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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Neptunium redox speciation and determination of its total concentration in dissolved fuel simulant solutions by spectrophotometry

Here, two new approaches to measure Np concentration in dissolved used nuclear fuel simulant (aqueous feed for PUREX process) by spectrophotometry are developed. The first approach is based on chemical reduction of Np in the feed to its tetravalent state using ascorbic acid with simultaneous conversion of Pu(IV) to Pu(III). Interfering effects from light absorbing fission and corrosion products are accounted for by measuring optical absorbance spectrum of aqueous raffinate after extraction of U, Np, and Pu by tributyl phosphate in dodecane. The second approach uses no chemical treatment at all and relies on spontaneous valency adjustment of Np to Np(V) by dilution of the feed with water to reduce its acidity to low decimolar range of nitric acid concentration. Results of Np determination in the feed by spectrophotometry are in good agreement with its concentration measured by ICP-MS.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Slitless spectrophotometry with forward modelling: Principles and application to measuring atmospheric transmission

Context.In the next decade, many optical surveys will aim to answer the question of the nature of dark energy by measuring its equation-of-state parameter at the per mill level. This requires trusting the photometric calibration of the survey with a precision never reached so far on many sources of systematic uncertainties. The measurement of the on-site atmospheric transmission for each exposure, or for each season or for the full survey on average, can help reach the per mill precision for the magnitudes. Aims.This work aims at proving the ability to use slitless spectroscopy for standard-star spectrophotometry and its use to monitor on-site atmospheric transmission as needed, for example, by theVera C. RubinObservatory Legacy Survey of Space and Time supernova cosmology program. We fully deal with the case of a disperser in the filter wheel, which is the configuration chosen in theRubinAuxiliary Telescope. Methods.The theoretical basis of slitless spectrophotometry is at the heart of our forward-model approach to extract spectroscopic information from slitless data. We developed a publicly available software calledSpectractor, which implements each ingredient of the model and finally performs a fit of a spectrogram model directly on image data to obtain the spectrum. Results.We show through simulations that our model allows us to understand the structure of spectrophotometric exposures. We also demonstrate its use on real data by solving specific issues and illustrating that our procedure allows the improvement of the model describing the data. Finally, we discuss how this approach can be used to directly extract atmospheric transmission parameters from the data and thus provide the base for on-site atmosphere monitoring. We show the efficiency of the procedure in simulations and test it on the limited available data set.

Astronomy & Astrophysics↗
DOE OSTI2022

Feasibility Study of Spectrophotometry to Support a Promethium Production Program at ORNL

Optical spectroscopy can be used to optimize analytical measurements for lanthanide elements and provide real-time feedback to help guide production operations. This study evaluates spectrophotometry for the determination of samarium (Sm 3+ ) and neodymium (Nd 3+ ) in aqueous and organic solutions at concentrations relevant to a promethium (Pm) program separation scheme. Detection limits approached 0.5 mM for Nd 3+ and 2 mM for Sm 3+ using Ocean Insight spectrophotometers. Additionally, Sm 3+ detection limits using laser fluorescence spectra for Sm 3+ approached single ppm (mg∙L -1 ) levels. An absorption spectrum containing Nd and Pm is also reported and discussed. This work demonstrates proofof-principle concepts for applying spectrophotometry to online monitoring applications in support of a future Pm production program.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Comparing Designed Training Sets to Optimize Multivariate Regression Models for Pr, Nd, and Nitric Acid Using Spectrophotometry

Chemometric regression models were developed for the quantification of praseodymium (Pr, 0–1000 µg/mL), neodymium (Nd, 0–1000 µg/mL), and nitric acid (HNO 3 , 0.1–5 M) using spectrophotometry. Designed calibration sets were composed of 20 samples each: 10 model points and 10 lack-of-fit (LOF) points. The D-optimal designs effectively minimized the number of samples required to build models, and each design resulted in similar prediction performance, suggesting that statistical design of experiments can provide a reliable framework for selecting training set samples in three-variable systems. Partial least squares regression (PLSR) models were validated against a one-factor-at-a-time validation set composed of 125 samples (three variables, five levels). The top PLS-1 models resulted in average percent root mean square error of prediction error values of 3.5%, 1.7%, and 1.2% for Pr(III), Nd(III), and HNO 3 , respectively. Power set augmentations of the model and LOF samples were investigated to optimize the number of training set samples. PLSR models built using just required model points (10) had similar predictive capabilities as models including the LOF points (20) but with fewer samples. The number of validation samples was also varied systematically to learn how many samples are needed to validate regression models. This work addresses long-standing questions in the field of chemometrics to help make this approach amenable to the near-real-time quantification of hazardous species in remote settings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Partial Least Squares, Experimental Design, and Near-Infrared Spectrophotometry for the Remote Quantification of Nitric Acid Concentration and Temperature

Near-infrared spectrophotometry and partial least squares regression (PLSR) were evaluated to create a pleasantly simple yet effective approach for measuring HNO3 concentration with varying temperature levels. A training set, which covered HNO3 concentrations (0.1–8 M) and temperature (10–40 °C), was selected using a D-optimal design to minimize the number of samples required in the calibration set for PLSR analysis. The top D-optimal-selected PLSR models had root mean squared error of prediction values of 1.4% for HNO 3 and 4.0% for temperature. The PLSR models built from spectra collected on static samples were validated against flow tests including HNO 3 concentration and temperature gradients to test abnormal conditions (e.g., bubbles) and the model performance between sample points in the factor space. Based on cross-validation and prediction modeling statistics, the designed near-infrared absorption approach can provide remote, quantitative analysis of HNO 3 concentration and temperature for production-oriented applications in facilities where laser safety challenges would inhibit the implementation of other optical techniques (e.g., Raman spectroscopy) and in which space, time, and/or resources are constrained. The experimental design approach effectively minimized the number of samples in the training set and maintained or improved PLSR model performance, which makes the described chemometric approach more amenable to nuclear field applications.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2020

Cloud Atlas: Unraveling the Vertical Cloud Structure with the Time-series Spectrophotometry of an Unusually Red Brown Dwarf

Rotational modulations of emission spectra in brown dwarf and exoplanet atmospheres show that clouds are often distributed non-uniformly in these ultracool atmospheres. The spatial heterogeneity in cloud distribution demonstrates the impact of atmospheric dynamics on cloud formation and evolution. In this study, we update the Hubble Space Telescope (HST) time-series data analysis of the previously reported rotational modulations of WISEP J004701+680352—an unusually red late-L brown dwarf with a spectrum similar to that of the directly imaged planet HR 8799e. We construct a self-consistent spatially heterogeneous cloud model to explain the HST and the Spitzer time-series observations, as well as the time-averaged spectra of WISE 0047. Additionally, in the heterogeneous cloud model, a cloud thickness variation of around one pressure scale height explains the wavelength dependence in the HST near-IR spectral variability. By including disequilibrium CO/CH 4 chemistry, our models also reproduce the redder $J-{K}_{{\rm{s}}}$ color of WISE 0047 compared to that of field brown dwarfs. We discuss the impact of vertical cloud structure on atmospheric profile and estimate the minimum eddy diffusivity coefficient for other objects with redder colors. Our data analysis and forward modeling results demonstrate that time-series spectrophotometry with a broad wavelength coverage is a powerful tool for constraining heterogeneous atmospheric structure.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Ultracool Dwarfs Observed with the Spitzer Infrared Spectrograph. I. An Accurate Look at the L-to-T Transition at ~300 Myr from Optical Through Mid-infrared Spectrophotometry

Here we present Spitzer IRS 5–14 μm spectra and 16 μm and 22 μm photometry of the T2.5 companion to the ~300 Myr old G0V star HN Peg. We incorporate previous 0.8–5 μm observations to obtain the most comprehensive spectral energy distribution (SED) of an intermediate-gravity L/T-transition dwarf that, together with an accurate Gaia EDR3 parallax of the primary, enables us to derive precise fundamental parameters. We find that young (≈0.1–0.3 Gyr) early-T dwarfs on average have ≈140 K lower effective temperatures, ≈20% larger radii, and similar bolometric luminosities compared to ≳1 Gyr old field dwarfs with similar spectral types. Our accurate infrared spectrophotometry offers new detail at wavelengths where the dominant carbon-bearing molecules have their strongest transitions: at 3.4 μm for methane and at 4.6 μm for carbon monoxide. We assess the performance of various widely available photospheric models and find that models with condensates and/or clouds better reproduce the full SED of this moderately young early-T dwarf. However, cloud-free models incorporating a more general convective instability treatment reproduce at least the low-resolution near-infrared spectrum similarly well. Our analysis of R ≈ 2300 J-band spectra shows that the near-infrared potassium absorption lines in HN Peg B have similar strengths to those seen in both younger and older T2–T3 dwarfs. We conclude that while alkali lines are well established as surface gravity indicators for L-type or warmer stars, they are insensitive to surface gravity in early-T dwarfs.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Uniform Recalibration of Common Spectrophotometry Standard Stars onto the CALSPEC System Using the SuperNova Integral Field Spectrograph

Abstract We calibrate spectrophotometric optical spectra of 32 stars commonly used as standard stars, referenced to 14 stars already on the Hubble Space Telescope–based CALSPEC flux system. Observations of CALSPEC and non-CALSPEC stars were obtained with the SuperNova Integral Field Spectrograph over the wavelength range 3300–9400 Å as calibration for the Nearby Supernova Factory cosmology experiment. In total, this analysis used 4289 standard-star spectra taken on photometric nights. As a modern cosmology analysis, all presubmission methodological decisions were made with the flux scale and external comparison results blinded. The large number of spectra per star allows us to treat the wavelength-by-wavelength calibration for all nights simultaneously with a Bayesian hierarchical model, thereby enabling a consistent treatment of the Type Ia supernova cosmology analysis and the calibration on which it critically relies. We determine the typical per-observation repeatability (median 14 mmag for exposures ≳5 s), the Maunakea atmospheric transmission distribution (median dispersion of 7 mmag with uncertainty 1 mmag), and the scatter internal to our CALSPEC reference stars (median of 8 mmag). We also check our standards against literature filter photometry, finding generally good agreement over the full 12 mag range. Overall, the mean of our system is calibrated to the mean of CALSPEC at the level of ∼3 mmag. With our large number of observations, careful cross-checks, and 14 reference stars, our results are the best calibration yet achieved with an integral-field spectrograph, and among the best calibrated surveys.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

A transmission hologram for slitless spectrophotometry on a convergent telescope beam. 1. Focus and resolution

We report in this paper the test of a plane holographic optical element to be used as an aberration-corrected grating for a slitless spectrograph, inserted in a convergent telescope beam. Our long-term objective is the optimization of a specific hologram to switch the auxiliary telescope imager of the Vera Rubin Observatory into an accurate slitless spectrograph, dedicated to the atmospheric transmission measurement. We present and discuss here the promising results of tests performed with prototype holograms at the CTIO $0.9\,$m telescope during a run of 17 nights in 2017 May–June. After their on-sky geometrical characterization, the performances of the holograms as aberration-balanced dispersive optical elements have been established by analysing spectra obtained from spectrophotometric standard stars and narrow-band emitter planetary nebulae. Thanks to their additional optical function, our holographic disperser prototypes allow us to produce significantly better focused spectra within the full visible wavelength domain $[370,1050]\,$nm than a regular grating, which suffers from strong defocusing and aberrations when used in similar conditions. We show that the resolution of our slitless on-axis spectrograph equipped with the hologram approaches its theoretical performance. While estimating the benefits of a hologram for the spectrum resolution, the roadmap to produce a competitive holographic element for the Vera Rubin Observatory auxiliary telescope has been established.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Hierarchical Modeling to Enhance Spectrophotometry Measurements—Overcoming Dynamic Range Limitations for Remote Monitoring of Neptunium

A robust hierarchical model has been demonstrated for monitoring a wide range of neptunium concentrations (0.75–890 mM) and varying temperatures (10–80 °C) using chemometrics and feature selection. The visible–near infrared electronic absorption spectrum (400–1700 nm) of monocharged neptunyl dioxocation (Np(V) = NpO2+) includes many bands, which have molar absorption coefficients that differ by nearly 2 orders of magnitude. The shape, position, and intensity of these bands differ with chemical interactions and changing temperature. These challenges make traditional quantification by univariate methods unfeasible. Measuring Np(V) concentration over several orders of magnitude would typically necessitate cells with varying path length, optical switches, and/or multiple spectrophotometers. Alternatively, the differences in the molar extinction coefficients for multiple absorption bands can be used to quantify Np(V) concentration over 3 orders of magnitude with a single optical path length (1 mm) and a hierarchical multivariate model. In this work, principal component analysis was used to distinguish the concentration regime of the sample, directing it to the relevant partial least squares regression submodels. Each submodel was optimized with unique feature selection filters that were selected by a genetic algorithm to enhance predictions. Through this approach, the percent root mean square error of prediction values were ≤1.05% for Np(V) concentrations and ≤4% for temperatures. This approach may be applied to other nuclear fuel cycle and environmental applications requiring real-time spectroscopic measurements over a wide range of conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

The Spectroscopic Classification of Astronomical Transients (SCAT) Survey: Overview, Pipeline Description, Initial Results, and Future Plans

Here, we present the Spectroscopic Classification of Astronomical Transients (SCAT) survey, which is dedicated to spectrophotometric observations of transient objects such as supernovae and tidal disruption events. SCAT uses the SuperNova Integral-Field Spectrograph (SNIFS) on the University of Hawai’i 2.2 m (UH2.2m) telescope. SNIFS was designed specifically for accurate transient spectrophotometry, including absolute flux calibration and host-galaxy removal. We describe the data reduction and calibration pipeline including spectral extraction, telluric correction, atmospheric characterization, nightly photometricity, and spectrophotometric precision. We achieve ≲5% spectrophotometry across the full optical wavelength range (3500–9000 Å) under photometric conditions. The inclusion of photometry from the SNIFS multi-filter mosaic imager allows for decent spectrophotometric calibration (10%–20%) even under unfavorable weather/atmospheric conditions. SCAT obtained ≈640 spectra of transients over the first 3 yr of operations, including supernovae of all types, active galactic nuclei, cataclysmic variables, and rare transients such as superluminous supernovae and tidal disruption events. These observations will provide the community with benchmark spectrophotometry to constrain the next generation of hydrodynamic and radiative transfer models.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

UV-Vis spectrophotometric determination of rare earth elements (REE) speciation at near-neutral to alkaline pH. Part II: hydrolysis of Er from 25 to 75 °C

Aqueous speciation of rare earth elements (REE) controls their mobilization, fractionation, and enrichment in the natural waters. Geochemical modeling of their speciation is key to improve our understanding of the formation of economic mineral deposits, for developing mineral separation and mine tailing recovery technologies, and for characterizing the geochemistry of thermal water. However, our ability to predict the fate of REE in a wide pH and temperature range is limited by the scarcity of thermodynamic data for the REE hydroxyl complexes. In part I of this study (H. J. Han and A. P. Gysi, Dalton Trans., 2024, 53, 13129–13141), the optical properties of m-cresol purple (mCP) were determined using UV-Vis spectrophotometry between 25 and 75 °C in order to develop a method for deriving the hydrolysis constants of erbium (Er). Here, UV-Vis spectrophotometry experiments were conducted as a function of temperature between 35 and 75 °C to determine the hydrolysis of Er in near-neutral to alkaline solutions using mCP as an in situ pH color indicator. Here, the experiments were conducted with Er concentrations from 0 to ~0.253 mmol kg –1 in low ionic strength solutions (≤0.001 mol kg –1 ).

58 GEOSCIENCES↗
DOE OSTI2022

Extended Accelerated Stress Testing (EAST) of Glass/Glass, Glass/Backsheet and Glass/Transparent Backsheet PV Modules: Influence of EVA and POE Encapsulants: Preprint

This paper presents the indoor extended accelerated stress testing (EAST) results of glass/glass (GG), glass/backsheet (GB) and glass/transparent backsheet (GT) modules having identical cells and two different encapsulant types, ethyl-vinyl-acetate (EVA) and polyolefin-elastomer (POE). Six 4-cell modules having the above-mentioned construction combinations were subjected to extended ultraviolet (UV; 600 kWh/m2), damp-heat (DH; 2000 hours) and thermal-cycling (TC; 600 cycles) tests. The post-stress UV fluorescent imaging, electroluminescent imaging, reflectance spectrophotometry and colorimetry results indicated that the grid finger degradation and encapsulant browning are slightly higher in the GG modules compared to the GB modules. The post-stress IV test results indicated, in general, that the GG/EVA modules tend to perform inferior to the GG/POE modules with the EAST evaluation.

EVA↗
DOE OSTI2021

Liquid Crystal Films as Active Substrates for Nanoparticle Control

Organizing nanoparticles in a controlled way allows us to monitor their optical properties. It is particularly interesting to organize them on top of liquid crystal films to take advantage, in a second step, of the easy actuation of liquid crystals with external parameters such as temperature, electric fields, and so forth. We show that despite their fluidity, nematic and smectic films allow the formation of well-ordered hexagonal domains of gold spherical nanoparticles (AuNPs) at their surface, but we also show that both nematic films and AuNP domains impact each other. Using optical microscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM), and spectrophotometry, we compare nematic, polymer-stabilized nematic, and smectic films with AuNP domains made of NPs of diameter 6 nm. On the liquid crystal films, depressions are revealed below the AuNP domains, whereas the AuNP domains appear well-organized but with a hexagonal period shortened with respect to AuNP monolayers formed on hard substrates. We interpret these features by the anchoring tilt imposed by the AuNP domains on the liquid crystal molecules. The smectic-A layers characteristic of the nematic surface transform into smecticC layers, which induce the formation of depression. Here, the energy penalty associated with the local smectic-A/smectic-C transition induces the shortening of the AuNP domain period in order to decrease the AuNP domain surface. The observed large depth of the polymer-stabilized nematic depressions below AuNP domains may be explained either by an increased size of the polymer-stabilized smectic layers close to the surface or by an increased number of polymer-stabilized smectic liquid crystal smectic layers close to the surface with respect to pure nematic films.

36 MATERIALS SCIENCE↗
DOE OSTI2026

The Stability of Nd Hydroxyl Complexes at Near Neutral to Alkaline pH from 25 to 75 °C: Implications for Monazite Solubility in Hydrothermal Aqueous Fluids

Speciation of rare earth elements (REE) in aqueous fluids controls their mobilization during fluid-rock interaction. Thermodynamic modeling provides important insights into the factors controlling REE mobility and fractionation in aqueous fluids, in which aqueous REE hydroxyl complexes are particularly important across a broad pH range. However, the stability of these REE hydroxyl complexes remains poorly determined due to limited experimental data above ambient temperature. In this work, UV–vis spectrophotometry experiments were conducted to determine the cumulative hydrolysis constants for neodymium (Nd) from 25 to 75 °C in near-neutral to alkaline solutions. The color indicator m -cresol purple was used to determine in situ pH. Alkaline NaOH-bearing aqueous solutions were doped with varying initial Nd concentrations (0 to ∼0.155 mmol/kg), which resulted in the release of protons (H + ) and pH decrease during hydrolysis of Nd 3+ according to Nd 3+ + n H 2 O = Nd(OH) n 3– n + H + . The average OH – ligand number coordinated to Nd 3+ was found to increase from 1.0 to 1.6 at 25 °C and from 1.2 to 2.8 at 75 °C over a pH range from 6.3 to 9.0. The measured speciation shows an increased predominance of Nd(OH) 3 0 over the Nd(OH) 2 + and Nd(OH) 2+ species with increased temperature and pH. The increasing cumulative formation constants (log*β° n , n = 1 to 3) retrieved from 25 to 75 °C differ by 0.1 to 1.9 logarithmic units in comparison to existing thermodynamic databases. These updated thermodynamic data have important implications for geochemical modeling of the speciation of Nd hydroxyl complexes and the solubility of monazite as a function of pH.

58 GEOSCIENCES↗
DOE OSTI2020

Fast microflow kinetics and acid catalyst deactivation in glucose conversion to 5-hydroxymethylfurfural

5-Hydroxymethyl furfural (HMF) is an important platform chemical because it can be upgraded to various drop-in and performance-advantaged products. The cascade reaction of HMF production from glucose over a Lewis acid (CrCl 3 ) and a Brønsted acid (HCl) catalyst in aqueous media is investigated in a microreactor at short residence times and high temperatures. We study the formation of various chromium species using UV-visible spectrophotometry and elucidate the Cr(III) speciation. The catalyst reactivity increases sharply at short residence times, and then drops at long times. This indicates that the catalyst treatment plays a vital role in getting optimal reactivity, and recording the catalyst history is necessary. We develop a kinetic model to describe the catalyst speciation as well as the Lewis and Brønsted acid-catalyzed reaction kinetics using a hierarchical approach. Here, the model is in good agreement with experiments. We demonstrate the benefits of tandem Lewis-external added Brønsted acid catalysis in processing time, productivity, and catalyst stability. We apply this model to optimize the HMF yield and obtain ~36% yield at 200 °C in 7 min and report the highest productivity of ~15% yield per min, demonstrating the opportunity of reaching high productivity at short residence times.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Interrelationships among methods of estimating microbial biomass across multiple soil orders and biomes: Supporting data

This dataset contains environmental and soil measurements from 18 different locations across the globe including the SPRUCE experiment site and multiple sampling depths, with 17 of these locations having samples processed between 2012-2013 and one location (SPRUCE) collected in 2021 and processed in 2022. Environmental measurements include: mean annual temperature, mean annual precipitation, and 30-day presampling temperature. Soil physicochemical measurements include: particle size analysis (PSA), pH, gravimetric moisture content (GMC), bulk soil carbon (C) and nitrogen (N), total organic C and N, C:N ratio, and dissolved organic carbon (DOC). Soil biological measurements include: microbial biomass carbon (MBC) measured through chloroform fumigation extraction (CFE), gene copy numbers (GCN) of bacteria, fungi, and archaea measured through quantitative polymerase chain reaction (qPCR), DNA yield measured through Nanodrop spectrophotometry, and phospholipid fatty acids (PLFA) of bacteria and fungi measured through PLFA analysis. This data set contains one file in comma separate (*.csv) format.

archaea gene copy number↗