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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Strengthening of enterococcal biofilms by Esp

Multidrug-resistant (MDR) Enterococcus faecalis are major causes of hospital-acquired infections. Numerous clinical strains of E . faecalis harbor a large pathogenicity island that encodes enterococcal surface protein (Esp), which is suggested to promote biofilm production and virulence, but this remains controversial. To resolve this issue, we characterized the Esp N-terminal region, the portion implicated in biofilm production. Small angle X-ray scattering indicated that the N-terminal region had a globular head, which consisted of two DEv-Ig domains as visualized by X-ray crystallography, followed by an extended tail. The N-terminal region was not required for biofilm production but instead significantly strengthened biofilms against mechanical or degradative disruption, greatly increasing retention of Enterococcus within biofilms. Biofilm strengthening required low pH, which resulted in Esp unfolding, aggregating, and forming amyloid-like structures. The pH threshold for biofilm strengthening depended on protein stability. A truncated fragment of the first DEv-Ig domain, plausibly generated by a host protease, was the least stable and sufficient to strengthen biofilms at pH ≤ 5.0, while the entire N-terminal region and intact Esp on the enterococcal surface was more stable and required a pH ≤ 4.3. These results suggested a virulence role of Esp in strengthening enterococcal biofilms in acidic abiotic or host environments.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Development of High-Quality, Very Large-Grained Cd(Se,Te) Thin Films for CdTe Solar Modules (Final Technical Report)

TCF-21-25048 is a one-year project to quantify the potential attributes of recent NREL inventions where CdTe devices with grain sizes exceeding 100's of microns in lateral dimension can be fabricated using a novel seeded-epitaxial process. A CdSe0.1Te0.9 film is evaporated on commercially available transparent conducting oxide (TCO) where the latter surface roughness (Ra) has been reduced to < 1-nm. After NREL's colossal grain growth (CGG) process, the grain size of this "seed" layer is increased to 100-1000 um. CdTe is then deposited epitaxially resulting in a large-grain CdTe device structure without use of CdCl2. As of this report, we have: Demonstrated the feasibility of using Tec-15 substrates after surface roughness (Ra) reduction (nexTC); Developed reproducible CGG processes for this commercially available substrate; Developed a close-spaced sublimation (CSS) process for CdTe epitaxy using these substrates; Demonstrated that large-grain CdTe films have less sub-band (band tail) absorption than conventional, small-grain CdTe; Demonstrated that large-grain CdTe films (no CdCl2) have carrier lifetimes up to 1.5 ns; Demonstrated that carrier lifetimes in epi-CdTe films (no CdCl2) have comparable lifetimes when compared to the best pX-CdTe films (FSLR) treated with CdCl2; Started making large-grain CdTe devices using CGG templates and epitaxially deposited CdTe.

14 SOLAR ENERGY↗
DOE OSTI2021

CO adsorption on MnO(100): Experimental benchmarks compared to DFT

In this study, CO adsorption on the MnO(100) surface was studied using temperature programmed desorption (TPD) and density functional theory (DFT). TPD results show that CO is weakly-bound on MnO(100), with an experimental adsorption energy of -35.6 ± 2.1 kJ/mol at terrace sites in the low coverage limit. PBE simulations suggest that CO adsorption causes an implausible (2 × 2) surface reconstruction. PBE+U simulations show no signs of surface reconstruction, and provide an accurate estimate of the adsorption energy (-36.4 kJ/mol) when combined with the DFT-D3 method with Becke-Jonson damping to correct for van der Waals interactions. This simulation also shows that CO adsorbs C-down onto the Mn 2+ terrace site in a tilted geometry, which is also observed experimentally and computationally on the similarly-structured NiO(100) transition metal oxide surface. TPD results for large doses show a plateauing of the coverage at about 0.4 monolayers of CO at 85 K, with a defect coverage equivalent to 0.08 monolayers. Adsorption associated with defect sites is indicated by a high-temperature desorption tail which is not satisfactorily explained by DFT simulations of simple step or oxygen vacancy defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Quantum critical collapse abhors a naked singularity

Classical critical collapse yields naked singularities from smooth initial data, challenging cosmic censorship, and shaping the spectrum of primordial black holes. We show that one-loop vacuum polarization near the threshold qualitatively changes this outcome by dressing the singularity with a horizon within a controlled semiclassical regime. In analytically tractable Einstein-scalar critical spacetimes, a one-loop $s$-wave treatment linearized around self-similar backgrounds shows that regularity uniquely selects an asymptotically Minkowskian, vacuum-polarization state. Its renormalized stress tensor carries a universal quantum growing mode that competes with the classical unstable mode, shifts the critical point, and generates a trapped surface along with a finite mass gap at the new threshold, thereby enforcing horizon formation even under arbitrary fine-tuning. In primordial collapse, the threshold shift enters exponentially into the formation fraction, while the mass gap truncates the low-mass tail, suggesting potentially important consequences for the predicted mass spectrum. Furthermore, these results provide a self-consistent semiclassical treatment of critical collapse and yield sharp predictions within the one-loop, near-critical, linearized regime.

Anomalies↗
DOE OSTI2020

X-Ray Afterglows from the Gamma-Ray Burst “Large-angle” Emission

In this work, we derive basic analytical results for the timing and decay of the gamma-ray burst (GRB) counterpart and delayed afterglow light curves for a brief emission episode from a relativistic surface endowed with angular structure, consisting of a uniform core of size ${\theta }_{c}$ (Lorentz factor ${{\rm{\Gamma }}}_{c}$ and surface emissivity ${i}_{\nu ^{\prime} }^{{\prime} }$ are angle independent) and an axially symmetric power-law envelope (${\rm{\Gamma }}\sim {\theta }^{-g}$). In this "large-angle emission" model, radiation produced during the prompt emission phase (GRB) at angles $\theta \gt {\theta }_{c}$ arrives at the observer well after the burst (delayed emission). The dynamical time range of the very fast decaying GRB "tail" and of the flat afterglow "plateau" and the morphology of the GRB counterpart/afterglow are all determined by two parameters: the core's parameter ${{\rm{\Gamma }}}_{c}{\theta }_{c}$ and the envelope's Lorentz factor index g, leading to three types of light curves that display three post-GRB phases (type 1: tail, plateau/slow decay, post-plateau/normal decay), two post-GRB phases (type 2: tail and fast decay), or just one (type 3: normal decay). We show how X-ray light-curve features can be used to determine core and envelope dynamical and spectral parameters. Testing of the large-angle emission model is done using the Swift/XRT X-ray emission of two afterglows of type 1 (GRB 060607A, GRB 061121), one of type 2 (GRB 061110A), and one of type 3 (GRB 061007). We find that the X-ray afterglows with plateaus require an envelope Lorentz factor ${\rm{\Gamma }}\sim {\theta }^{-2}$ and a comoving-frame emissivity ${i}_{\nu ^{\prime} }^{{\prime} }\sim {\theta }^{2}$; thus, for a typical afterglow spectrum ${F}_{\nu }\sim {\nu }^{-1}$, the lab-frame energy release is uniform over the emitting surface.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

Measurement of the full electron spectrum associated with the Ag N 3 VV Auger transitions: Evidence for the contribution of multi-electron Auger processes

In this paper, we report the first measurement of the full energy spectrum (down to 0 eV) of electrons emitted from the surface of Ag(100) as a result of the N 3 VV Auger transition. A comparison with a Monte-Carlo model was used to obtain an estimate of the contribution of multi-electron Auger processes to the low energy part of the Auger spectrum. The experimental Auger spectrum was obtained in time coincidence with photo-emitted 4p 3/2 core electrons from Ag using Auger-Photoelectron coincidence spectroscopy (APECS). The coincidence condition in APECS can remove most, but not all, spectral contributions from events unrelated to the Auger transition. The remaining contributions to the APECS spectrum from Auger-unrelated events, which are significant, were determined from a series of coincidence measurements of inelastically scattered valence band photoelectrons. The contribution from Auger-unrelated events was subtracted from the APECS Auger spectrum of Ag(100) to obtain the full Auger spectrum down to 0 eV. The resulting spectrum includes, in addition to Auger electrons emitted without energy loss, inelastically scattered Auger electrons. We observe that the spectral weight of the low energy tail (LET) in the APECS spectrum is reduced by more than a factor of two after subtracting the Auger-unrelated contributions. However, the intensity of the LET after this subtraction is still two times the integrated intensity in the Auger peak. A Monte Carlo model that includes the inelastic transport of the N 3 VV Auger electrons through the surface showed that LET produced by the inelastic scattering of the Auger electrons has the same intensity as the integrated intensity in the Auger peak. The excess intensity in the experimental LET provides strong evidence that the Auger related spectrum also includes contribution from multiple electron emissions that are intrinsic to the creation and/or the Auger decay of the core hole. In conclusion, our estimate shows that as low as 20% to as high as 60% of the core hole decay events result in the emission of more than one Auger electron from Ag (100). This result demonstrates the need for a better understanding of the contribution of valence-electron correlations to the entire CVV Auger spectrum down to 0 eV.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Molecular Dynamics Simulation of the Structures, Dynamics, and Aggregation of Dissolved Organic Matter

Dissolved organic matter (DOM) plays a significant role in the transport and transformation of pollutants in the aquatic environment. However, the experimental characterization of DOM has been limited mainly to bulk properties, and the molecular-level interactions among various components of DOM remain to be fully characterized. In this study, we use molecular dynamics (MD) simulations to probe the structural properties of model DOM systems at atomic detail. The 200 ns simulations, validated by available experimental data, reveal processes and mechanisms by which chemical species (cations, peptides, lipids, lignin, carbohydrates, and some low-molecular-weight aliphatic and aromatic compounds) aggregate to form complex DOM. The DOM aggregates are dynamic, consisting of a hydrophobic core and amphiphilic exterior. The lipid tails and other hydrophobic fragments form the core, with hydrophilic and amphiphilic groups exposed to water, making DOM accessible to both polar and nonpolar species. Thus, the lipid component acts as a nucleator, whereas cations (especially Ca 2+ ) connect the molecular fragments on the surface by coordinating with the O-containing functional groups of DOM. The structural details revealed here provide new insights including surface accessible atoms, overall assemblage, and interactions among the molecules of DOM for understanding the kinetics and mechanisms through which DOM interacts with metal and other contaminants.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Molecular-level origin of the carboxylate head group response to divalent metal ion complexation at the air-water interface

We exploit gas-phase cluster ion techniques to provide insight into the local interactions underlying divalent metal ion-driven changes in the spectra of carboxylic acids at the air-water interface. This information is used to clarify the experimental findings of surface sensitive spectroscopies that the CO stretching bands of long chain acids appear at very similar energies when the head group is deprotonated by high sub-phase pH or is exposed to relatively high concentrations of Ca2+ divalent metal ions (e.g., Ca2+ and Mg2+). To this end, we report the evolution of the vibrational spectra of size-selected [Ca2+·RCO2¯]+·(H2O)n=0-14 and RCO2¯·(H2O)n=0-14 cluster ions obtained using infrared photofragmentation mass spectrometry toward the features observed at the air-water interface. The carboxylate with R = -CD2CD3 was chosen in order to capture the longer chain behavior and to suppress band congestion that complicates the spectra of the light isotopologue. Surprisingly, not only does stepwise hydration of the RCO2¯ anion and the [Ca2+·RCO2¯]+ contact ion pair yield solvatochromic responses in opposite directions, but in both cases the responses of the two CO bands (?_s^COO and ?_as^COO) to hydration are opposite to each other! The result is that the two CO bands evolve toward their interfacial and bulk asymptotes from opposite directions. Theoretical simulations of the [Ca2+·RCO2¯]+·(H2O)n clusters indicate that the metal ion remains directly bound to the head group in a contact ion pair motif as the asymmetric CO stretch converges at the bulk value by n = 12, establishing that direct metal complexation can account for the interfacial and bulk behavior. We discuss these effects in the context of a qualitative model that invokes the water network-dependent local electric field along the C-C bond connecting the head group to the tail as the key parameter driving the observed trends. M.A.J. and H.C.A. thank the National Science Foundation through the NSF Center for Aerosol Impacts on Chemistry of the Environment (NSF-CAICE), CHE-1305427 for supporting this work. M.A.J. thanks the Air Force Office of Scientific Research for the cryogenic spectrometer used in the gas phase experiments. K.D.J. thanks the Department of Energy under grant no. DE-FG02-00ER15066. C.J. Mundy and S.M. Kathmann are supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. M.D. Baer was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Biomolecular Materials Program at PNNL. PNNL is operated by Battelle Memorial Institute for the U.S. Department of Energy under Contract No. DE-AC05- 76RL01830. Computing resources for the calculation of harmonic spectra were allocated by PNNL’s Institutional Computing program.

Denton, Joanna↗
DOE OSTI2023

Microextraction–TQ–ICP–MS for the Direct Analysis of U and Pu from Cotton Swipes

Here, the microextraction sampling technique was integrated with triple quadrupole–inductively coupled plasma–mass spectrometry (TQ–ICP–MS) to directly sample and measure the isotopic compositions of uranium (U) and plutonium (Pu) from cotton swipes. Once extracted, the U/Pu were directed into the TQ–ICP–MS instrument for isotopic determination. Carbon dioxide (CO 2 ) and helium (He) gases were delivered to a collision reaction cell within the ICP–MS system for ion separation. The CO 2 reacts with the U + forming UO + which is ultimately separated from the Pu + ions of interest in the third quadrupole. This study demonstrates direct liquid extraction of U/Pu from a solid surface and subsequent measurement by TQ–ICP–MS in <60 s. Flow rates were optimized (0.3 mL min –1 CO 2 and 5 mL min –1 He) in the reaction cell of the ICP–MS system to maximize the Pu signal while minimizing U interferences (i.e., 238 U + tail and 238 UH + ) at m/z 239. Low levels of Pu (~2 pg) were deposited on a cotton swipe along with U at concentrations ranging from 20 to 200 ng. The 240 Pu/ 239 Pu ratio was measured with <7% relative difference from the certified value at all U concentrations. Major and minor U isotope ratios were also measured with <4% relative difference. This highlights that the microextraction–TQ–ICP–MS method can extract a mixed U/Pu sample directly from a cotton swipe and measure both isotopic systems without chemical separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Predicting Water Cycle Characteristics from Percolation Theory and Observational Data

The fate of water and water-soluble toxic wastes in the subsurface is of high importance for many scientific and practical applications. Although solute transport is proportional to water flow rates, theoretical and experimental studies show that heavy-tailed (power-law) solute transport distribution can cause chemical transport retardation, prolonging clean-up time-scales greatly. However, no consensus exists as to the physical basis of such transport laws. In percolation theory, the scaling behavior of such transport rarely relates to specific medium characteristics, but strongly to the dimensionality of the connectivity of the flow paths (for example, two- or three-dimensional, as in fractured-porous media or heterogeneous sediments), as well as to the saturation characteristics (i.e., wetting, drying, and entrapped air). In accordance with the proposed relevance of percolation models of solute transport to environmental clean-up, these predictions also prove relevant to transport-limited chemical weathering and soil formation, where the heavy-tailed distributions slow chemical weathering over time. The predictions of percolation theory have been tested in laboratory and field experiments on reactive solute transport, chemical weathering, and soil formation and found accurate. Recently, this theoretical framework has also been applied to the water partitioning at the Earth’s surface between evapotranspiration, ET, and run-off, Q, known as the water balance. A well-known phenomenological model by Budyko addressed the relationship between the ratio of the actual evapotranspiration (ET) and precipitation, ET/P, versus the aridity index, ET 0 /P, with P being the precipitation and ET 0 being the potential evapotranspiration. Existing work was able to predict the global fractions of P represented by Q and ET through an optimization of plant productivity, in which downward water fluxes affect soil depth, and upward fluxes plant growth. In the present work, based likewise on the concepts of percolation theory, we extend Budyko’s model, and address the partitioning of run-off Q into its surface and subsurface components, as well as the contribution of interception to ET. Using various published data sources on the magnitudes of interception and information regarding the partitioning of Q, we address the variability in ET resulting from these processes. The global success of this prediction demonstrated here provides additional support for the universal applicability of percolation theory for solute transport as well as guidance in predicting the component of subsurface run-off, important for predicting natural flow rates through contaminated aquifers.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

WRF-Comfort: simulating microscale variability in outdoor heat stress at the city scale with a mesoscale model

Abstract. Urban overheating and its ongoing exacerbation due to global warming and urban development lead to increased exposure to urban heat and increased thermal discomfort and heat stress. To quantify thermal stress, specific indices have been proposed that depend on air temperature, mean radiant temperature (MRT), wind speed, and relative humidity. While temperature and humidity vary on scales of hundreds of meters, MRT and wind speed are strongly affected by individual buildings and trees and vary on the meter scale. Therefore, most numerical thermal comfort studies apply microscale models to limited spatial domains (commonly representing urban neighborhoods with building blocks) with resolutions on the order of 1 m and a few hours of simulation. This prevents the analysis of the impact of city-scale adaptation and/or mitigation strategies on thermal stress and comfort. To solve this problem, we develop a methodology to estimate thermal stress indicators and their subgrid variability in mesoscale models – here applied to the multilayer urban canopy parameterization BEP-BEM within the Weather Research and Forecasting (WRF) model. The new scheme (consisting of three main steps) can readily assess intra-neighborhood-scale heat stress distributions across whole cities and for timescales of minutes to years. The first key component of the approach is the estimation of MRT in several locations within streets for different street orientations. Second, mean wind speed and its subgrid variability are downscaled as a function of the local urban morphology based on relations derived from a set of microscale LES and RANS simulations across a wide range of realistic and idealized urban morphologies. Lastly, we compute the distributions of two thermal stress indices for each grid square, combining all the subgrid values of MRT, wind speed, air temperature, and absolute humidity. From these distributions, we quantify the high and low tails of the heat stress distribution in each grid square across the city, representing the thermal diversity experienced in street canyons. In this contribution, we present the core methodology as well as simulation results for Madrid (Spain), which illustrate strong differences between heat stress indices and common heat metrics like air or surface temperature both across the city and over the diurnal cycle.

Geology↗
DOE OSTI2022

Fabrication of Biofunctionalized PVA/PEI Nanofibers for Rare Earth Element Extraction from Coal Mine Tailings

The need for rare earth elements (REEs) for new technology is becoming increasingly stiff with demand at a record high. Biological ligands like lanmodulin and lanthanide binding tags (LBT) have gained noticeable attention for their selective extraction of valuable lanthanide metals in aqueous solution. Building on previous work using microbeads as the extraction media, we propose that nanofibers can improve extraction capabilities. Nanofibers could provide more efficient flow and higher extraction yields due to their high surface area to volume ratio. Relying on thiolmaleimide click chemistry as the biological ligand immobilization route, electrospinning as the nanofiber manufacturing method, and numerous characterization techniques, we produced electrospinning polymer solutions and nanofibers with a maximum neodymium adsorbent capacity of 12.1 μmol/g of extraction media immobilized with LBT. Although the prior work produced an extraction media with an equivalent capacity of ~40 μmol/g, the electrospinning process is much more economical and scalable. This work paves the way for an industrially relevant, environmentally-friendly REE extraction material. Further work is required to produce higher quality nanofibers, to investigate common ion interference with REE adsorbance, and to scale production up to a relevant scale.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2019

Initial Assessment of Cover Degradation Features at the Mexican Hat, Utah, UMTRCA Disposal Site - 19556

The Mexican Hat, Utah, Uranium Mill Tailings Radiation Control Act (UMTRCA) Title I Disposal Site is located on the Navajo Reservation in southeast Utah. The US Nuclear Regulatory Commission licensed the site to the US Department of Energy Office of Legacy Management (LM) for custody and long-term care. LM manages long-term surveillance and maintenance activities at the site with the principal goal of protecting human health and the environment. The disposal cell was designed to encapsulate low-level radioactive mill tailings and other residual radioactive materials (RRM) in a way that minimizes the need for active maintenance and limits radon gas emanation and precipitation infiltration. The disposal cell has a multicomponent cover, consisting of a 60 cm thick (24 inch), low-permeability, bentonite-amended radon barrier, overlain by a 15 cm thick (6 inch) sandy gravel bedding/filter layer and a 30 cm thick (12 inch) riprap erosion-protection layer. Under UMTRCA, designs intended to control and contain RRM shall be effective for up to 1000 years, to the extent reasonably achievable and, in any case, for at least 200 years. In 2016, multiple subtle depressions were identified on the rock cover along the toe and lower portions of the northeast side slope of the disposal cell. Due to concerns regarding potential impacts to disposal cell performance and erosion resistance, evaluations of the depressions and cell cover design and construction were initiated. The evaluations included reviews of the disposal cell as-built drawings and supporting design calculations for the rock cover components. Also, in 2017, a weather monitoring station was installed at the site to collect continuous site-specific meteorological data, and repeatable ground-based light imaging, detection, and ranging (lidar) topographical and aerial photogrammetry surveys were implemented to monitor for potential changes in the surface depression features. The evaluations also included visual inspections of the depressions, and in 2018, small-area manual excavations of the rock cover components (test pits) were performed to observe the conditions of the cover components, scan for radioactivity, and observe evidence of erosion on the surface of the radon barrier material. Voids and incisions were discovered within the radon barrier on the north and northeast side slopes of the disposal cell. Visual observations at test pits indicate that the bedding/filter material is highly segregated and may not be in conformance with the disposal cell engineering and construction design specifications. Post-construction development of a weak to strongly cemented material has also been observed immediately below the base of the bedding layer in test pits with observed radon barrier degradation. A series of radiological surveys have been performed at the site, and radiological readings have not exceeded natural background conditions in the vicinity of the site. Thus, the site remains protective of human health and the environment. Implementation of continuous radiological monitoring at the site will be initiated in fall 2018 through the deployment of radon cups and thermoluminescent dosimeters to obtain data that provides supporting evidence that the disposal cell remains protective of human health and the environment. Evaluations to determine the cause(s) of the depression features and associated radon barrier erosion are ongoing. Possible mechanisms of cover degradation identified thus far include segregated bedding material that would allow for higher precipitation runoff velocities, resulting in erosion of the radon barrier; post-construction cementation of radon barrier or aeolian material that could negatively affect the performance of the radon barrier; cation exchange leading to the development of cementation; and aeolian deposition affecting precipitation runoff. Moreover, geotechnical sampling and testing is planned to verify spatial cover conditions relative to design specifications. The resulting information will be used to identify possible causes for the surface depressions and associated radon barrier degradation, gain insight on potential long-term performance implications along the side slopes of the disposal cell, and identify potential corrective actions. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Unveiling mechanisms and onset threshold of humping in high-speed laser welding

The fabrication of fuel cells relies on a rapid laser welding process. However, challenges arise with the occurrence of humping when the welding speed surpasses a critical threshold, which poses difficulties in achieving a smooth surface finish and a consistent weld strength. This study aims to elucidate the humping mechanisms by analyzing the morphology of molten pool and the characteristics of melt flow at varying welding speeds via in situ synchrotron high-speed X-ray imaging and computational fluid dynamics simulations. Our findings indicate that the short keyhole rear wall, the high backward melt velocity, and the prolonged tail of molten pool are the primary factors contributing to the onset of humping. Furthermore, a dimensionless humping index (π h ) was introduced, which successfully captured the onset threshold of humping across different literatures. This index not only provides a quantitative description of the humping formation tendency but also serves as a valuable tool for optimizing the laser welding process.

42 ENGINEERING↗
DOE OSTI2025

Metal ion dopant-induced famatinite to chalcostibite phase transformation of copper antimony sulphide colloidal nanostructures: effect on photophysical and pseudocapacitance properties

Here, the strategic doping of transition metal ions into copper antimony sulphide (CAS) semiconducting nanostructures can significantly influence their photophysical and pseudocapacitive properties, for which there are few reports and therefore is the focus of this study. Accordingly, highly crystalline metal ion (Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ and Zn 2+ ) doped off-stoichiometric copper rich/poor, antimony-rich/poor, and sulphur-poor CAS nanostructures (10–23 nm) were grown via colloidal (hot-injection) synthesis using metal diethyldithiocarbamate precursors. Importantly, metal ion doping significantly influences the structure and composition of the off-stoichiometric CAS nanostructures. Data from powder X-ray diffraction, Raman spectroscopy, high-resolution scanning/transmission electron microscopy, and energy dispersive X-ray spectroscopy confirm that the heavier metal ion dopants induce a novel phase transformation from famatinite (fCAS) to chalcostibite (cCAS) nanostructures. The influence of the metal ion dopants is also observed in the optical properties of as-synthesized nanostructures. This involves blue-shifted ultraviolet-visible absorption, reduced Urbach tailing, and tunable bandgaps between 2.17 and 2.38 eV. Also, the doped nanostructures display broad visible-near infrared photoluminescence via a triple radiative pathway with relatively short decay lifetimes between 0.2 and 6.1 ns. This is mediated by electronic transitions involving intrinsic (copper/antimony/sulphur interstitial) and extrinsic (metal ion interstitial) defect states. Additionally, electrodes prepared from Mn 2+ -doped fCAS nanostructures show enhanced pseudocapacitance via Na+ surface adsorption and intercalation relative to undoped fCAS electrodes, while Zn 2+ -doped cCAS electrodes exhibit pseudocapacitance via a combination of Na+ surface adsorption, intercalation, and redox reactions. These electrodes exhibit reduced charge transfer resistance, improved electronic conductivity and notably enhanced specific capacitance (∼222 F g −1 ), and charge transport, as measured in 1 M Na 2 SO 4 electrolyte via cyclic voltammetry and electrochemical impedance spectroscopy. To this end, the discovery of the metal ion-induced phase transformation presents a new avenue for optimizing the functional properties of fCAS and cCAS nanostructures, highlighting the critical role of metal ion-related defects in controlling the optical and electrochemical properties, towards potential solar absorption and energy storage applications.

25 ENERGY STORAGE↗
DOE OSTI2022

Squeezing Out Interfacial Solvation: The Role of Hydrogen-Bonding in the Structural and Orientational Freedom of Molecular Self-Assembly

We report bioinspired membrane molecules with improved physical properties and enhanced stability can serve as functional models for conventional lipid or amphiphilic species. Importantly, these molecules can also provide new insights into emergent phenomena that manifest during self-assembly at interfaces. Here, we elucidate the structural response and mechanistic steps underlying the self-assembly of the amphiphilic, charged oligodimethylsiloxane imidazolium cation (ODMS-MIM+) at the air–aqueous interface using Langmuir trough methods with coincident surface-specific vibrational sum-frequency generation (SFG) spectroscopy. We find evidence for a new compression-induced desolvation step that precedes commonly known disordered-to-ordered phase transitions to form nanoscopic assemblies. The experimental data was supported by atomistic molecular dynamics (MD) simulations to provide a detailed mechanistic picture underlying the assembly and the role of water in these phase transitions. The sensitivity of the hydrophobic ODMS tail conformations to compression-owing to distinct water–ODMS interactions and tail–tail solvation properties-offers new strategies for the design of interfaces that can be further used to develop soft-matter electronics and low-dimensional materials using physical and chemical controls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Positron stopping in multilayer materials

Positron annihilation spectroscopy provides a sensitive toolset for defect characterization. In beam based studies of single-layer targets, the form of implantation profiles is well established, depending on the kinetic energy and angle of incident positrons relative to the target surface and the density and average atomic number of the target. For multilayer systems, the difference in density and across the layers makes derivation of an analytical form difficult. To date, the determination of positron stopping profiles in multilayer targets has primarily involved Monte Carlo simulations. We present here an alternative approach that estimates the energy distribution dN/dE of those positrons transmitted past each layer boundary, by fitting the remaining tail of the stopping profile after each layer with a basis set comprised of calculated stopping profiles in the same material they are transmitted through. The stopping profile in the next layer is then found by summing a series of stopping profiles in the new medium in proportion to the determined distribution dN/dE. The results of our model are compared with simulation results in a system of alternating layers of Al and Au and find reasonable agreement in the predicted profile and excellent agreement in the predicted mean implantation depth. Finally, we derived a simple formula-based approach for the calculation of the mean implantation depth in two-layer systems that provides results in excellent agreement with the full model.

Jones, A. C. L. [Arizona State University, Tempe, ↗
DOE OSTI2026

Relativistic Magnetohydrodynamic Simulations of Giant Magnetar Bursts

Gradual crustal deformation can generate strongly twisted magnetic fields around magnetars, potentially triggering giant flares with total energies exceeding 10 44 erg. In this letter, we present the first relativistic magnetohydrodynamic simulation of a surface shear-driven magnetar eruption, capturing reconnection-driven plasma heating, the ejection of relativistically hot plasma, and the formation of a hot fireball confined within the inner magnetosphere. We find that magnetic reconnection in the equatorial current sheet launches a hot trailing outflow capable of powering the initial spike observed in giant flares, while simultaneously leaving behind a thermally stratified fireball with sufficient thermal energy to produce the pulsating, decaying tail. Together, these features provide a self-consistent physical framework for understanding the observed energetics of magnetar giant flares. The eruption also expels a magnetically dominated giant plasmoid carrying up to ∼9% of the magnetosphere’s total magnetic energy. Furthermore, our simulation demonstrates how the plasmoid drives the formation of a blast wave—an important ingredient in models linking magnetar eruptions to fast radio bursts.

79 ASTRONOMY AND ASTROPHYSICS↗