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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 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Influence of Methylammonium Chloride on Wide-Bandgap Halide Perovskites Films for Solar Cells

Wide-bandgap perovskites are of paramount importance as the photoactive layer of the top cell in high-efficiency tandem solar cells. Comparably high Br contents are required to widen the perovskite bandgap. However, the increase in Br content causes heterogeneous halide distribution and photoinstability. Here, in this study, the positive effect of the additive methylammonium chloride (MACl) on the optical and electronic properties of Br-rich perovskite, deposited using N-methyl-2-pyrrolidone (NMP) as co-solvent and the gas quenching method, is investigated. Simultaneous in situ grazing-incidence wide-angle X-ray scattering and photoluminescence spectroscopy are used to track the evolution of the structural and optoelectronic properties of the perovskites with different amounts of Br and MACl during the spin-coating and thermal annealing steps. The formation mechanism is elucidated in the presence of MACl. It is observed that chloride ions inhibit the intermediate phases, favoring the formation of a perovskite phase with higher crystallinity. Nano X-ray fluorescence mapping recognizes Br-richer and poorer nanometric domains, whose average sizes reduce for samples with MACl. In conclusion, it is demonstrated that adding MACl affects the formation of wide-bandgap perovskites via destabilization of the intermediate phases and acts on the homogenization of the halide distribution, leading to improved solar cell performances.

14 SOLAR ENERGY↗
DOE OSTI2021

Raman Microscopy Investigation of GLP-1 Peptide Association with Supported Phospholipid Bilayers

A wide range of important biological processes occur at phospholipid membranes including cell signaling, where a peptide or small molecule targets a membrane-localized receptor protein. In this work, we report the adaptation of confocal-Raman microscopy to quantify populations of unlabeled glucagon-like peptide-1 (GLP-1), a membrane-active 30-residue incretin peptide, in supported phospholipid bilayers deposited on the interior surfaces of wide-pore porous silica particles. Quantification of lipid bilayer-associated peptide is achieved by measuring the Raman scattering intensity of the peptide relative to that of the supported-lipid bilayer, which serves as an internal standard. The dependence of the bilayer-associated GLP-1 population on the solution-concentration of GLP-1 produces an isotherm used to determine the equilibrium constant for peptide-bilayer association and the maximum peptide surface coverage. The maximum coverage of GLP-1 in the lipid bilayer was found to be only 1/5th of a full monolayer based on its hydrodynamic radius. The saturation coverage, therefore, is not limited by the size of GLP-1 but by the ability of the bilayer to accommodate the peptide at high concentrations within the bilayer. Raman spectra show that GLP-1 association with the supported bilayer is accompanied by structural changes consistent with the intercalation of the peptide into bilayer, where the observed increase in acyl-chain order would increase the lipid density and provide free volume needed to accommodate the peptide. Furthermore, these results were compared with previous measurements of the association of fluorescently-labeled GLP-1 with a planar-supported bilayer; the unlabeled peptide exhibits a 3-fold greater affinity for the lipid-bilayer on the porous-silica support suggesting that the fluorescent label alters GLP-1 lipid-bilayer association.

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

Shinkolobweite, from the Shinkolobwe Mine, Democratic Republic of Congo: A New Mineral Containing Uranium in the Rare Pentavalent Oxidation State

ABSTRACT Shinkolobweite, Pb1.333[U5+O(OH)(UO2)5O4.67(OH)5.33](H2O)5, is a new lead uranyl oxide-hydroxide hydrate mineral containing hexavalent and pentavalent uranium from the Shinkolobwe mine, Democratic Republic of Congo. Crystals of shinkolobweite are dark reddish-brown prisms up to 0.5 mm in length, occurring on a matrix of massive uraninite associated with fourmarierite, rutherfordine, soddyite, and sklodowskite. Crystals are translucent with subadamantine luster and light bronze-yellow streak, are flattened on {010}, are elongated on [001], and exhibit the forms {100}, {010}, {101}, and . The mineral is non-fluorescent under both longwave and shortwave ultraviolet illumination. It has a Mohs hardness of ∼2 and exhibits brittle tenacity with perfect cleavage on {010}, imperfect cleavage on {100}, and even fracture. The calculated density is 5.853 g/cm3 based on the empirical formula. Electron probe microanalysis provided the empirical formula Pb1.290U6+4.876U5+1.166O27H16.633 based on 27 O apfu and U5+:U6+ determined by X-ray photoelectron spectroscopy. Shinkolobweite is orthorhombic, superspace group Pnnm(0b0)000, a = 14.4808(4), b = 7.0681(8), c = 11.9423(3) Å, V = 1222.32(15) Å3, modulation wave vector [0 1/3 0], and Z = 2. The structure was refined from 8959 reflections to a final R1 = 0.0736 for all reflections. Uranyl oxide-hydroxide sheets in shinkolobweite adopt the β-U3O8 topology and possess (3 + 1) commensurately modulated ordering that results from the long-range ordering of U5+ and U6+ in the sheet, as well as the position and occupancy of interlayer Pb2+ cations. Observations of a topological transition between α-U3O8 and β-U3O8 type sheets in shinkolobweite supplements our understanding of U5+ mineral oxidation and stability.

Mineralogy↗
DOE OSTI2021

Nonlinear Optical Microscopy with Ultralow Quantum Light

Nonlinear optical (NLO) microscopy relies on multiple light–matter interactions to provide unique contrast mechanisms and imaging capabilities that are inaccessible to traditional linear optical imaging approaches, making them versatile tools to understand a wide range of complex systems. However, the strong excitation fields that are necessary to drive higher-order optical processes efficiently are often responsible for photobleaching, photodegradation, and interruption in many systems of interest. This is especially true for imaging living biological samples over prolonged periods of time or in accessing intrinsic dynamics of electronic excited-state processes in spatially heterogeneous materials. This perspective outlines some of the key limitations of two NLO imaging modalities implemented in our lab and highlights the unique potential afforded by the quantum properties of light, especially entangled two-photon absorption based NLO spectroscopy and microscopy. Here, we further review some of the recent exciting advances in this emerging filed and highlight some major challenges facing the realization of quantum-light-enabled NLO imaging modalities.

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

Combining diagnostics, modeling, and control systems for automated alignment of the TES beamline

X-ray beamlines are essential components of all synchrotron light sources. Practical operations involve frequent variation in beamline component positions and orientation, particularly when photon beam parameters shift due to experimental needs, or due to variations in the incoming photon beam. The alignment process can be time consuming and takes away from valuable beam time for experimental data collection. We describe progress in the automation of certain alignment tasks on the tender-energy X-ray spectroscopy (TES) beamline at the National Synchrotron Light Source II (NSLS-II). The beamline is controlled using the BlueSky software in which high level experimental plans guide the beamline components during an experiment. Numerous software packages exist for beamline modeling, and they may be tied to the beamline control system using a package we are continuing to develop called Sirepo-Bluesky. The photon beam distribution may be measured with fluorescent screens, and a relation between beam and machine state can be found by varying the mirror and aperture settings over a multi-dimensional range. We describe the results of such parameter varying measurements and how we are combining Sirepo-Bluesky with machine learning methods and reduced models to automate mirror alignment on the TES beamline.

36 MATERIALS SCIENCE↗
DOE OSTI2019

High-throughput investigation of crystal-to-glass transformation of Ti–Ni–Cu ternary alloy

A high-throughput investigation of metallic glass formation via solid-state reaction was reported in this paper. Combinatorial multilayered thin-film chips covering the entire Ti-Ni-Cu ternary system were prepared using ion beam sputtering technique. Microbeam synchrotron X-ray diffraction (XRD) and X-ray fluorescence (XRF) measurements were conducted, with 1,325 data points collected from each chip, to map out the composition and the phase constitution before and after annealing at 373 K for 110 hours. The composition dependence of the crystal-to-glass transition by solid-state reaction was surveyed using this approach. The resulting composition-phase map is consistent with previously reported results. Time-of-flight secondary ion mass spectroscopy (ToF-SIMS) was performed on the representative compositions to determine the inter-diffusion between layers, the result shows that the diffusion of Ti is the key factor for the crystal-to-glass transition. In addition, both layer thickness and layer sequence play important roles as well. This work demonstrates that combinatorial chip technique is an efficient way for systematic and rapid study of crystal-to-glass transition for multi-component alloy systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Absolute intensity calibration for carbon-edge soft X-ray scattering

Resonant soft X-ray scattering (RSOXS) has become a premier probe to study complex three-dimensional nanostructures in soft matter through combining the robust structural characterization of small-angle scattering with the chemical sensitivity of spectroscopy. This technique borrows many of its analysis methods from alternative small-angle scattering measurements that utilize contrast variation, but thus far RSOXS has been unable to reliably achieve an absolute scattering intensity required for quantitative analysis of domain compositions, volume fraction, or interfacial structure. Here, a novel technique to calibrate RSOXS to an absolute intensity at the carbon absorption edge is introduced. It is shown that the X-ray fluorescence from a thin polymer film can be utilized as an angle-independent scattering standard. Verification of absolute intensity is then accomplished through measuring the Flory–Huggins interaction parameter in a phase-mixed polymer melt. As a result, the necessary steps for users to reproduce this intensity calibration in their own experiments to improve the scientific output from RSOXS measurements are discussed.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

The nanoscale distribution of copper and its influence on charge collection in CdTe solar cells

For decades, Cu has been the primary dopant in CdTe photovoltaic absorbers. Typically, Cu acceptor concentrations in these devices are on the order of 1 1014 cm-3, which has made it notoriously difficult to directly correlate nanoscale Cu distributions to the local charge transport properties of these devices. To measure and correlate these properties, measurement techniques require high sensitivity to elemental concentration, large penetration depth, and operando compatibility. Techniques such as secondary-ion mass spectroscopy and X-ray energy dispersive spectroscopy are widely adopted to measure Cu concentrations, but they are limited by penetration depth, sensitivity, or spatial resolution. Additionally, they lack the operando capabilities required to correlate one-to-one Cu concentrations to electrical performance. In this work, correlative X-ray microscopy is used to investigate the spatial distribution of Cu and its impact on charge collection through the depth and breadth of CdTe photovoltaic devices. Plan-view, nanoscale X-ray fluorescence maps clearly demonstrate the spatial segregation of copper around regions thought to be CdTe grain boundaries. Complementary cross-section imaging unveils the transition of the maximum charge-collection efficiency from the ZnTe-CdTe interface to the CdS-CdTe interface as a function of Cu incorporation. The copper concentration through the depth of the CdTe layer is characterized by slow and fast diffusion components, and cross-section charge-transport modeling shows that the experimentally obtained charge collection can be explained by the modeled acceptor distribution through the depth of the CdTe layer.

14 SOLAR ENERGY↗
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 OSTI2023

Heavy Versus Light Lanthanide Selectivity for Graphene Oxide Films is Concentration Dependent

Rare earths are important materials in various technologies such as catalysis and optoelectronics. Graphene oxide (GO) is a promising material for separation applications, including the isolation of lanthanides from complex mixtures. Previous works using fatty acid monolayers have demonstrated preferential heavy versus light lanthanide adsorption, which has been attributed to differences in lanthanide ion size. In this work, we used interfacial X-ray fluorescence measurements to reveal that GO thin films at the air/water interface have no lanthanide selectivity for dilute subphases. However, at high subphase concentrations, ~8 times more Lu is adsorbed than La. By comparing the GO results with an ideal monolayer with a carboxylic acid headgroup, arachidic acid (AA), we demonstrate that the number of Lu ions adsorbed to GO is significantly higher than the number expected to compensate for the surface charge. Vibrational sum frequency generation (SFG) spectroscopy results on both GO thin films and AA monolayers reveal a red-shifted SFG signal in the OH region, which we attribute to partial dehydration of the adsorbed ions and carboxylic acid headgroups. Liquid surface X-ray reflectivity data show that the GO thin film structure does not significantly change between the very dilute and concentrated subphases. We speculate that the functional groups of both GO and AA facilitate cation dehydration, which is essential for ion adsorption. Heavy lanthanide Lu has stronger ion–ion correlations that can overcome the electrostatic repulsion between cations at higher concentrations compared to light lanthanide La, meaning GO and AA can exhibit apparent overcharge with Lu. Lastly, the layered structure of the GO films and reactive chemical nature of GO itself can accommodate ion adsorption.

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

An approach towards plastic scintillators from thermally activated delayed fluorescent dyes and cross-linkable bismuth compounds

Cross-linked polyvinyltoluene (PVT) based plastic scintillators loaded with dyes exhibiting thermally activated delayed fluorescence (TADF) and various amounts of (caproate)di-(methacrylate) bismuth (CMB) were developed. The co-polymerization of vinyl toluene monomer loaded with different weight ratios of CMB and 1 wt% of TADF dye yielded highly transparent cross-linked plastic scintillators with intense green photoluminescence. The thermal and mechanical properties of the scintillators were investigated using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and micro indentation techniques. Here, their performance for radiation detection was assessed by performing gamma spectroscopy using a Cs-137 source and benchmarked to commercial plastic scintillators. The loading of CMB was guided by Monte Carlo N-Particle (MCNP) simulations. The results of this study show that the cross-linking approach and the use of TADF dyes yield scintillators with good mechanical properties with a uniaxial yield strength up to ~66 MPa for compositions loaded with 40 wt% of CMB and high optical quality. However, the light yield in gamma spectroscopy experiments is found to be reduced with the addition of CMB, suggesting a trade-off between mechanical yield strength and light yield in gamma spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Resonant X-ray emission spectroscopy from broadband stochastic pulses at an X-ray free electron laser

Abstract Hard X-ray spectroscopy is an element specific probe of electronic state, but signals are weak and require intense light to study low concentration samples. Free electron laser facilities offer the highest intensity X-rays of any available light source. The light produced at such facilities is stochastic, with spikey, broadband spectra that change drastically from shot to shot. Here, using aqueous ferrocyanide, we show that the resonant X-ray emission (RXES) spectrum can be inferred by correlating for each shot the fluorescence intensity from the sample with spectra of the fluctuating, self-amplified spontaneous emission (SASE) source. We obtain resolved narrow and chemically rich information in core-to-valence transitions of the pre-edge region at the Fe K-edge. Our approach avoids monochromatization, provides higher photon flux to the sample, and allows non-resonant signals like elastic scattering to be simultaneously recorded. The spectra obtained match well with spectra measured using a monochromator. We also show that inaccurate measurements of the stochastic light spectra reduce the measurement efficiency of our approach.

Fuller, Franklin D. (ORCID:0000000237737087)↗
DOE OSTI2022

A Hybrid Structural Method for Investigating Low Molecular Weight Oligomeric Structures of Amyloid Beta

Spurred in part by the failure of recent therapeutics targeting amyloid β plaques in Alzheimer's Disease (AD), attention is increasingly turning to the oligomeric forms of this peptide that form early in the aggregation process. However, while numerous amyloid β fibril structures have been characterized, primarily by NMR spectroscopy and cryo-EM, obtaining structural information on the low molecular weight forms of amyloid β that presumably precede and/or seed fibril formation has proved challenging. Furthermore, these transient forms are heterogeneous, and depend heavily on experimental conditions such as buffer, temperature, concentration, and degree of quiescence during measurement. Here, we present the concept for a new approach to delineating structural features of early-stage low molecular weight amyloid β oligomers, using a solvent accessibility assay in conjunction with simultaneous fluorescence measurements.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2026

Nuclear recoil detection with color centers in bulk lithium fluoride

We present initial results on the detection of nuclear recoils in lithium fluoride (LiF) through the fluorescence of color centers created by particle interactions in the crystal lattice. Using light-sheet fluorescence microscopy, we image nuclear recoil tracks from both fast and thermal neutron interactions deep within a cubic-centimeter-scale sample. Automated three-dimensional feature extraction based on machine-learning tools enables the identification and classification of individual events. We observe that the fluorescence response of LiF to gamma irradiation is strongly suppressed, by a factor of 30–50 compared to neutron exposure, demonstrating intrinsic insensitivity to electromagnetic backgrounds. The observed and simulated event characteristics are consistent, including their number, size, and topology. These results establish the feasibility of LiF as a scalable detection medium for rare nuclear-recoil events and constitute a first step toward 10–1000 g scale detectors with single-event sensitivity for applications in reactor-neutrino detection, neutron spectroscopy, and dark matter searches.

Aroujo, G R [University of Zurich]↗
DOE OSTI2025

Distinct Fracture Mineralogy That is Out of Equilibrium With Modern Groundwaters Provides Important Context for Subsurface Life

Rock fracture surfaces in the crust are essential habitat for microorganisms. Fracture‐groundwater interfaces provide physical substrates for biofilm growth and are sources of carbon, nutrients, and electron donors and acceptors. To better understand geochemical processes impacting fracture surfaces and the subsurface microbiome, we identified fractures in archived rock cores from the Soudan formation, which is known to host saline groundwaters and isolated microbial communities dependent on rock‐water interactions. Cores with open fractures were thin sectioned and studied via electron microprobe and synchrotron X‐ray fluorescence microprobe. Most fracture surfaces had mineralogy distinct from that of the bulk rock. Chlorite minerals were abundant on fracture surfaces and had elemental compositions suggesting deposition during late‐stage hydrothermal alteration. Fracture‐lining chlorites likely limit access to iron oxide and sulfide minerals that are active in subsurface biogeochemical cycles. Calcium‐rich rinds were also observed along fracture edges. These rinds were too thin and poorly ordered to be identified via light microscopy or X‐ray diffraction; however, Ca K‐edge micro‐X‐ray absorption near‐edge structure spectroscopy identified them as carbonates, minerals not observed in the bulk rock. Thermodynamic modeling shows that carbonate precipitation is largely unfavorable in Soudan groundwaters, indicating that fracture edge conditions differed from those in modern water samples. Because of the low carbon concentrations in Soudan groundwaters, carbonate rinds likely play an important role in subsurface carbon cycling and may mark fracture surfaces that once hosted biofilms. Overall, this study suggests that fracture alteration can both play an active role in and suppress rock‐water interactions essential to subsurface life.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Salt Stress Induces Paramylon Accumulation and Fine-Tuning of the Macro-Organization of Thylakoid Membranes in Euglena gracilis Cells

The effects of salt stress condition on the growth, morphology, photosynthetic performance, and paramylon content were examined in the mixotrophic, unicellular, flagellate Euglena gracilis. We found that salt stress negatively influenced cell growth, accompanied by a decrease in chlorophyll (Chl) content. Circular dichroism (CD) spectroscopy revealed the changes in the macro-organization of pigment-protein complexes due to salt treatment, while the small-angle neutron scattering (SANS) investigations suggested a reduction in the thylakoid stacking, an effect confirmed by the transmission electron microscopy (TEM). At the same time, the analysis of the thylakoid membrane complexes using native-polyacrylamide gel electrophoresis (PAGE) revealed no significant change in the composition of supercomplexes of the photosynthetic apparatus. Salt stress did not substantially affect the photosynthetic activity, as reflected by the fact that Chl fluorescence yield, electron transport rate (ETR), and energy transfer between the photosystems did not change considerably in the salt-grown cells. We have observed notable increases in the carotenoid-to-Chl ratio and the accumulation of paramylon in the salt-treated cells. We propose that the accumulation of storage polysaccharides and changes in the pigment composition and thylakoid membrane organization help the adaptation of E. gracilis cells to salt stress and contribute to the maintenance of cellular processes under stress conditions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

pH-Dependent Vibrational Dynamics Drives Excited-State Quenching in the Phycobiliprotein Complex PC645

Phycocyanin 645 (PC645) is a closed-form lightharvesting complex found in the lumen of the photosynthetic membrane of cryptophyte algae. These peripheral antenna complexes contain bilin chromophores that absorb sunlight and transfer excitation energy to the core antenna complexes embedded in the thylakoid membrane. The location of cryptophyte antenna complex on the luminal side of the membrane is unusual. During photosynthetic activity, the pH of the lumen drops, by up to two pH units. There is little known about how this pH-change affects the light-harvesting complexes. In this study, we report multiscale simulations using a computationally efficient density functional tight-binding framework to investigate the spectroscopy and excitation energy transfer in the PC645 complex. Complementary experiments were conducted using both steady-state and time-resolved spectroscopic measurements at low, neutral, and high pH values. Our study shows that (de)protonation of specific bilin pigments, namely, the mesobiliverdins (MBVs), modulates the excitation energies, excitonic couplings, and spectral densities. These changes cause excitation transfer rates to increase by up to a factor of two to three, leading to pH-dependent energy transfer pathways in the complex. Using this model, we calculated the pH-dependent fluorescence quantum yield of the system, obtaining quantitative agreement with the experimental results. These computational simulations, supported by experiments, identify MBVs as a more prominent excitation sink than previously realized, and that this role is tuned by pH.

Maity, Sayan [Constructor Univ., Bremen (Germany);↗