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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 127 records · Page 7

Ultrafast multi-cycle terahertz measurements of the electrical conductivity in strongly excited solids

Key insights in materials at extreme temperatures and pressures can be gained by accurate measurements that determine the electrical conductivity. Free-electron laser pulses can ionize and excite matter out of equilibrium on femtosecond time scales, modifying the electronic and ionic structures and enhancing electronic scattering properties. The transient evolution of the conductivity manifests the energy coupling from high temperature electrons to low temperature ions. Here we combine accelerator-based, high-brightness multi-cycle terahertz radiation with a single-shot electro-optic sampling technique to probe the evolution of DC electrical conductivity using terahertz transmission measurements on sub-picosecond time scales with a multi-undulator free electron laser. Our results allow the direct determination of the electron-electron and electron-ion scattering frequencies that are the major contributors of the electrical resistivity.

36 MATERIALS SCIENCE↗

Computing Potential of the Mean Force Profiles for Ion Permeation Through Channelrhodopsin Chimera, C1C2

Umbrella sampling, coupled with a weighted histogram analysis method (US-WHAM), can be used to construct potentials of mean force (PMFs) for studying the complex ion permeation pathways of membrane transport proteins. Despite the widespread use of US-WHAM, obtaining a physically meaningful PMF can be challenging. Here, we provide a protocol to resolve that issue. Then, we apply that protocol to compute a meaningful PMF for sodium ion permeation through channelrhodopsin chimera, C1C2, for illustration.

59 BASIC BIOLOGICAL SCIENCES↗

FREDA: A Web Application for the Processing, Analysis, and Visualization of Fourier‐Transform Mass Spectrometry Data

The high-resolution measurement capability of Fourier-transform mass spectrometry (FT-MS) has made it a necessity for exploring the molecular composition of complex organic mixtures, like soil, plant, aquatic, and petroleum samples. This demand has driven a need for informatics tools to explore and analyze FT-MS data in a robust and reproducible manner. FREDA is an interactive web application developed to enable spectrometrists to format, process, and explore their FT-MS data without the need for statistical programming expertise. FREDA was built to explore outputs from a molecular identification tool, like CoreMS, and provide a suite of methods to filter data, compute chemical properties of peaks, statistically compare samples and groups of samples, conduct exploratory data analysis, and download the results with a report detailing all steps conducted. To demonstrate the utility of FREDA, an example analysis was conducted using FT-MS data from a soil microbiology study of samples collected in two different soil depths at the Sphagnum bog forest north of Grand Rapids, Minnesota. Differences between the two depths are observed using Kendrick, Gibbs free energy, and van Krevelen plots. G-tests are used to quantify a significant difference between the groups. All analyses and plotting are conducted using only the FREDA application. FREDA is an open-source and readily available web application that allows users to explore and make statistically valid conclusions about their FT-MS data. The application is available online (https://map.emsl.pnnl.gov/app/freda) with a tutorial web series (https://youtu.be/k5HLE2kNSBY?si=yB6sGoyvzxrFf5MP) and freely accessible code on Github (https://github.com/EMSL-Computing/FREDA).

47 OTHER INSTRUMENTATION↗

Overcoming time and complexity limitations in molecular dynamics investigations of equilibrium melting

Abstract A hybrid Monte-Carlo molecular-dynamics method for determining solidus and liquidus compositions in multicomponent systems is presented that overcomes both the time limitations in conventional molecular dynamics that prevent the evolution of distinct solid and liquid compositions via diffusion and the complexity challenge that prevents use of thermodynamic assessment in systems of many components. This hybrid method is validated in the Cu–Ni system against an independent assessment of solidus and liquidus compositions based on the regular solution model. Strategies for efficient mapping of different phase diagrams, based on the thermodynamic parameter T 0 , the temperature at which two phases of the composition X 0 have equal free energies, are presented and then demonstrated for the copper-nickel fully miscible system and the gold–silicon eutectic system. A calculation of the solidus and liquidus sampled during the equilibrium melting of equiatomic CrMnFeCoNi is performed, indicating that this method has potential to be extended to the study of many component alloys.

Au-Si↗

Rapid Design and Manufacturing of High-Performance Materials for Turbine Blades

This research demonstrated the concept of carbide precipitation-strengthened refractory high entropy alloys (RHEA). The advantage of a precipitation strengthened alloy is all phases are in thermodynamic equilibrium promoting microstructural stability, and consequently retention of properties at elevated temperatures. Additionally, as with any precipitation strengthened – or age hardened - alloy, components can be heat-treated after manufacturing to manipulate the microstructure and optimize properties for performance. This is an advantage of the precipitation strengthened alloys over composites and ceramics materials, where the microstructure and properties are essentially fixed upon the initial materials manufacturing stage. High throughput (HT), multi-scale computer modeling was used to identifying novel RHEA compositions with desired characteristics needed for precipitation strengthening. Designs were validated by producing small ingots via are melting. The results showed that carbides precipitated and consequently, the strength of the alloys (measured in compression) increased after heat-treatment, which is the desired effect. The project also demonstrated the feasibility of producing articles from RHEA by additive manufacturing (AM). Electron beam melting (EBM) and laser direct energy deposition (L-DED) additive manufacturing methods, were explored with various processing parameters were interrogated for both methods. Sound (crack-free and dense) precipitation strengthened RHEA samples were produced via EDM AM, demonstrating the feasibility of the concept.

36 MATERIALS SCIENCE↗

Removing Fluoride from Double Four-Membered Rings Yielding Defect-Free Zeolites under Mild Conditions Using Ozone

We have investigated ozone treatment of as-made LTA zeolites under mild temperature conditions (175 °C) using experiments and periodic DFT as a method of energy savings and engineering defects such as silanol nests in comparison with conventional calcination at 550 °C. We have studied ozone treatment on LTA samples synthesized with 1,2-dimethyl-3-(4-methylbenzyl) imidazolium (denoted as “BULKY”) as the primary organic structure-directing agent (OSDA) and with various amounts of tetramethylammonium (TMA) as a secondary OSDA. Ozone treatment of LTA-BULKY at 175 °C was found to give defect-free, pristine LTA materials as determined by 29 Si NMR, 13 C NMR, Raman spectra, and DFT to assign the spectra. This represents a significant and unexpected finding: that fluoride ions can be completely removed from double four-membered rings (D4Rs) under such mild conditions. Furthermore, ozone treatment of LTA-BULKY-TMA samples removed BULKY but left behind TMA/F, giving a new and more diverse structural landscape of Si environments in LTA. Ab initio MetaDynamics calculations provide pathways with relatively low barriers, explaining how fluoride ions can be removed from D4Rs, leaving behind defect-free LTA materials under mild conditions.

36 MATERIALS SCIENCE↗

Calibration-Free Quantitative Analysis of Lithium-Ion Battery (LiB) Electrode Materials Using Laser-Induced Breakdown Spectroscopy (LIBS)

Recent years have seen a surge in the demand for high-performance battery electrode materials for automotive and various electronic device applications. Improving battery performance requires precise knowledge of the structure–composition properties of active electrode materials. To this effect, quantitative and precise estimation of the composition of advanced electrode materials, containing trace amounts of dopants, provide immense value toward developing next-generation high-capacity battery materials. Herein, we demonstrate the application of calibration-free laser-induced breakdown spectroscopy (LIBS) as a powerful analytical tool for rapid and reliable quantitative spectrochemical characterizations of layered Li metal oxide cathodes containing Mo and Cr dopants (<5 atom %). Specifically, we employ the LIBS using an internal calibration methodology to establish the quantitative elemental ratios of major (Ni, Mn, Co) and trace dopant (Cr, Mo) transition metals to bulk Li contents in diverse cathode material samples such as LiNi 0.5 Mn 0.5 O 2 (NM-50/50), LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC), LiNi 0.317 Mn 0.317 Co 0.317 Cr 0.05 O 2 (Cr-doped NMC), and LiNi 0.5– x /2 Mn 0.5– x /2 Mo x O 2 ( x = 0.03, 0.04, 0.05) (Mo-doped NM-50/50) that were synthesized via sol–gel routes. The LIBS-estimated elemental compositions are in good agreement with the nominal stoichiometric values. Furthermore, ex situ LIBS characterizations presented here pave the path for future high-efficacy application of calibration-free quantitative LIBS for rapid in situ analyses of elemental composition changes in battery electrode materials under operation that need not resort to off-site analytical techniques requiring cumbersome sample preparations and/or external standards.

25 ENERGY STORAGE↗

Minority carrier lifetime and photoluminescence of mid-wave infrared InAsSbBi

Time-resolved photoluminescence measurements are reported for InAsSbBi alloys grown by molecular beam epitaxy with Bi mole fractions ranging from 0 to 0.8%, yielding minority carrier lifetimes on the order of hundreds of nanoseconds. The minority carrier lifetimes extracted from the time-resolved photoluminescence measurements are comparable to those of lattice-matched InAsSb grown at the same respective temperatures. Nomarski imaging shows that smooth, droplet-free surface morphologies are obtained in 1 μm thick InAsSbBi epilayers grown at temperatures between 360 and 380 °C. The alloy composition-dependent bandgap energies for the InAsSbBi samples are determined from temperature-dependent steady-state photoluminescence measurements and compared with the tetragonal distortion measured by x-ray diffraction to determine the Sb and Bi mole fractions of each sample. The minority carrier lifetime and the achievable extension of the InAsSb(Bi) cut-off wavelength are analyzed as functions of alloy composition and compared with the performance of InAsSb layers with similar growth parameters.

Petluru, Priyanka (ORCID:0000000257154284)↗

Atomistic origins of biomass recalcitrance in organosolv pretreatment

Separation of lignocellulosic biomass components for use in sustainable energy and biomaterials applications remains challenging, since biopolymers such as cellulose and hemicellulose carbohydrates and polyaromatic lignin are found in close proximity within the plant secondary cell wall. Organic solvents have been used to pretreat recalcitrant biomass and separate the interacting polymers, solubilizing the lignin fraction for lignin-first valorization approaches. However, no single organosolv pretreatment approach has proven superior for heterogeneous biomass samples. Here we present a complementary atomic view of interactions between biomass components using molecular simulations, specific to lignin and cellulose, resolving mechanistic hypotheses for how lignin-cellulose composition influences separation processes. Further, using lignin-cellulose binding free energy calculated using molecular simulations, we find polar protic solvents such as methanol and ethanol separate lignin from cellulose, irrespective of the charge on the lignin monomer. Aprotic organic solvents (DMSO, THF, 1,4-dioxane) separate uncharged lignin (phenols and monolignols) from cellulose, while charged lignin (cinnamates) prefer binding to cellulose.

09 BIOMASS FUELS↗

Solvent-Mediated Control of Nanocellulose Dispersion: An Integrated Computational and Experimental Investigation

Fibrillated cellulose derived from forestry feedstocks represents a renewable and high-strength materials platform for circular bioeconomies. However, its practical implementation is hindered by the irreversible aggregation of nanocellulose architectures, including cellulose nanofibers (CNFs). Solvent-based dispersion offers a simple and practical route to prevent CNF aggregation. Here, in this work, we integrate classical and enhanced sampling molecular dynamics (MD) simulations with experimental suspension rheology and atomic force microscopy (AFM) to elucidate how solvent environments tune CNF–CNF interactions and dispersion stability. CNF–CNF contact free energies computed from MD simulations reveal reduced aggregation in acetone/water, γ-valerolactone (GVL)/water, and tetrahydrofuran (THF)/water and pure acetone compared with pure water, reflecting stronger CNF-solvent relative to inter-CNF interactions. Correspondingly, CNF-solvent suspensions in these solvent systems exhibit stronger inter-fibril network structures and enhanced recovery compared to water, indicating improved CNF-solvent affinity. Liquid cell AFM imaging in acetone–water mixtures and in pure acetone further confirm the presence of well-dispersed CNFs. By combining multiscale computation with targeted experiments, this study establishes a rational framework for solvent design to achieve stable nanocellulose dispersions for high-strength biobased materials and efficient bioenergy conversion.

cellulose↗

Atomic-scale visualization of a cascade of magnetic orders in the layered antiferromagnet GdTe3

Abstract GdTe 3 is a layered antiferromagnet which has attracted attention due to its exceptionally high mobility, distinctive unidirectional incommensurate charge density wave (CDW), superconductivity under pressure, and a cascade of magnetic transitions between 7 and 12 K, with as yet unknown order parameters. Here, we use spin-polarized scanning tunneling microscopy to directly image the charge and magnetic orders in GdTe 3 . Below 7 K, we find a striped antiferromagnetic phase with twice the periodicity of the Gd lattice and perpendicular to the CDW. As we heat the sample, we discover a spin density wave with the same periodicity as the CDW between 7 and 12 K; the viability of this phase is supported by our Landau free energy model. Our work reveals the order parameters of the magnetic phases in GdTe 3 and shows how the interplay between charge and spin can generate a cascade of magnetic orders.

36 MATERIALS SCIENCE↗

Thermomechanical response of thickly tamped targets and diamond anvil cells under pulsed hard x-ray irradiation

In the laboratory study of extreme conditions of temperature and density, the exposure of matter to high intensity radiation sources has been of central importance. Here, we interrogate the performance of multi-layered targets in experiments involving high intensity, hard x-ray irradiation, motivated by the advent of extremely high brightness hard x-ray sources, such as free electron lasers and 4th-generation synchrotron facilities. Intense hard x-ray beams can deliver significant energy in targets having thick x-ray transparent layers (tampers) around samples of interest for the study of novel states of matter and materials’ dynamics. Heated-state lifetimes in such targets can approach the microsecond level, regardless of radiation pulse duration, enabling the exploration of conditions of local thermal and thermodynamic equilibrium at extreme temperature in solid density matter. The thermal and mechanical responses of such thick layered targets following x-ray heating, including hydrodynamic relaxation and heat flow on picosecond to millisecond timescales, are modeled using radiation hydrocode simulation, finite element analysis, and thermodynamic calculations. Assessing the potential for target survival over one or more exposures and resistance to damage arising from heating and resulting mechanical stresses, this study doubles as an investigation into the performance of diamond anvil high pressure cells under high x-ray fluences. Long used in conjunction with synchrotron x-ray radiation and high power optical lasers, the strong confinement afforded by such cells suggests novel applications at emerging high intensity x-ray facilities and new routes to studying thermodynamic equilibrium states of warm, very dense matter.

Meza-Galvez, J. (ORCID:000000032699849X)↗

Quantifying Energetic and Entropic Pathways in Molecular Systems

When examining dynamics occurring at nonzero temperatures, both energy and entropy must be taken into account to describe activated barrier crossing events. Furthermore, good reaction coordinates need to be constructed to describe different metastable states and the transition mechanisms between them. Here we use a physics-based machine learning method called state predictive information bottleneck (SPIB) to find nonlinear reaction coordinates for three systems of varying complexity. SPIB is able to correctly predict an entropic bottleneck for an analytical flat-energy double-well system and identify the entropy- and energy-dominated pathways for an analytical four-well system. Lastly, for a simulation of benzoic acid permeation through a lipid bilayer, SPIB is able to discover the entropic and energetic barriers to the permeation process. Given these results, we thus establish that SPIB is a reasonable and robust method for finding the important entropy, energy, and enthalpy barriers in physical systems, which can then be used to enhance the understanding and sampling of different activated mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface defects in holographic 5d SCFTs

We use holography to study codimension-2 surface defects in 5d SCFTs engineered by (p, q) 5-brane webs. The three-dimensional defects are realized by D3-branes ending on the brane web. We identify the holographic representation of the defects in Type IIB AdS 6 solutions as probe D3-branes, and study conformal and non-conformal defects which, respectively, preserve one half and one quarter of the supersymmetry. For a sample of 5d SCFTs, including the T N theories, we provide explicit solutions for conformal and non-conformal defects. For the conformal defects we obtain their contribution to the free energy on S 5 .

79 ASTRONOMY AND ASTROPHYSICS↗

Considerations for Defining G-Values for Aluminum-Clad Spent Nuclear Fuel

Sealed-canister dry storage of aluminum-clad spent nuclear fuel (ASNF) generated by research reactors is an alternative to current storage and disposition pathways as directed by the U.S. Department of Energy. The major challenge faced for this storage approach is radiolytic H 2 generation, including from the aluminum (oxy)hydroxide layers on the surface of ASNF. Experimental and modeling activities have been carried out to characterize the radiolytic yield as part of a DOE-sponsored research program to develop the technical basis for ASNF dry storage. The G-value is a commonly way to report results of radiolysis testing and is defined as the radiolytic yield of a species (e.g. molecular hydrogen) per unit radiation energy deposited into the material system. An independent technical review of the ASNF dry storage technical basis performed by Pacific Northwest National Laboratory raised questions about differences in G-value definitions used for experiments on ASNF surrogates consisting of aluminum samples with adherent (oxy)hydroxides compared to G-values reported in prior literature and how the magnitudes compared between different studies. Material systems resembling ASNF pose complications for measuring/defining G-values to predict the evolution of H 2 in a sealed canister, including i) accounting for radiolytic yields potentially arising from multiple sources, i.e., residual free (vapor), physisorbed, and chemisorbed/chemically bound waters; ii) deciding what portions of the multi-material system to include in the absorbed energy (radiation dose) calculation, considering possible energy exchange between materials as well as measurement limitations, and iii) capturing variations in G-value associated with non-linear yield vs. dose curves and/or dependence on the cover gas. This report summarizes previous literature information on radiolytic H 2 generation and associated G-values from mixed-material systems (generally oxides in contact with water or organic compounds) and from (oxy)hydroxides/hydrates to compare with the definitions and values for ASNF surrogate samples containing adherent aluminum (oxy)hydroxides.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High-dimensional Data-driven Energy optimization for Multi-Modal Transit Agencies (HD-EMMA) (Final Technical Report)

Public bus transit services in the U.S. are responsible for at least 19.7 million metric tons of CO 2 emission annually. Electric vehicles (EVs) can have a much lower environmental impact than comparable internal combustion engine vehicles (ICEVs), especially in urban areas. Unfortunately, EVs are also much more expensive than ICEVs. As a result, many public transit agencies can afford only mixed fleets of transit vehicles, consisting of EVs, hybrids (HEVs), and ICEVs. Transit agencies that operate such mixed fleets of vehicles face a challenging optimization problem: these agencies need to decide which vehicles are assigned to serving which transit trips. Since the advantage of EVs over ICEVs varies depending on the route and time of day (e.g., the benefit of EVs is higher in slower traffic with frequent stops and lower on highways), the assignment can have a significant effect on energy use and, hence, environmental impact. Through this project, we have developed reference data about energy collections and constructed a set of machine learning models that can accurately predict the energy consumption for the whole fleet at the level of each trip. We have used these models to develop a scheduling and assignment strategy that can rotate the different vehicle types across the transit agencies’ routes. The optimization algorithm ensures that the vehicles are matched to trips considering weather patterns, expected congestion, and road gradients to minimize the overall energy usage. We list the key observations from our project for other practitioners below. Details are available in the report, and the list of source code and our publications are included in the appendix. 1. We have demonstrated the feasibility of collecting, merging and analyzing large volumes of high-resolution real-world telemetry data from a mixed vehicle fleet. To mitigate the inherent noise of the recorded GPS points, the team developed an algorithm that filters data and maps the points onto a street. The algorithm considers previous and subsequent location measurements and different characteristics of nearby streets to determine how likely the vehicle travels on them. Then, the team segmented the time series into disjoint contiguous samples based on adjacent road segments and repeated the outlier detection and removal. For each data point, the team added features corresponding to elevation changes within the samples, weather features, such as temperature, and traffic data, such as speed ratio between actual speed and free-flow speed. 2. We have developed two forms of machine learning models that be used to understand and analyze the energy operations of a mixed vehicle transit fleet. The micro prediction model provides estimates of instantaneous energy prediction for all types of buses (diesel, hybrid, and electric). Such a model is important in evaluating the energy impacts of real-time bus operation strategies, but it is challenging due to diversified driving cycles of transit buses. The model can help the drivers understand the impact of their driving behaviors and short-term congestions. The macro prediction models estimate average energy consumption across the whole trip considering the features: distance traveled, various road-type features, elevation change, day of the week, time of day, various weather features (temperature, humidity, etc.), and traffic features (speed ratio and jam factor). 3. We have demonstrated that it is possible to transfer the machine learning models we have developed in this project to other teams and cities by using inductive transfer learning. We also showed that the performance of the macro energy prediction models can be improved using a multi-task learning approach where the learning parameters are shared between the models being developed for different vehicle types. The advantage of this approach is improved learning performance as the models can exploit common spatio-temporal and environmental characteristics. 4. Finally, we have developed trip and vehicle assignment and scheduling algorithms that use the energy prediction models and develop a trip to vehicle type (diesel, electric, hybrid) assignment for the whole operation to reduce overall emissions and cost. We have shown through simulations that the proposed algorithms can save $\$$ 48,910 in energy costs and 175 metric tons of CO 2 emission annually for CARTA.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Machine learning guided discovery of ternary compounds involving La and immiscible Co and Pb elements

Abstract Ternary compounds with an immiscible pair of elements are relatively unexplored but promising for novel quantum materials discovery. Exploring what third element and its ratio that can be added to make stable ternary compounds out of an immiscible pair of elements remains a great challenge. In this work, we combine a machine learning (ML) method with ab initio calculations to efficiently search for the energetically favorable ternary La-Co-Pb compounds containing immiscible elements Co and Pb. Three previously reported structures are correctly captured by our approach. Moreover, we predict a ground state La 3 CoPb compound and 57 low-energy La-Co-Pb ternary compounds. Attempts to synthesize La 3 CoPb via multiple techniques produce mixed or multi-phases samples with, at best, ambiguous signals of the predicted lowest-energy La 3 CoPb and the second lowest-energy La 18 Co 28 Pb 3 phases. The calculated results of Gibbs free energy are consistent with experiments, and will provide very useful guidance for further experimental synthesis.

36 MATERIALS SCIENCE↗

TeraChem protocol buffers ( TCPB ): Accelerating QM and QM/MM simulations with a client–server model

The routine use of electronic structures in many chemical simulation applications calls for efficient and easy ways to access electronic structure programs. Here, we describe how the graphics processing unit (GPU) accelerated electronic structure program TeraChem can be set up as an electronic structure server, to be easily accessed by third-party client programs. We exploit Google’s protocol buffer framework for data serialization and communication. The client interface, called TeraChem protocol buffers (TCPB), has been designed for ease of use and compatibility with multiple programming languages, such as C++, Fortran, and Python. To demonstrate the ease of coupling third-party programs with electronic structures using TCPB, we have incorporated the TCPB client into Amber for quantum mechanics/molecular mechanics (QM/MM) simulations. The TCPB interface saves time with GPU initialization and I/O operations, achieving a speedup of more than 2× compared to a prior file-based implementation for a QM region with ~250 basis functions. We demonstrate the practical application of TCPB by computing the free energy profile of p-hydroxybenzylidene-2,3-dimethylimidazolinone (p-HBDI - )—a model chromophore in green fluorescent proteins—on the first excited singlet state using Hamiltonian replica exchange for enhanced sampling. All calculations in this work have been performed with the non-commercial freely-available version of TeraChem, which is sufficient for many QM region sizes in common use.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗