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Resolving local structural motifs across the phase evolution of zinc titanates with computational x-ray absorption spectroscopy

Resolving the local structure motifs that characterize phase evolution as a function of composition is a key challenge in structure characterization of complex materials. Here, in this study, we combine first-principles simulations and x-ray absorption near-edge structures (XANES) analysis to gain insights into the structure evolution revealed by measurements across a combinatorial zinc titanate thin film, which was grown with smoothly varying composition over a wide range of the Ti:Zn ratio. Specifically, we propose a cluster blind-signal-separation (cBSS) method for XANES spectral analysis based on a library of the structures and spectra of representative local motifs. In addition to motifs from zinc titanate crystals, two types of Ti-defect models constructed in this study are key to the understanding of the structure characteristics in the Zn-rich region. The cBSS method makes use of both spectral clustering of the simulated site-XANES spectra library and the BSS procedure to construct high-fidelity spectral basis functions from an experimental spectral sequence. The method provides a rigorous measure of the spectral sensitivity and basis completeness. The results of the XANES analysis are corroborated with other experimental modalities, including x-ray diffraction and spectroscopic ellipsometry, to validate the cBSS method. The calculated motif weights resulting from fitting the XANES spectra with the cBSS basis probe the atomic structure characteristics of both crystalline and amorphous phases as a function of the Ti/Zn composition. The insights of the local structure motif evolution are pivotal to the understanding of the nonmonotonic trend in the optical gap, which may lead to potential applications through tuning the optical properties of zinc titanate. The workflow of the XANES spectral analysis developed in this work can be generalized to construct the structure-property relationship in a broad material space.

36 MATERIALS SCIENCE↗

LiDAR-Based Map Relative Localization Performance Analysis for Landing on Europa

This paper presents preliminary simulations andanalyses done to assess the feasibility of performing Map RelativeLocalization (MRL) with the Europa Lander LiDAR beingdeveloped for the Europa Lander Pre-Phase A concept. MapRelative Localization is the process of determining the horizontalposition of a lander with respect to an onboard, a-priori map,by comparing the map to sensor observations of the terrain duringdeorbit, descent, and landing (DDL). Although kilometerscaleposition knowledge is commonly available during DDL,landing in hazard-rich environments requires position errors of100 m or less. Prior knowledge in the case of Europa Landerwill be visual and topographic maps collected by the upcomingEuropa Clipper mission. The Mars 2020 Lander Vision System(LVS) uses images from a camera to localize with respect tovisual maps. This technology, as well as a 3D imaging LiDAR indevelopment for hazard detection, is currently baselined for theEuropa Lander Pre-Phase A concept. This paper investigatesthe potential use of the hazard detection LiDAR to performMRL with respect to a 3D digital elevation model (DEM)provided by the Europa Clipper mission, as an alternative orbackup solution to passive optical MRL. Compared to passiveoptical MRL, one advantage of LiDAR-based localization isthat it is insensitive to lighting conditions, potentially relaxingrequirements on synchronizing map acquisition and landingtime of day. To analyze LiDAR based MRL performance,six representative terrains are synthetically up-sampled fromGalileo-derived maps of Europa to a resolution of 0.5 m/pxand covering an area of 4 km by 4 km. These maps are usedas ground-truth to generate simulated noisy a-priori onboardtopographic maps expected from Europa Clipper as well assimulated LiDAR DEMs generated at an altitude of 5 km duringEuropa Lander DDL. The simulated LiDAR DEM is matchedagainst the simulated map via 2D normalized cross-correlation,exploiting the accurately known spacecraft attitude to avoidthe need for more computationally intensive algorithms such asIterative Closest Point (ICP). Two sources of measurement errorare identified for analysis: 1) additive Gaussian noise in therange measurements from the Europa Lander LiDAR and theEuropa Clipper derived maps and 2) errors in the LiDAR DEMinduced by errors in the Europa Lander state estimate which isused to de-warp the LiDAR scan data into a DEM format. Weassess the effect of each of these types of errors independently onmatching performance as well as the overall performance whenall types of error are introduced. Additionally, we present theresult of a sensitivity study to terrain frequency content.

Trawny, Nikolas↗

High-Temperature Thermometer Using Cr-Doped GdAlO3 Broadband Luminescence

A new concept has been developed for a high-temperature luminescence-based optical thermometer that both shows the desired temperature sensitivity in the upper temperature range of present state-of-the-art luminescence thermometers (above 1,300 C), while maintaining substantial stronger luminescence signal intensity that will allow these optical thermometers to operate in the presence of the high thermal background radiation typical of industrial applications. This objective is attained by using a Cr-doped GdAlO3 (Cr:GdAlO3) sensor with an orthorhombic perovskite structure, resulting in broadband luminescence that remains strong at high temperature due to the favorable electron energy level spacing of Cr:GdAlO3. The Cr:GdAlO3 temperature (and pressure) sensor can be incorporated into, or applied onto, a component s surface when a non-contact surface temperature measurement is desired, or alternatively, the temperature sensor can be attached to the end of a fiber-optic probe that can then be positioned at the location where the temperature measurement is desired. In the case of the fiber-optic probe, both the pulsed excitation and the luminescence emission travel through the fiber-optic light guide. In either case, a pulsed light source provides excitation of the luminescence, and the broadband luminescence emission is collected. Real-time temperature measurements are obtain ed using a least-squares fitting algorithm that determines the luminescence decay time, which has a known temperature dependence established by calibration. Due to the broad absorption and emission bands for Cr:GdAlO3, there is considerable flexibility in the choice of excitation wavelength and emission wavelength detection bands. The strategic choice of the GdAlO3 host is based on its high crystal field, phase stability, and distorted symmetry at the Cr3+ occupation sites. The use of the broadband emission for temperature sensing at high temperatures is a key feature of the invention and is novel since broadband luminescence emission normally shows severe thermal quenching. The tightly bound AlO6 octahedra in GdAlO3 results in a larger energy barrier to nonradiative decays than in other materials and therefore makes using broadband emission for temperature sensing possible at high temperatures. This approach results in a substantial increase in temperature capability. For example, the most commonly used Cr-doped crystal used for luminescence-based temperature measurements, ruby, has only been demonstrated up to 600 C, whereas the Cr:GdAlO3 optical thermometer under development has already been shown to exhibit useful luminescence up to 1,300 C. Because GdAlO3 is non-reactive and is stable in harsh, high-temperature environments, sensors composed of Cr:GdAlO3 will be very well suited for remote high-temperature measurements in engine or industrial environments where its intense high-temperature luminescence will stand out above significant thermal radiation background levels.

Eldridge, Jeffrey↗

Switching of Magnetic Order via Non‐Magnetic Al Addition in FeCoNiMnAl x Films

Magnetic high entropy alloys (HEAs) consisting of 3 d transition metals offer an exciting platform to explore novel magnetic phases as they often house competing exchange interactions in combination with random site disorders. In this work, a sensitive and tunable magnetic order is demonstrated in sputtered single-layer FeCoNiMnAl x films, as a function of non-magnetic Al addition, along with an unexpected exchange bias effect. Thin films of 50 nm FeCoNiMn exhibit a face-centered-cubic ( fcc ) phase, reentrant spin glass (SG) transition near 100 K, and a large exchange bias of over 500 Oe after field-cooling to 5 K. The exchange bias is increased to 930 Oe through a small addition of 5 at.% Al. Further Al addition to 12 at.% results in a body-centered-cubic ( bcc ) phase, coinciding with a large increase in the saturation magnetization, decrease of exchange bias to 50 Oe, and suppression of SG behavior. The change in magnetic order across the Al-induced structural transformation is mediated by the switching of Mn ground state from AF to FM, which is supported by first-principles calculations and experimentally confirmed via X-ray magnetic circular dichroism. These results open up new HEA strategies for explorations of novel magnetic phases.

competing exchange interactions↗

Applicability of Micro X-Ray Fluorescence Spectroscopy to Astromaterials Curation and Research

Introduction: The Astromaterials Acquisition and Curation Office at NASA’s Johnson Space Center (JSC) curates NASA’s astromaterial sample collections which includes: Apollo samples, Luna samples, Ant-arctic meteorites, cosmic dust particles, microparticle impacts into space-flown materials, Genesis solar wind atoms, Stardust comet Wild-2 particles, Stardust inter-stellar particles, Hayabusa asteroid Itokawa particles, Hayabusa 2 asteroid Ryugu particles, and future OSIRIS-Rex asteroid Bennu particles (landing in Sep-tember, 2023) [1–3]. To enhance JSC’s advanced cu-ration capabilities, we have recently installed a high-performance micro-X-ray fluorescence (µXRF) spec-trometer to assist in sample characterization through rapid, non-destructive, in-situ elemental analyses that do not require the sample preparation protocols (i.e., polishing and carbon-coating) commonly needed for electron beam analyses. With this new instrument, we are capable of detecting all elements down to carbon in a variable-pressure or He-purged chamber for anal-ysis of a wide range of sample types. Here we describe the instrumental set-up, capabilities, and applicability of µXRF analysis to astromaterials curation and re-search. Instrumentation and Methodology: The X-ray fluorescence and computed tomography lab (X-FaCT) lab at JSC is now equipped with a Bruker M4 Tornado Plus µXRF (Fig. 1). This system is an energy-dispersive x-ray spectrometer equipped with two 60 mm2 silicon drift detectors (SDD) that are able to be used simulta-neously for output count rates ~500,000 cps. New light element windows allow detecting and analyzing the entire elemental range from carbon to americium. Two x-ray tubes (micro-focus Rh with polycapillary lenses and W with collimators of 0.5, 1.0, 2.0, and 4.5 mm) with max excitation parameters of 50 kV, 30 W and 50 kV, 40 W, respectively, allow for more flexibility of the analysis of high energy lines. The motorized X-Y-Z stage has a mapping range of 190 x 160 mm and can support samples up to 7 kg (~15.5 lbs) and a height of 120 mm [4]. Analytical modes include elemental analysis (down to ~20 µm spot size) via point, line, or area of bulk materials (rock surfaces, thin sections, thick sections, etc.) as well as coating analysis (determination of thickness and composition) of samples. This system has a variable vacuum chamber (1 mbar to 1 atm) that is also equipped with a He-purge system which accommodates vacuum sensitive samples while still allowing detection of light elements at atmospheric pressure. Utility and Applicability of µXRF in Astro-materials research and exploration science (ARES): Elemental analysis using µXRF is commonly em-ployed for both terrestrial and planetary geological science disciplines [5]. It is especially useful for analy-sis of astromaterials given the limited sample prepara-tion required, which is not feasible for certain materi-als. Here we show select applications of µXRF anal-yses of astromaterials that can, have, and will be done at JSC’s X-FaCT lab. Point analysis: In-situ spot analyses (~20 µm spot size) on a cut slab of Martian meteorite NWA 10922 allowed for the discovery, qualitative elemental analy-sis and determination of different feldspar minerals [6]. These point analyses served as an effective prelim-inary step for subsequent quantitative analyses. Ana-lytical standards can be employed for more accurate quantification of µXRF spot analyses. Area analysis: This analytical mode measures all detectable elements (from C to Am) at each pixel (>5 µm pixel size) in a user-defined area. The results are shown as elemental maps which can be extracted as 16-bit TIFF’s for further data processing. In Fig. 2. we show elemental distribution maps of the high-Ti basalt 73001,531 that have been processed using ImageJ software. From these maps you can accurately and quickly (this map took ~50 mins.) identify mineral components, such as pyroxene, plagioclase, oxides, and phosphates, compositional zoning, and mineral textures. Detection of high-Z phases: µXRF techniques are es-pecially effective at analyzing trace minerals with high-atomic-number (high-Z) elements because the high-energy characteristic X-rays used (relative to SEM EDS) allow for mapping of K lines in elements up to La (typically SEM maps use L X-ray lines for elements >Zn, and these can often have interferences). Thus, µXRF is especially suited for identifying minerals like zircon, baddeleyite, REE-rich phosphates, Fe-rich met-als, oxides, sulfides, and phosphides [4]. In Fig. 3 we show elemental distribution maps for 73001,530 where we are able to correlate the original video image with, Zr, Si, Y and Hf elemental maps together identi-fying the location of a zircon. In this location you would expect lower Si compared to surrounding mate-rial, as well as higher Zr, Y, and Hf content compared to surrounding material, all of which is confirmed by our XRF ele-mental distribution maps (Figure 2.) Conclusions: The new M4 Tornado Plus µXRF within the Astromaterials Acquisition and Curation office at NASA JSC allows for rapid and non-destructive elemental analysis of astromaterials with limited or no sample preparation. µXRF analyses pro-vide crucial compositional knowledge for the prelimi-nary examination and curation of astromaterials. This instrument enhances the advanced curation capabili-ties in the X-FaCT laboratory at JSC by allowing pro-ductive, cohesive, and non-destructive multi-modal x-ray analyses on astromaterial samples, which is neces-sary for the comprehensive curation and study of our current and future astromaterial collections. Addition-ally, µXRF can provide complimentary information to researchers for studies on astromaterials. References: [1] Allen, C. et al., (2011). Chemie De Erde Geochemistry, 71, 1-20. [2] McCubbin, F. M. et al., (2016) 47th LPSC, abstract #2668 [3] Zeigler, R. A. et al., (2017) 48th LPSC, abstract #2772 [4] Bruker User Manual [5] Young et al., (2016) Appl. Geochemistry, 72, 77-87 [6] Mor-ris, R. V. et al., (2023) 54th LPSC.

E W O'Neal↗

SIM-Lite Mission Spectral Calibration Sensitivities and Refinements

SIM-Lite missions will perform astrometry at microarcsecond accuracy using star light interferometry. For typical baselines that are shorter than 10 meters, this requires to measure optical path difference (OPD) accurate to tens of picometers calling for highly accurate calibration. A major challenge is to calibrate the star spectral dependency in fringe measurements -- the spectral calibration. Previously, we have developed a spectral calibration and estimation scheme achieving picometer level accuracy. In this paper, we present the improvements regarding the application of this scheme from sensitivity studies. Data from the SIM Spectral Calibration Development Unit (SCDU) test facility shows that the fringe OPD is very sensitive to pointings of both beams from the two arms of the interferometer. This sensitivity coupled with a systematic pointing error provides a mechanism to explain the bias changes in 2007. Improving system alignment can effectively reduce this sensitivity and thus errors due to pointing errors. Modeling this sensitivity can lead to further improvement in data processing. We then investigate the sensitivity to a model parameter, the bandwidth used in the fringe model, which presents an interesting trade between systematic and random errors. Finally we show the mitigation of calibration errors due to system drifts by interpolating instrument calibrations. These improvements enable us to use SCDU data to demonstrate that SIM-Lite missions can meet the 1pm noise floor requirement for detecting earth-like exoplanets.

wave front aberration↗

Imaging Valence Electron Rearrangement in a Chemical Reaction Using Hard X-Ray Scattering

We have observed the signatures of valence electron rearrangement in photoexcited ammonia using ultrafast hard x-ray scattering. Time-resolved x-ray scattering is a powerful tool for imaging structural dynamics in molecules because of the strong scattering from the core electrons localized near each nucleus. Such core-electron contributions generally dominate the differential scattering signal, masking any signatures of rearrangement in the chemically important valence electrons. Ammonia represents an exception to the typically high core-to-valence electron ratio. Here, we measured 9.8 keV x-ray scattering from gas-phase deuterated ammonia following photoexcitation via a 200 nm pump pulse to the 3s Rydberg state. We observed changes in the recorded scattering patterns due to the initial photoexcitation and subsequent deuterium dissociation. Ab initio calculations confirm that the observed signal is sensitive to the rearrangement of the single photoexcited valence electron as well as the interplay between adiabatic and nonadiabatic dissociation channels. The use of ultrafast hard x-ray scattering to image the structural rearrangement of single valence electrons constitutes an important advance in tracking valence electronic structure in photoexcited atoms and molecules.

Gabalski, Ian [SLAC National Accelerator Laborator↗

Evaluation of Mixed-Phase Microphysics Within Winter Storms Using Field Data and In Situ Observations

Snow prediction within models is sensitive to the snow densities, habits, and degree of riming within the BMPs. Improving these BMPs is a crucial step toward improving both weather forecasting and climate predictions. Several microphysical schemes in the Weather Research and Forecasting (WRF) model down to 1.33-km grid spacing are evaluated using aircraft, radar, and ground in situ data from the Global Precipitation Mission Cold-season Precipitation Experiment (GCPEx) experiment over southern Ontario, as well as a few years (12 winter storms) of surface measurements of riming, crystal habit, snow density, and radar measurements at Stony Brook, NY (SBNY on north shore of Long Island) during the 2009-2012 winter seasons. Surface microphysical measurements at SBNY were taken every 15 to 30 minutes using a stereo microscope and camera, and snow depth and snow density were also recorded. During these storms, a vertically-pointing Ku band radar was used to observe the vertical evolution of reflectivity and Doppler vertical velocities. The GCPex presentation will focus on verification using aircraft spirals through warm frontal snow band event on 18 February 2012. All the BMPs realistically simulated the structure of the band and the vertical distribution of snow/ice aloft, except the SBU-YLIN overpredicted slightly and Thompson (THOM) underpredicted somewhat. The Morrison (MORR) scheme produced the best slope size distribution for snow, while the Stony Brook (SBU) underpredicted and the THOM slightly overpredicted. Those schemes that have the slope intercept a function of temperature (SBU and WSM6) tended to perform better for that parameter than others, especially the fixed intercept in Goddard. Overall, the spread among BMPs was smaller than in other studies, likely because there was limited riming with the band. For the 15 cases at SBNY, which include moderate and heavy riming events, the non-spherical snow assumption (THOM and SBU-YLIN) simulated a more realistic distribution of reflectivity than spherical snow assumptions in the WSM6 and MORR schemes. The MORR, WSM6, and SBU schemes are comparable to the observed velocity distribution in light and moderate riming periods. The THOM is approx. 0.25 m/s too slow with its velocity distribution in these periods. In heavier riming, the vertical Doppler velocities in the WSM6, THOM, and MORR schemes were approx. 0.25 m/s too slow, while the SBU was 0.25 to 0.5 m/s too fast because of some excessive cloud water issues.

Colle, Brian A.↗

Effects of Melt Processing on Evolution of Structure in PEEK

We report on the effects of melt processing temperature on structure formation in Poly(ether-ether-ketone), PEEK. Real time Small Angle X-ray Scattering, SAXS, and thermal analysis are used to follow the melting behavior after various stages of processing. Assignment of peaks to structural entities within the material, the relative perfection of the crystals, and the possibility of their reorganization, are all influenced by the melt processing history. With the advent of high intensity synchrotron sources of X-radiation, polymer scientists gain a research tool which, when used along with thermal analysis, provides additional structural information about the crystals during growth and subsequent melting. PEEK is an engineering thermoplastic polymer with a very high glass transition temperature (145 C) and crystal melting point (337 C). PEEK has been the subject of recent studies by X-ray scattering in which melt and cold crystallization were followed in real-time. X-ray scattering and thermal studies have been used to address the formation of dual endothermic response which has been variously ascribed to lamellar insertion, dual crystal populations, or melting followed by re-crystallization. Another important issue is whether all of the amorphous phase is located in interlamellar regions, or alternatively whether some is located in "pockets" away from the crystalline lamellar stacks. The interpretation of scattering from lamellar stacks varies depending upon whether such amorphous pockets are formed. Some groups believe all of the amorphous phase is interlamellar. This leads to selection of a smaller thickness for the crystals. Other groups suggest that most amorphous phase is not interlamellar, and this leads to the suggestion that the crystal thickness is larger than the amorphous layer within the stacks. To investigate these ideas, we used SAXS and Differential Scanning Calorimetry to compare results of single and dual stage melt crystallization of PEEK using a treatment scheme involving annealing/crystallization at T(sub a1) followed by annealing at T(sub a2) where either T(sub a1) < T(sub a2) or T(sub a1) > T(sub a2). We proposed a model to explain multiple melting endotherms in PPS, treated according to one or two-stage melt or cold crystallization. Key features of this model are that multiple endotherms: (1) are due to reorganization/recrystallization after cold crystallization; and, (2) are dominated by crystal morphology after melt crystallization at high T. In other words, multiple distinct crystal populations are formed by the latter treatment, leading to observation of multiple melting. PEEK 45OG pellets (ICI Americas) were the starting material for this study. Films were compression molded at 400 C, then quenched to ice water. Samples were heated to 375 C in a Mettler FP80 hot stage and held for three min. to erase crystal seeds before cooling them to T(sub a1) = 280 C . Samples were held at T(sub a2) for a period of time, then immediately heated to 360 C. In the second treatment samples were held at T(sub a1) = 31 C for different crystallization times t(sub c) then cooled to 295 C and held 15 min. In situ (SAXS) experiments were performed at the Brookhaven National Synchrotron Light Source with the sample located inside the Mettler hot stage. The system was equipped with a two-dimensional position sensitive detector. The sample to detector distance was 172.7 cm and the X-ray wavelength was 1.54 Angstroms. SAXS data were taken continuously during the isothermal periods and during the heating to 360 C at 5 C/min. Each SAXS scan was collected for 30 sec. Since the samples were isotropic, circular integration was used to increase the signal to noise ratio. After dual stage melt crystallization with T(sub a1) < T(sub a2) the lower melting endotherm arises from holding at T(sub a1). During cooling a broad distribution of crystals forms, and the low-melting tail is perfected during T(sub al). Heating to T(sub a2) melts these imperfect crystals and allows others with greater average long spacing to form in their place. After dual stage crystallization with T(sub a1) > T(sub a2), the amount of space remaining for additional growth at T(sub a2) depends upon the holding time at T(sub a1). The long period of crystals formed at T(sub a2) is smaller than that formed at T(sub a1) due to growth in a now-restricted geometry. Perfection of crystals is seen as an increase of the intensity of the population scattering at higher s, while the intensity of the population scattering at lower s stays constant. During heating from below to above the minor endotherm, we see rapid decrease of the intensity of the X-ray scattering corresponding to the population of crystals scattering in the shoulder. Another important observation is that after the sample is annealed at 295 C, the shoulder intensity is restored once again. The population scattering at higher s remains longer before it disappears in the sample treated to the second stage of melt crystallization, compared to the sample crystallized with a single stage. This could be interpreted as an effect of continued perfection of the less perfect population, which is also reflected in the increased melting temperature of the smaller endotherm as the holding time at 295 C increases. In the corresponding DSC scans we see a shift in the area and the peak temperature of the lower melting endotherm with an increase of the annealing time.

Georgiev, Georgi↗

Phase Function Determination in Support of Orbital Debris Size Estimation

To recover the size of a space debris object from photometric measurements, it is necessary to determine its albedo and basic shape: if the albedo is known, the reflective area can be calculated; and if the shape is known, the shape and area taken together can be used to estimate a characteristic dimension. Albedo is typically determined by inferring the object s material type from filter photometry or spectroscopy and is not the subject of the present study. Object shape, on the other hand, can be revealed from a time-history of the object s brightness response. The most data-rich presentation is a continuous light-curve that records the object s brightness for an entire sensor pass, which could last for tens of minutes to several hours: from this one can see both short-term periodic behavior as well as brightness variations with phase angle. Light-curve interpretation, however, is more art than science and does not lend itself easily to automation; and the collection method, which requires single-object telescope dedication for long periods of time, is not well suited to debris survey conditions. So one is led to investigate how easily an object s brightness phase function, which can be constructed from the more survey-friendly point photometry, can be used to recover object shape. Such a recovery is usually attempted by comparing a phase-function curve constructed from an object s empirical brightness measurements to analytically-derived curves for basic shapes or shape combinations. There are two ways to accomplish this: a simple averaged brightness-versus phase curve assembled from the empirical data, or a more elaborate approach in which one is essentially calculating a brightness PDF for each phase angle bin (a technique explored in unpublished AFRL/RV research and in Ojakangas 2011); in each case the empirical curve is compared to analytical results for shapes of interest. The latter technique promises more discrimination power but requires more data; the former can be assembled in its essentials from fewer measurements but will be less definitive in its assignments. The goal of the present study is to evaluate both techniques under debris survey conditions to determine their relative performance and, additionally, to learn precisely how a survey should be conducted in order to maximize their performance. Because the distendedness of objects has more of an effect than their precise shape in calculating a characteristic dimension, one is interested in the techniques discrimination ability to distinguish between an elongated rectangular prism and a short rectangular prism or cube, or an elongated cylinder from a squat cylinder or sphere. Sensitivity studies using simulated data will be conducted to determine discrimination power for both techniques as a function of amount of data collected and range (and specific region) of phase angles sampled. Empirical GEODSS photometry data for distended objects (dead payloads with solar panels, rocket bodies) and compact objects (cubesats, calibration spheres, squat payloads) will also be used to test this discrimination ability. The result will be a recommended technique and data collection paradigm for debris surveys in order to maximize this type of discrimination.

Hejduk, M. D.↗

Understanding the superconductivity and charge density wave interaction through quasi-static lattice fluctuations

In unconventional superconductors, coupled charge and lattice degrees of freedom can manifest in ordered phases of matter that are intertwined. In the cuprate family, fluctuating short-range charge correlations can coalesce into a longer-range charge density wave (CDW) order which is thought to intertwine with superconductivity, yet the nature of the interaction is still poorly understood. Here, by measuring subtle lattice fluctuations in underdoped YBa 2 Cu 3 O 6+y on quasi-static timescales (thousands of seconds) through X-ray photon correlation spectroscopy, we report sensitivity to both superconductivity and CDW. The atomic lattice shows remarkably faster relaxational dynamics upon approaching the superconducting transition at T c ≈ 65 K. By tracking the momentum dependence, we show that the intermediate scattering function almost monotonically scales with the relaxation distance of atoms away from their average positions above T c and in the presence of the CDW state, while this peculiar trend is reversed for other temperatures. These observations are consistent with an incipient CDW stabilized by local strain. This work provides insights into the crucial role of relaxational atomic fluctuations for understanding the electronic physics cuprates, which are inherently disordered due to carrier doping.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

On the Cycling of 231 Pa and 230 Th in Benthic Nepheloid Layers

The naturally-occurring radionuclides protactinium-231 ( 231 Pa) and thorium-230 ( 230 Th) are produced at approximately uniform rates in the ocean and thought to be removed from the water column through a reversible exchange with settling particles. Recent measurements along the U.S. GEOTRACES North Atlantic transect (GA03) revealed two features which are at odds with current understanding about 231 Pa and 230 Th cycling in the ocean: (i) a sharp decrease in dissolved 231 Pa ( 231 Pa d ) and 230 Th ( 230 Th d ) activities with depth below 2000-4000 m and (ii) very high particulate 231 Pa ( 231 Pa p ) and 230 Th ( 230 Th p ) activities near the bottom, at a number of stations between the New England continental shelf and Bermuda. Concomitant measurements of light attenuation from beam transmissometry showed that both features occur in benthic nepheloid layers (BNLs), which suggests that these features may stem, at least partly, from the presence of resuspended sediment in the deep water column. Here we explore the behaviour of 231 Pa and 230 Th in BNLs by using (i) radionuclide, optical, and hydrographic data from the western segment of GA03 (west of Bermuda) and (ii) a simplified model of particle and radionuclide cycling that includes a lateral particle source. First, the BNLs observed at GA03 stations are characterized from measurements of the beam attenuation coefficient converted to particle concentrations. At all stations, particle concentrations below the clear water minimum were the highest in the bottom mixed layer, whose thickness ranged from 95 to 320 m, and decreased generally with height above the bottom. The thickness of strong BNLs varied from 482 to 1358 m and the vertical integral of particle concentration in excess to that at the clear water minimum varied from 1 x 10 4 to 2 x 10 6 mg m −2 , among different stations. Second, the particle-radionuclide model is fitted to data from stations GT11-04 (New England continental rise) and GT11-08 (Hatteras abyssal plain), where samples for radionuclide analyses were collected in the BNL. The model can reproduce simultaneously the increase of particle concentration with depth, the low 231 Pa d and 230 Th d in the BNLs, and the high 231 Pa p and 230 Th p near the bottom. According to the model, at heights less than about 300 m above the seafloor, the dissolved phase was set primarily by a balance between adsorption and desorption, with vertical turbulent mixing playing a secondary role, whilst the particulate phase behaved largely as a non-reactive constituent supplied laterally and transported vertically by particle settling and turbulent mixing. Sensitivity tests with the model suggest that lateral particle sources near continental slopes and similar reliefs can produce significant biases both in the 230 Th normalization method and in the interpretation of sediment 231 Pa/ 230 Th records. Our findings yield insights into the influence of sediment resuspension and transport on 231 Pa and 230 Th in the deep ocean and highlight the need for considering these processes in paleoceanographic applications.

Nepheloid layer↗

Electron-doping-induced destabilization of the dimerized insulating state in monolayer IrTe 2

The ability to tune the electronic phases of two-dimensional (2D) materials through external perturbations provides a powerful route to engineer functional nanoscale systems. In particular, the ground state of monolayer (ML) 1T-IrTe 2 is highly sensitive to the interplay between local chemical bonding and global electronic topology, leading to a unique 2 × 1 dimerized insulating phase. Here, we present an angle-resolved photoemission study on the evolution of the electronic structure in ML IrTe 2 induced by in situ Rb adsorption. We find that Rb adsorption suppresses the 2 × 1 dimerized phase in ML IrTe 2 , inducing a clear insulator-to-metal transition. This transition is characterized by a reconstruction of the band topology toward a bilayer-like metallic configuration. Combined with first-principles calculations, our results demonstrate that the collapse of the insulating state originates from Ir valence change and suppression of Fermi surface nesting-driven instabilities. Our findings establish ML IrTe 2 as a model system for investigating instability-driven phase control in 2D materials and highlight its potential for tunable electronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Colloidal Behavior of Plutonium Oxide in Concentrated Electrolyte Solutions

The Hanford Site in Washington State manages legacy high-level radioactive waste streams that display major chemistry and engineering challenges, including the high salt levels and pH values that correspond to conditions under which many classical concepts describing chemical reactivity cannot be applied. One particular challenge that needs to be tackled at Hanford is that Pu concentrations, [Pu], in the soluble phases of the tank wastes are higher than expected based on the solubility of crystalline PuO2, which is widely accepted to be caused by the formation of PuO2 colloid, consisting of nano- to submicron-sized particles (PuO2 NPs). Fundamental research underpinning the behavior of PuO2 NPs under conditions not only relevant to the Hanford tank waste but at high ionic strength in general is needed to reliably predict the chemical reactivity of PuO2 NPs and develop engineering solutions to safely and efficiently process high-level radioactive waste into forms suitable for long-term storage. In this work, we study the behavior of PuO2 NPs (particle size ~100 nm) under high ionic strength conditions by reacting it with highly concentrated (up to 5 M) salt solutions. We explore different electrolyte compositions to elucidate the impact of different anions (NO3-, Cl-, ClO4-, SO42-, C2O42-, CO32-) on the stability of PuO2 NP in the acidic and alkaline pH regime. PuO2 NP aggregation and precipitation as function electrolyte concentration is tracked by a combination of liquid scintillation counting, dynamic light scattering for determination of particle size distributions, and zeta potentials as a proxy for particle charge. At acidic pH, electrolytes containing non-coordinating anions, such as NaNO3, NaCl, and NaClO4 mostly stabilize PuO2 NPs over a large electrolyte concentration range, showing only subtle differences in their reactivity. Other electrolyte anions show a more pronounced effect on the PuO2 NP stability: SO42-, binds directly to the particles’ surface, reverses the particle charge, and precipitates the PuO2 NPs efficiently even at intermediate sulfate concentrations (>0.1 M). In contrast, C2O42- is found to lead to high [Pu] in solution, in the milli-molar range, even at mildly acidic pH (~4). Thermodynamic modeling of the dissolved Pu concentrations using PHREEQC is unable to predict the observed [Pu] in the acidic pH regime, supporting the influence of colloids in maintaining elevated [Pu]. It is noteworthy that the current thermodynamic databases do not include constants for colloidal Pu phases and cannot accurately predict many of the high ionic strength solutions relevant to this work. The mechanisms and models responsible for these observations will need further investigation in the future. At high pH values (~12), PuO2 NPs exhibits classical sol-gel chemistry, meaning that upon destabilization of the colloidal sol, for example by addition of concentrated NaOH, highly porous and viscid PuO2 coagulates are formed that consist of a three-dimensional network likely held together by physical interactions. The PuO2 NP coagulate shows no significant reversibility of the aggregation when contacted with concentrated brines; however, PuO2 NPs can be efficiently resuspended in solution by addition of diluted electrolytes, alkaline solutions containing high amounts of carbonate, or simple addition of water. Especially carbonate is shown to stabilize PuO2 NPs in solution at high pH, characterized by stable colloidal suspensions that are resistant against sedimentation during centrifugation. Thermodynamic modeling of the carbonate system was able to predict an increasing dissolved Pu concentration with increasing carbonate concentration. However, the model was profoundly sensitive to the fixed redox potential and does not include any thermodynamic constants for colloidal Pu species.

Neumann, Julia↗

Directed Self-Assembly of the Organic Semiconductor C8-BTBT-C8 in Anodic Aluminum Oxide Nanopores

Controlling the self-assembly of organic semiconductors at the nanoscale is critical for advancing high-performance electronic and photonic devices, yet it remains challenging due to their intrinsic anisotropic crystallization and sensitivity to processing conditions. Here, in this study, we demonstrate that cylindrical nanoconfinement within anodic aluminum oxide membranes provides a versatile platform to precisely tune the molecular orientation and phase behavior of the prototypical organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT-C8). Combining temperature-dependent high-resolution synchrotron X-ray scattering with optical birefringence measurements, we uncover that confinement geometries (pore diameters 25–180 nm) and surface chemistry govern the emergence of distinct smectic A textures, featuring molecular layers either parallel or perpendicular to the pore axis. The competition between axial and radial smectic layering is modulated by pore size, surface hydrophilicity, and thermal history, enabling reversible control over domain orientations and transitions between liquid crystalline and crystalline states. Notably, nanoconfinement stabilizes the smectic phase over an expanded temperature range compared to bulk, while inducing complex multidomain configurations owing to geometric constraints and anchoring conditions. Our results elucidate fundamental mechanisms by which anisotropic nanoscale confinement directs the self-organization of highly conjugated organic molecules, with implications for optimizing directional charge transport and anisotropic optical responses in organic–inorganic hybrid nanoarchitectures. This study establishes nanoconfinement as a powerful strategy to engineer morphology and functional properties in organic semiconducting materials with nanoscale precision.

36 MATERIALS SCIENCE↗

Dynamic Atomistic Polar Structure Underpins Ultrahigh Linear Electro-Optic Coefficient in Transparent Ferroelectric Ceramics

Transparent ferroelectrics with high linear electro-optic (EO) coefficients are critical for advanced electro-optical devices. However, achieving optical transparency in ferroelectric ceramics remains challenging due to visible light scattering caused by defects such as domain walls, grain boundaries, and pores. Here, we report the successful fabrication of transparent ferroelectric ceramics through innovative chemical composition design and an advanced two-step sintering process in the La-doped Pb(Mg 1/3 Nb 2/3 )O 3 –PbTiO 3 system. The optical transparency, which is near the theoretical upper limit, can be attributed to the wide band gap and the minimization of light scattering of defects. By minimizing porosity and engineering grain/domain sizes to differ significantly from the wavelengths of visible light, we suppress scattering, achieving optical transparency near the theoretical upper limit. Strikingly, these ceramics exhibit an ultrahigh linear EO coefficient of ∼1417 pm/V, over 65 times greater than that of LiNbO 3 single crystals, the current industry standard. We attribute this exceptional performance to dynamic atomistic polar structures within switchable, thermally stable domains, which enhance electronic polarization sensitivity. This mechanism is corroborated by dielectric spectroscopy, high-resolution transmission electron microscopy and simulation. Our findings offer insights into the design of cost-effective transparent materials with exceptional EO properties, paving the way for next-generation electro-optical devices.

36 MATERIALS SCIENCE↗

What we Hope to Learn about Global Mineral Dust Aerosols from EOS Multi-Angle Imaging SpectroRadiometer (MISR)

On global scales, just a few broad atmospheric aerosol compositional groups are commonly observed. Of these, "mineral dust" is the only group which both contains non-spherical particles, and typically has size distributions with enough large particles for particle shape to affect its visible-light-scattering properties. The MISR instrument is scheduled for launch into a 10:30 AM sun-synchronous, polar orbit aboard the EOS Terra satellite in 1999. MISR will measure the upwelling visible radiance from Earth in 4 spectral bands centered at 446, 558, 672, and 866 nm, at each of 9 emission angles spread out in the forward and aft directions along the flight path at +/-70.5 deg, +/-60.0 deg, +/-45.6 deg, +/-26.1deg, and nadir. Over a period of 7 minutes, as the spacecraft flies along, a 360 km wide swath of Earth will successively be viewed by each of the cameras, allowing MISR to sample a very large range of scattering angles; in mid latitudes, the instrument will observe scattering angles between about 60 deg and 160 deg. Global coverage will be acquired about once in 9 days at the equator; the nominal mission lifetime is 6 years. The distinction in single scattering phase function between natural distributions of spherical and randomly oriented, non-spherical particles, with a broad range of aspect ratios, shows up strongly for scattering angles ranging from about 90 deg to near 180 deg. For non-spherical particle distributions, single scattering phase functions tend to be much flatter in this region than for spherical particles. Since MISR samples the relevant range of scattering angles very well, we expect to be able to make critical distinctions between natural distributions of spherical and randomly oriented, non-spherical particles with MISR data. We anticipate that the new multiangle, multispectral data from MISR will also contain other information about particle properties, a major step beyond current spacecraft remote sensing retrievals, which obtain aerosol optical depth based on entirely assumed particle microphysical properties. According to simulations over cloud-free, calm ocean, for pure particles with natural ranges of optical depth, particle size, and indices of refraction, MISR should retrieve column optical depth for all but the darkest particles, to an uncertainty of at most 0.05 or 20%, whichever is larger, even if the particle properties are poorly known. For one common particle type, soot, constraints on the optical depth over dark ocean are very poor. The simulated measurements also should allow us to separate two to four compositional groups based on indices of refraction, and to identify three to four distinct size groups between 0.1 and 2.0 microns characteristic radius at most latitudes. The technique is most sensitive to particle microphysical properties in the "accumulation mode" sizes. where particle scattering undergoes the transition from Rayleigh to large-particle regimes for the MISR wavelengths. Based on these results, we expect to distinguish air masses containing different aerosol types, routinely and globally, with multiangle remote sensing data. Such data complements in situ and field data, which can provide details about aerosol size and composition locally that are needed to assess the radiative effects of aerosols quantitatively. Both field data and correlations in space and time with likely source and sink regions will also be helpful in developing a global picture of mineral dust aerosol budgets. Further work on the expected sensitivity of MISR to natural mixtures of pure particles, including climatologically likely mineral dust components, is currently underway.

Kahn, Ralph↗

Characterization of Fuel-to-Coolant Heat Transfer During Reactivity-Initiated Accidents Using Tightly Coupled Thermal Hydraulics and Fuel Thermomechanics

The reactivity-initiated accident (RIA) is a complex scenario with several tightly interacting physical phenomena. Accurately predicting fuel behavior during these transients is difficult due to limitations in the modeling of fuel-to-coolant heat transfer. Common approaches to simulate RIAs involve standalone calculations using either a fuel performance code or a thermal-hydraulic code. The complex interdependencies of thermal-hydraulic and fuel mechanical behavior suggest that a tight coupling between these codes may provide more accurate predictions of fuel-to-coolant heat transfer and cladding mechanical response. Here, RELAP5-3D and BISON are coupled in this paper to simulate RIAs, and a sensitivity analysis is performed to rank key thermal properties and two-phase heat transfer parameters relevant for fuel-to-coolant heat transfer and cladding failure mechanisms in UO 2 –Zircaloy-4 systems. Gas gap conductance, film boiling heat transfer uncertainty, pulse width, fuel-specific heat capacity, and cladding-specific heat capacity were identified as important parameters. Variations in figures of merit resulting from changes to pulse width and the material thermal properties indicate that time-dependent heat transfer rates are significant for safety-relevant mechanical parameters due to the time dependence of cladding ductility and pellet-cladding mechanical interaction loading. The results suggest that the thermal-hydraulic factors have a nonnegligible influence on the thermomechanical solution and vice versa. Tight coupling of both sets of physics is recommended to improve prediction of fuel behavior during RIAs. Highlights include the following: 1. The RELAP5-3D thermal-hydraulic code and the BISON fuel performance code are tightly coupled for simulation of RIA transients with energy depositions at the Zircaloy-4 cladding failure threshold. 2. Departure from nucleate boiling occurred for all simulated cases. Due to the ductility of fresh fuel, substantial ballooning occurred in most cases. 3. Gas gap conductance, fuel-specific heat capacity, cladding-specific heat capacity, transient pulse width, and film boiling heat transfer were the dominant thermal factors impacting the safety figures of merit at energy depositions.

Critical Heat Flux (CHF)↗