the primary lamellar bone demonstrated that physiological mineralization, as evidenced by crystal growth and maturation, is a continuous process that may persist as long as two decades, and the growth and maturation process stops after the organic matrix becomes "fully mineralized." The average mineral content and the average mineral crystallinity of the homogenized tissue did not change with age. It was also observed that the mineral content of the homogenized tissue was consistently greater than the osteons and similar to the "fully mineralized" stage of primary bone. The results of this study demonstrated that unremodeled compartments of bone grow older through maturation and growth of mineral crystals in a protracted fashion. However, the secondary osteonal remodeling impedes this aging process and maintains the mean tissue age fairly constant over decades. Therefore, slowing of remodeling may lead to brittle bone tissue through accumulation of fully mineralized tissue fragments.

Non-NASA Center

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.

Design and Commissioning of a Deuterium-Tritium Gas Delivery System for Muon Catalyzed Fusion in a Diamond Anvil Cell

We report the design, commissioning, and operation of deuterium-deuterium (DD) and deuterium-tritium (DT) gas delivery systems developed to load a diamond anvil cell (DAC) beam target for muon-catalyzed fusion (muCF). The DAC approach enables DT fuel to be compressed to GPa pressures at more than twice the liquid density and heated from cryogenic temperatures through 500 K, opening access to a substantially expanded parameter range for muCF kinetics and yield measurements. In this approach, DT is cryo-condensed to a liquid in a minichamber and then compressed in the DAC using a helium-driven pneumatic membrane, achieving high pressures in a millimeter-scale DT sample volume. A DD gas delivery system was designed and used to validate the experimental apparatus, measure the gas quantities needed for filling, develop operational experience, and collect kinetics and yield data with DD targets. The DT gas delivery system adds tritium-specific capabilities for inventory minimization, secondary containment, and activity monitoring. The DT system integrates depleted uranium storage beds and a liquid helium cryogenic condenser used for pressure building and cryopumping. High-purity delivery is provided by a rapid-response palladium permeator. The system is housed in a helium-atmosphere glovebox held at negative pressure with continuous cleanup. We present the process and instrumentation design, a failure modes and effects analysis (FMEA), and data from the experiment's in situ Raman spectrometer, which provides direct confirmation of target loading and composition through the optically clear diamond anvils. The 2024 and 2025 DT campaigns achieved repeatable target fills and operation with no measurable tritium releases to the stack, demonstrating safe, high-purity DT loading at novel density-temperature conditions for muCF studies.

Koukina, Elena [Acceleron Fusion]

Theoretical studies of Resonance Enhanced Stimulated Raman Scattering (RESRS) of frequency doubled Alexandrite laser wavelengths in cesium vapor

This work focused on understanding the effects of arbitrary transverse and longitudinal relaxation rates on the susceptibilities of coherently driven three-level systems. The approximation of a single relaxation rate often made in previous work is strongly invalidated by the variation in the spontaneous emission lifetime between various atomic level pairs in systems such as cesium. It is of great importance to the problem of nonlinear infrared generation to determine the dependence of both real and imaginary susceptibility on relaxation rates. The imaginary susceptibility on the pump transition determines the absorption of pump photons and the imaginary susceptibility on the laser transition determines the spectral dependence of the gain. This is of particular importance for pure Raman emission (i.e., absorption at linecenter of the gain transition) as it determines the tunability characteristics we are aiming to predict. The real susceptibility is important when cavities are used at the signal field as this will determine the loaded resonance of the Raman oscillator. Researchers show that in some cases which result from having different relaxation rates mode splitting may result, allowing more than one frequency to have the same Raman wavelength, possibly resulting in a temporal instability.

Lawandy, N. M.

An Investigation of Thermal Properties of 2D Materials [Dissertation]

Studying the thermal conductivity of 2D materials is important due to the applications of 2D materials in fields such as thermal management, thermoelectricity, renewable energy, and sensors. As such, measurements of the thermal conductivity of these 2D materials become important to measure. Thermal conductivity is often difficult to measure for 2D materials due to their atomically thin nature and many experimental methods for doing so requiring contact with the sample, which can alter the thermal properties. A non-contact method for calculating the thermal conductivity of 2D materials supported on substrates in order to model the thermal conductivity of 2D materials for devices, is proposed and experimentally performed in this dissertation. The optothermal Raman technique is a useful non-contact diagnostic technique useful in determining the thermal conductivity of 2D materials. The optothermal Raman typically does not account for heat losses due to convection or radiation or substrate resistance, which are shown to be important factors to consider when developing an optothermal Raman model. Additionally, the calculation of the interfacial thermal conductance between the bottom surface of the sample and the top surface of the substrate, plays an important role in determining the final value of the thermal conductivity of a supported sample, and will yield differing results based on whether or not the conductance is calculated using an approach such as the Diffuse Mismatch Model (DMM) or calculated directly by varying the laser heating profile (usually done by changing the laser objective). This is shown to be the case for both graphene on Ni, graphene on Cu, and SnSe 2 on Cu. In addition to experimentally calculating the thermal conductivity of a 2D material with the optothermal Raman technique, the thermal conductivity of 2D materials can also be calculated using computational methods. The three-phonon method is a method which can be used to simulate phonon scattering processes and determine the thermal conductivity of semiconductors, wherein phonon scattering is the dominant mechanism which determines the thermal conductivity. The three-phonon method uses relaxation times for phonon scattering with other phonons, electrons, and other material system elements, such as isotopes or material defects, in order to create a single-mode relaxation time approximation (SMRTA), which is used to calculate the final value of the thermal conductivity. An important consideration when determining the thermal conductivity of a 2D material using this method is the device geometry, which is reflected in this work as the phonon-boundary scattering relaxation time. This inclusion is important along with the inclusion of phonon-electron scattering in accurately determining the thermal conductivity of a 2D material. In both the optothermal Raman experiments and the three-phonon method computations, strain is shown to have a demonstrable effect on the thermal conductivity of 2D materials. When a 1.1% strain was applied to the mechanical properties of SnSe, the three-phonon processes yielded a lower thermal conductivity than the no-strain case. For the optothermal Raman experiments, the strain induced in the Cu substrate and transferred to a single-layer graphene (SLG) sample yields a trend where the thermal conductivity of the SLG decreases with respect to strain applied. In the case where the interfacial thermal conductance was calculated directly, the conductance increased with respect to strain applied. This presents strain as a reliable and viable method for tuning the thermal properties of 2D materials for device applications.

36 MATERIALS SCIENCE

Gravity Effects in Carbon Nanotube Growth by Thermal Chemical Vapor Deposition

Carbon nanotubes are synthesized using thermal chemical vapor deposition. The sizes of these carbon nanotubes (CNT) are quite uniform and the length of the tube is up to several tens of micrometers. With the substrate surface normal either along or against the gravity vector, different growth orientations of CNT are observed by scanning electron microscopy although the Raman spectra are similar for samples synthesized at different locations. These results suggest the gravitation effects in the growth of long and small diameter CNT.

Zhu, S.

CART and GSFC raman lidar measurements of atmospheric aerosol backscattering and extinction profiles for EOS validation and ARM radiation studies

The aerosol retrieval algorithms used by the Moderate-Resolution Imaging Spectroradiometer (MODIS) and Multi-Angle Imaging SpectroRadiometer (MISR) sensors on the Earth Observing Satellite (EOS) AM-1 platform operate by comparing measured radiances with tabulated radiances that have been computed for specific aerosol models. These aerosol models are based almost entirely on surface and/or column averaged measurements and so may not accurately represent the ambient aerosol properties. Therefore, to validate these EOS algorithms and to determine the effects of aerosols on the clear-sky radiative flux, we have begun to evaluate the vertical variability of ambient aerosol properties using the aerosol backscattering and extinction profiles measured by the Cloud and Radiation Testbed (CART) and NASA Goddard Space Flight Center (GSFC) Raman Lidars. Using the procedures developed for the GSFC Scanning Raman Lidar (SRL), we have developed and have begun to implement algorithms for the CART Raman Lidar to routinely provide profiles of aerosol extinction and backscattering during both nighttime and ,daytime operations. Aerosol backscattering and extinction profiles are computed for both lidar systems using data acquired during the 1996 and 1997 Water Vapor Intensive Operating Periods (IOPs). By integrating these aerosol extinction profiles, we derive measurements of aerosol optical thickness and compare these with coincident sun photometer measurements. We also use these measurements to measure the aerosol extinction/backscatter ratio S(sub a) (i.e. 'lidar ratio'). Furthermore, we use the simultaneous water vapor measurements acquired by these Raman lidars to investigate the effects of water vapor on aerosol optical properties.

Ferrare, R. A.

Raman Spectroscopic In Situ Monitoring of Highly Turbid Media

The ability to run chemical processing more efficiently and cost effectively is a need that spans critical materials recovery and legacy nuclear waste cleanup. Sensors integrated to provide online monitoring are essential to addressing this need by providing near-real time feedback on process conditions, which can improve efficiency, aid in decision making, and reduce the need for grab sample measurements. Optical spectroscopy is well-suited for providing online chemical composition information and has been widely applied in varied chemical systems. However, applications in turbid matrices continue to represent substantial challenges to sensor performance, where absorption or scattering of excitation light can cause significant signal interference. Here, in this study, close-focus Raman probes are investigated for use in turbid media as a way to overcome the signal loss from the scattering of the Raman excitation source. This, paired with advanced data science techniques, allowed for the development of chemometric models for the accurate quantification of several analytes of interest (NO 3 – , NO 2 – , and PO 4 3– ) in highly turbid solutions with solids loadings of up to 20 wt %. This work focuses on offline sample measurement and characterization as an initial step toward the development of online monitoring capabilities. Chemical systems of interest were focused on nuclear waste at the Hanford Site, which represents highly complex matrices that could realize significant processing benefits through the integration of online monitoring.

Felmy, Heather M. [Pacific Northwest National Labo

Refinement of the Robert-Bonamy Formalism: Considering Effects from the Line Coupling

Since it was developed in 1979, the Robert-Bonamy (RB) formalism has been widely used in calculating pressure broadened half-widths and induced shifts for many molecular systems. However, this formalism contains several approximations whose applicability has not been thoroughly justified. One of them is that lines of interest are well isolated. When these authors developed the formalism, they have relied on this assumption twice. First, in calculating the spectral density F(ω), they have only considered the diagonal matrix elements of the relaxation operator. Due to this simplification, effects from the line mixing are ignored. Second, when they applied the linked cluster theorem to remove the cutoff, they have assumed the matrix elements of the operator exp(-iS(sub 1) - S(sub 2)) can be replaced by the exponential of the matrix elements of -iS(sub 1) - S(sub 2). With this replacement, effects from the line coupling are also ignored. Although both these two simplifications relied on the same approximation, their validity criteria are completely different and the latter is more stringent than the former. As a result, in many cases where the line mixing becomes negligible, significant effects from the line coupling have been completely missed. In the present study, we have developed a new method to evaluate the matrix elements of exp(-iS(sub 1) - S(sub 2)) and have refined the RB formalism such that line coupling can be taken into account. Our numerical calculations of the half-widths for Raman Q lines of the N(sub 2)-N(sub 2) pair have demonstrated that effects from the line coupling are important. In comparison with values derived from the RB formalism, new calculated values for these lines are significantly reduced. A recent study has shown that in comparison with the measurements and the most accurate close coupling calculations, the RB formalism overestimates the half-widths by a large amount. As a result, the refinement of the RB formalism goes in the right direction and these new calculated half-widths become closer to the "true" values.

spectra

Diethylenetriamine-functionalized graphene oxide: Insights into ion adsorption and applications in rare earth element separation

The growing demand for critical minerals and materials requires atom- and energy-efficient, selective separations to overcome the challenges posed by the similar chemical and physical properties of the rare earth elements (REEs) and their low concentrations in unconventional domestic feedstocks. Here, in this study, we developed diethylenetriamine-functionalized graphene oxide (DETA-GO) as a membrane material for REE adsorption and separation. Synthesis conditions were optimized to maximize nitrogen incorporation while also preserving GO dispersibility for facile membrane fabrication. We investigated the mechanism of amine functionalization, the nitrogen-bonding configurations, the organization of the interlayer transport channels, and the resulting effects on ion and water transport for REE separations. Neat-GO and DETA-GO multilayer laminate membranes were fabricated by vacuum filtration onto polymer supports. To investigate the effects of amine functionalization, the membranes were characterized using scanning electron microscopy, Raman, Fourier transform infrared, and X-ray photoelectron spectroscopy, as well as grazing-incidence X-ray diffraction measurements. Ion permeation experiments with representative lanthanum (La 3+ ) and ytterbium (Yb 3+ ) solutions revealed enhanced ion adsorption and water transport through DETA-GO membranes compared to neat-GO. The strong affinity of the membranes for multivalent REEs was also validated with conductivity and inductively coupled plasma mass spectrometry measurements. Atomistic insight into the role of amine functionalization in modulating nanochannel architecture and long-term stability, optimizing adsorption sites, and regulating REE and water transport was obtained using classical molecular dynamics simulations. Collectively, our joint experimental and theoretical study demonstrates the potential of DETA-GO membranes for selective REE separations, offering insights into ion-binding mechanisms, water-transport properties, and nanochannel optimization for the recovery of critical materials from aqueous feedstocks.

Adsorbent

Electron cyclotron resonance microwave plasma deposition of a-Si:H and a-SiC:H films

The paper reports electron cyclotron resonance (ECR) deposition of a-Si:H and a-SiC:H thin films using SiH4, CH4, and hydrogen mixed gas plasmas. The ECR deposition conditions were investigated in the pressure region of 0.1 to 100 mtorr, and the film properties were characterized by light and dark conductivity measurements, XRD, Raman spectroscopy, optical transmission, and IR spectroscopy. In addition, the hydrogen dilution effect on ECR-deposited a-SiC:H was investigated.

Shing, Y. H.

First Look at the Upper Tropospheric Ozone Mixing Ratio from OMI Estimated using the Cloud Slicing Technique

The Cloud Slicing technique has emerged as a powerful tool for the study of ozone in the upper troposphere. In this technique one looks at the variation with cloud height of the above-cloud column ozone derived from the backscattered ultraviolet instruments, such as TOMS, to determine the ozone mixing ratio. For this technique to work properly one needs an instrument with relatively good horizontal resolution with very good signal to noise in measuring above-cloud column ozone. In addition, one needs the (radiatively) effective cloud pressure rather than the cloud-top pressure, for the ultraviolet photons received by a satellite instrument are scattered from inside the cloud rather than from the top. For this study we use data from the OMI sensor, which was recently launched on the EOS Aura satellite. OMI is a W-Visible backscattering instrument with a nadir pixel size of 13 x 24 km. The effective cloud pressure is derived from a new algorithm based on Rotational Raman Scattering and O2-O2, absorption in the 340-400 nm band of OMI.

Bhartia, Pawan K.

Atom Interferometry for Detection of Gravitational Waves: NASA Institute for Advanced Concepts (NIAC) - Phase 1 Final Report

This report presents the results of the 2012-2013 NASA Institute for Advanced Concepts (NIAC) Phase 1 "Atom Interferometry for Detection of Gravitational Waves" project. The origin of this GW (Gravitational Wave) detection concept using atoms can be traced to theoretical work that first appeared in 2008 and also to a satellite mission-focused followup study that was done in 2011. The goal of the current project was to explore both theoretical and technical issues surrounding the implementation of this idea, as well as to begin performing proof-of-concept experiments to validate critical aspects of the proposal.The top level trade space for the detector design is driven by the strategy employed to mitigate laser frequency noise, which, if uncontrolled, can mask GW signatures. One of the advantages of the atom interferometric approach is the possibility of single baseline detection (Fig. 1.1), even in the presence of laser noise. This is enabled by the differential measurement between the two ensembles of atoms, which can result in substantial laser noise suppression. The details of this suppression depend on the atomic physics techniques used to implement the atom interferometry. Specifically, we considered the effect on noise suppression that results from using traditional two-photon Raman transitions (with alkali atoms) and also single-photon transitions (with alkaline earth-like atoms).The interferometers shown in Fig 1.1(b) take advantage of single-photon transitions (as opposed to traditional Raman transitions) because using light pulses from one direction at a time allows for near perfect common-mode cancellation of laser phase noise, even for long baselines. This calls for the use of atomic transitions with an (ideally large) optical energy level difference with a long (greater than 1 second) lifetime, such as high-transitions routinely used for optical atomic clocks in species like Sr, Ca and Yb. Notably, large momentum transfer (LMT) atom optics - and the sensitivity enhancement they confer – can still be realized by simply adding additional pairs of alternating pulses to each beam splitter process. Section 3 reports on the theoretical work we performed to justify this GW detection protocol using single-photon transitions. This approach represents a new method for GW detection using atoms that is distinct from the original proposal from 2008. At the system level, we evaluated three architectures, each of which implements a different solution to the laser frequency noise issue. The first two designs are based on two-photon Raman transitions with Rb atoms. One of these is a three-satellite, multiple baseline design while the other is a two-satellite, single baseline design. The third proposal is a two-satellite, single baseline design that uses single-photon transitions with Sr atoms. These three architectures are described in more detail in Section 2. There are a number of known technical issues that we have started to address using ground-based experiments. These issues include atom technology development needs such as, for example, lower ensemble temperature requirements and large momentum transfer (LMT) atom optics. To this end, we have built a 10-meter scale atom drop tower, where we can perform proof-of-principle demonstrations of the proposed AGIS detector in an environment that permits more than 2.5 seconds of free-fall time. This facility allows for demonstration of atom interferometry with long interrogation time (seconds) and large atom wavepacket

Saif, Babak N.

Strain-Modified Raman Responses in Monolayer MoS 2 Nanobubbles Resolved at 5 nm

The formation of nanoscale bubbles is an unavoidable consequence during the transfer of two-dimensional materials onto target substrates, driven by van der Waals interactions at the interface. While often viewed as imperfections, these nanoscale bubbles have garnered considerable scientific interest due to the substantial in-plane strain gradients they induce, which in turn give rise to a variety of intriguing optoelectronic effects, particularly in semiconducting transition metal dichalcogenides. Determining and analyzing the strain distribution within nanobubbles at the nanoscale is crucial for advancing our understanding of these underlying strain-induced effects. Here, we present a high-resolution scanning tunneling microscopy-based tip-enhanced Raman spectroscopic investigation of localized nanoscale strain distribution within the nanobubbles formed between monolayer MoS 2 and Au interface. By employing cryogenic temperature (78 K), we successfully differentiate the nanoscale Raman signatures between nanobubble edge and pristine MoS 2 . We verify a maximum tensile strain of ∽1.15–1.34% at the nanobubble edge, which gradually diminishes toward the center, yielding a cross-sectional strain profile consistent with a doughnut-shaped distribution. Furthermore, we report to achieve ∽5 nm spatial resolution in probing such edge-localized strain within the nanobubble. In addition, comparative average strain analysis of such MoS 2 nanobubbles is conducted via geometric mechanistic analysis such as membrane and nonlinear plate theories, providing key insight into the geometric nature near the bubble edge. Our work provide fundamental information about strain-induced nanoscale chemical understanding of 2D materials on the nanometer scale, paving the way for practical applications of nanobubbles in strain-engineered optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Observation of atmospheric ozone by dial with Raman lasers pumped by a KrF laser

Since the XeCl excimer laser (308 nm) was first used in Differential Absorption Lidar (DIAL) for stratospheric ozone detection, the XeCl ozone lidar became a useful tool for the monitoring of the stratospheric ozone concentration. Shorter wavelength lasers are needed for the observation of ozone in the troposphere where the ozone concentration is about one order of magnitude smaller than in the stratosphere. In 1983, tropospheric ozone was observed with the combination of the second Stokes line (290.4 nm) of stimulated Raman scattering from methane pumped by a KrF laser and the XeCl laser line. The measurement of the ozone distribution from ground to 30 km was reported, using three Stokes lines of Raman lasers pumped by a KrF laser. At wavelengths shorter than 295 nm, the background solar radiation is effectively suppressed by atmospheric ozone. Such a solar-blind effect can be expected when two wavelengths 277 and 290.4 nm are used for DIAL ozone detection. A preliminary measurement of the day time ozone distribution in the troposphere is presented using these wavelengths generated by a KrF laser with a Raman shifter. Analysis using the lidar equation predicts the maximum detectable range is 7 km.

Maeda, M.

Monitoring Sulfuric Acid and Temperature Using Raman Spectroscopy and Multivariate Chemometrics

Multivariate regression models were optimized for the quantification of sulfuric acid (H 2 SO 4 ) [0–8 M] and temperature (20 °C–80 °C) in the presence of ammonium sulfate ((NH 4 ) 2 SO 4 [0–0.6 M]) using Raman spectroscopy. Optical vibrational spectroscopy is a useful nondestructive technique for the in situ analysis of complex chemical systems notoriously difficult to monitor in situ and in real-time. Multivariate analysis, a chemometrics method, can be paired with these nondestructive optical methods for determining analyte concentration and speciation in complex solutions, such as dissociated species in polyprotic acids, e.g., H 2 SO 4 . The effect of temperature is often overlooked although it can have a major influence on speciation and the corresponding Raman spectra. Here, in this study, partial least squares regression models were optimized for the quantification of H 2 SO 4 and its two deprotonated forms as a function of temperature. Measuring bisulfate as a function of temperature is particularly challenging owing to changes in the second dissociation constant. A designed training set effectively minimized the sample set size and trained a robust predictive model with percent root mean square error of <3% for H 2 SO 4 . The practical strategy employed here was demonstrated to be effective for building chemometric models that directly account for dynamic temperatures with static samples and is shown to be amenable to flow cell analysis applications with a simple calibration transfer for process monitoring applications.

D-optimal design

Structural and phonon anomalies in the superconducting Bi 2 Sr 2 CaCu 2 O 8+σ with varying doping level at high pressures

Here we examined the effect of the lattice compression on the crystal structure of the Bi 2 Sr 2 CaCu 2 O 8+σ superconductor with nearly optimally doped and overdoped composition using X-ray diffraction technique. Our studies show that at high pressures (up to 30 GPa ) the doping level does not affect the crystal structure of this superconductor. Along with this, structural anomalies in ratio appear at a pressure that corresponds to that at which T c begins to decrease. This fact indicates a close connection between the observed anomalies and superconductivity. We also studied the effect of doping and pressure on the T c (P) and on the Raman active lattice modes of the Bi 2 Sr 2 CaCu 2 O 8+σ superconductors. We find universal suppression of the T c by the pressure starting from the critical pressure P c in the range from 9 to 16 GPa, depending on the doping level of the Bi 2 Sr 2 CaCu 2 O 8+σ samples. Concomitantly, we observe phonon anomalies around 10 to 20 GPa, which indicate possible pressure-induced charge redistribution in BiO layers. These newly detected anomalies may be related to the changes in the electronic structure which compete with the superconductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND