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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Evolving physical and mechanical rock properties during exposure at Earth's surface

Rocks at Earth's surface experience progressive damage due to exposure to environmental conditions. Although environmental damage to rocks is recognized as being time-dependent, our quantitative understanding of its effects on physical and mechanical properties remains limited by field and laboratory studies constrained to short timescales. In this study, we aim to rigorously quantify how these properties evolve under longer natural environmental exposure spanning from the Holocene to the late Pleistocene. We conducted a ‘time series’ analysis of key physical and mechanical rock properties using multiple interior samples from 10 cogenetic granitoid boulders exposed for different amounts of time at two sites in Eastern California, USA. We find that over the late Pleistocene (~30 ka), rocks exhibit porosity increases of 40 ± 4 % and seismic velocity decreases of 7 ± 1 % at both sites. Similarly, over the same time period, rock tensile and compressive strengths declined by an average of 11 ± 4 %, and rock permeability increased on average by 104 ± 50 %. Microscopic analysis of thin sections of the same rocks indicates that microfracture density and intensity also progressively increased over the same timescales. These results suggest that time-dependent fracture propagation due to environmental exposure is likely a central contributor to the observed changes in rock properties. This study provides quantitative documentation that pronounced changes in the physical and mechanical properties of rock progressively occur within thousands of years of exposure.

Critical zone↗
DOE OSTI2026

Activation dynamics of a water-soluble human mu-opioid receptor

The mu-opioid receptor (MOR), a class A G protein-coupled receptor mediates opioid analgesia and remains a central target for pain therapeutics. While crystal structures of MOR exist, they provide limited insight into the receptor’s dynamic conformational landscape underlying function. Here, we engineered a thermostable water-soluble MOR variant (wsMOR) that retains native-like ligand-binding and activation dynamics. This variant enables high-yield production and detailed solution-phase structural studies that are challenging with membrane-embedded MOR, providing a valuable tool for studying receptor activation and aqueous-phase drug screening. Using a combined computational and experimental approach, we performed long-timescale all-atom molecular dynamics simulations together with neutron scattering and single-molecule FRET, revealing a structurally stable receptor with a diverse ensemble of conformations at different temporal resolutions. In the ligand-free state, wsMOR displayed high conformational flexibility, which decreased upon agonist binding, particularly in transmembrane helix 6, a hallmark of G protein-coupled receptor activation. Positive allosteric modulation and G protein binding further stabilized active-like states. These findings highlight wsMOR’s conformational plasticity across picosecond to millisecond timescales and provide a foundation for structure-guided development of next-generation opioid ligands with improved efficacy and safety.

E, Agyemang [University of Tennessee Knoxville]↗
DOE OSTI2024

One-sweep moment-based semi-implicit-explicit integration for gray thermal radiation transport

Thermal radiation transport (TRT) is a time dependent, high dimensional partial integro-differential equation. In practical applications such as inertial confinement fusion, TRT is coupled to other physics such as hydrodynamics, plasmas, etc., and the timescales one is interested in capturing are often much slower than the radiation timescale. As a result, TRT is treated implicitly, and due to its stiffness and high dimensionality, is often a dominant computational cost in multiphysics simulations. Here we develop a new approach for implicit-explicit (IMEX) integration of gray TRT in the deterministic SN setting, which requires only one sweep per stage, with the simplest first-order method requiring only one sweep per time step. The partitioning of equations is done via a moment-based high-order low-order formulation of TRT, where the streaming operator and first two moments are used to capture the asymptotic stiff regimes of the streaming limit and diffusion limit. Absorption-reemission is treated explicitly, and although stiff, is sufficiently damped by the implicit solve that we achieve stable accurate time integration without incorporating the coupling of the high order and low order equations implicitly. Due to nonlinear coupling of the high-order and low-order equations through temperature-dependent opacities, to facilitate IMEX partitioning and higher-order methods, we use a semi-implicit integration approach amenable to nonlinear partitions. In conclusion, results are demonstrated on thick Marshak and crooked pipe benchmark problems, demonstrating orders of magnitude improvement in accuracy and wallclock compared with the standard first-order implicit integration typically used.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Comparison of continuum and cross-core theories of dynamic strain aging

Dynamic strain aging (DSA) is the process of solute atoms segregating around dislocations on the timescale of loading. Continuum theories of DSA derived from elasticity theory have been shown to severely overpredict both the timescale and strengthening of DSA. Recently, cross-core theory was developed to reconcile this gap, invoking a special single-atomic-hop diffusion mechanism across the core of an extended dislocation. In this work, we show that the classical continuum theory expression for the rate of solute segregation is in error. After correcting this error, we show that continuum theory predictions match cross-core theory when the elevated diffusivity near the dislocation core is accounted for. Finally, our findings indicate that continuum theory is still a useful tool for studying dislocation-solute interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Fabrication and thermophysical properties of UO 2 -UB 2 and UO 2 -UB 4 composites sintered via spark plasma sintering

Uranium dioxide (UO 2 ) composites with uranium diboride (UB 2 ) and uranium tetraboride (UB 4 ) have been proposed as advanced fuel candidates due to their high thermal conductivity, high melting point, high fissile density and their ability to incorporate a built-in burnable poison by tailoring the targeted 10 B/ 11 B ratio. As such, it is important to assess the fabrication, and thermal and micromechanical properties of such composites. In this work, UO 2 -UB 2 and UO 2 -UB 4 samples with boride phase fractions of 5, 15 and 30 wt% were fabricated to high densities (above 95 % theoretical density) via spark plasma sintering (SPS). This enabled sintering at relatively low temperatures and short timescales. SPS also aided in maintaining the target phase fractions of the samples as reactions between the constituent phases were suppressed due to the short timescales and reducing environment during sintering. Here, thermal diffusivity measurements from 299 to 1273 K were conducted through laser flash analysis (LFA). The diffusivity increased as a function of boride weight fraction, and UB 2 additions increased the thermal diffusivity of the composites more than UB 4 additions. Assessment of the LFA results indicated in-situ reactions between the UO 2 and boride phases that suppress the thermal diffusivity occur above 800 K for all samples. Oxidation of the boride phase was proposed as the underlying reaction. This was supported by thermodynamic assessments from the literature, as well as microstructural, crystallographic, and nanoindentation characterization performed on these samples.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Temporal and spatial separations between spin glass and short-range order

Broken-symmetry-induced order parameters account for many phenomena in physics. For spin glasses, this framework dictates the theoretical construction, whereas experiments have only established dynamical behaviors but not the physical entity. Experimental techniques have limitations when the spin glass is probed as an isolated state. Here, we create an evolution from a long-range order using well-controlled non-magnetic substitution on a sublattice. Neutron magnetic diffuse scattering of pico-second timescale reveals that the dynamics of short- and long-range order formation are not affected by disorder, but their spatial ranges are. Across all specimens, the inflection point of spin correlation length’s temperature dependence fully matches with the peak in heat capacity, while spin glass can freeze at millisecond timescale either above or below this characteristic temperature of spin-order formation. Our results identify the spin glass as single, uncorrelated spins at domain walls between spin clusters, and an uncorrelated coexistence of the two.

Dronova, Margarita G [Okinawa Institute of Science↗
DOE OSTI2022

Holocene paleoclimate change in the western US: The importance of chronology in discerning patterns and drivers

We report sediment in lakes and meadows forms a powerful archive that can be used to reconstruct environmental change through time. Reconstructions of lake level, of chemical, biological, and hydrological conditions, and of surrounding vegetation provide detailed information about past climate conditions, both locally and regionally. Indeed, most of our current knowledge of centennial- to millennial-scale climate variability in the arid western United States, where information about past hydroclimate is particularly important, comes from such sediment-based reconstructions. The pressing need for robust, precise predictions of future conditions is a significant motivation for paleoclimate science, and current research questions frequently require Holocene reconstructions to be resolved at sub-centennial timescales. Increasingly, regional syntheses seek to identify synoptic-scale patterns similar to those defined from modern observations (seasonal, interannual, multi-decadal, etc.) or to compare with the output of climate model simulations. However, the age control on existing records, especially those more than about 20 years old, is often sufficient only for millennial-scale interpretation. Here we assess the age control for 84 published and unpublished records from lakes and meadows in the Great Basin, California, and desert southwest, and use Bayesian modeling to evaluate the 95% uncertainty ranges for the 42 best-dated records. In the Late Holocene, about half of the 42 records have <400-year mean uncertainty ranges; however, high-precision age control is especially critical for young records, used to develop an accurate understanding of a proxy’s response to known climate variations. In the Middle Holocene, records vary from 400 to >800-year mean uncertainty and records of the Early Holocene have 600- to >1400-year mean uncertainty ranges. We find that the largest control on modeled uncertainties is dating density, with at least 2 dates/kyr being optimal and suggest obtaining “range-finder” dates at the onset of a study to better predict the total number of dates needed for an adequate age model. Such a density avoids a commonly observed phenomenon of significant peaks in uncertainty arising in gaps between age control points. Analysis of the uncertainties associated with proxy shifts reveal that more than half are >400 years. Although such large uncertainties currently prevent sub-centennial interpretations in most cases, increased dating density, strategic use of limited funds (including budgeting for a 2 date/kyr minimum at the proposal stage), construction of age-depth models with Bayesian methods, and critical evaluation of chronological uncertainty will shed light on past climate variability at finer timescales, enhancing our understanding of global and regional drivers of western U.S. climate.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Solid-State Hydroxide Ion Conductivity in Silver(I) Oxide, Ag 2 O

Silver (I) oxide, Ag 2 O, precipitated as microcrystals by combining aqueous silver(I) nitrate and KOH solutions, was found to be a solid-state hydroxide ion conductor with ionic conductivity on the order of 10 -3 S/cm. The proton chemical shifts at 4.87 and -7.35 ppm measured by solid-state 1H-NMR experiments are attributed to water molecules and in-lattice OH - coordinated to silver, respectively. The lack of spinning sidebands around the 4.87 ppm peak indicates rapid reorientation on the NMR timescale, suggesting that the water molecules are adsorbed to the surface of the Ag 2 O crystals. Pulsed field gradient measurements gave similar diffusion coefficients (2 x 10 -7 cm 2 /s at 298K) for all three proton environments indicating chemical exchange between sites on the millisecond timescale. The activation energy for OH - diffusion measured by NMR (0.18 eV) was comparable to that obtained by conductivity measurements and density functional theory (DFT) electronic structure calculations. Furthermore, the calculated Pourbaix diagram of Ag 2 O is consistent with the slightly lower sample density observed in He pycnometry and thermogravimetric measurements.

25 ENERGY STORAGE↗
DOE OSTI2020

Molecular Origins of the Barriers to Proton Transport in Acidic Aqueous Solutions

The self-consistent iterative multistate empirical valence bond (SCI-MS-EVB) method is used to analyze the structure, thermodynamics, and dynamics of hydrochloric acid solutions. The reorientation timescales of irreversible proton transport are elucidated by simulating 0.43 M, 0.85 M, 1.68 M, and 3.26 M HCl solutions at 270 K, 285 K, 300 K, 315 K, and 330 K. The results indicate increased counter-ion pairing with increasing concentration, which manifests itself via a reduced hydronium oxygen–chloride (O*-Cl) structuring in the radial distribution functions. Increasing ionic concentration also reduces the diffusion of the hydrated excess protons, principally by reducing the contribution of the Grotthuss proton hopping (shuttling) mechanism to the overall diffusion process. In agreement with prior experimental findings, a decrease in the activation energy of reorientation timescales was also observed, which is explicitly explained using activated rate theory and an energy-entropy decomposition of the state-averaged radial distribution functions. Furthermore, these results provide atomistic verification of suggestions from recent two-dimensional infrared spectroscopy experiments that chloride anions (as opposed to hydrated excess protons) create entropic barriers to proton transport.

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

Observation of Collective Molecular Dynamics in a Chalcogenide Glass: Results from X-ray Photon Correlation Spectroscopy

The structural relaxation processes in a Ge 3 As 52 S 45 molecular chalcogenide glass sample were directly studied by X-ray photon correlation spectroscopy (XPCS). XPCS was conducted at the first sharp diffraction peak at q = 1.16 Å -1 at temperatures ranging from 123 K to above the glass transition at 328 K, and the results showed two different dynamical regimes. At a low temperature, the observed glass dynamics are slow and dominated by X-ray-photon-induced effects, which are temperature independent. At a higher temperature, we observed a dramatic decrease in the fluctuation timescales, indicating that the dynamics were mainly due to the intermolecular correlation of the As 4 S 3 molecule in the glass. The timescales in this high-temperature range agree well with those determined from measurements of the Newtonian viscosity. Here our XPCS studies suggest an extended length scale of the relaxation process in glassy Ge 3 As 52 S 45 from the single molecule to the intermolecular range across the glass transition, providing a unique direct probe of the dynamics beyond the length scales of the individual molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

A Consistent Model of Ultrafast Energy Transfer in Peridinin Chlorophyll-a Protein Using Two-Dimensional Electronic Spectroscopy and Förster Theory

Solar light harvesting begins with electronic energy transfer in structurally complex light-harvesting antennae such as the peridinin chlorophyll-a protein from dinoflagellate algae. Peridinin chlorophyll-a protein is composed of a unique combination of chlorophylls sensitized by carotenoids in a 4:1 ratio, and ultrafast spectroscopic methods have previously been utilized in elucidating their energy transfer pathways and timescales. However, due to overlapping signals from various chromophores and competing pathways and timescales, a consistent model of intra-protein electronic energy transfer has been elusive. Here, we used broadband two-dimensional electronic spectroscopy, which alleviates the spectral congestion by dispersing excitation and detection wavelengths. Inter-chromophoric couplings appear as cross peaks in two-dimensional electronic spectra, and these spectral features were observed between the peridinin S2 states and chlorophyll-a Qx and Qy states. In addition, the inherently high time- and frequency-resolution of 2DES enabled accurate determination of the ultrafast energy transfer dynamics. Kinetic analysis near the peridinin S1 excited state absorption, which forms in 24 fs after optical excitation, reveals an ultrafast energy transfer pathway from the peridinin S2 state to the chlorophyll-a Qx state—a hitherto unconfirmed pathway critical for fast inter-chromophoric transfer. Lastly, we propose a model of ultrafast peridinin chlorophyll-a protein photophysics that (1) includes a conical intersection between peridinin S2 and S1 states in order to explain both the ultrafast peridinin S1 formation and the residual peridinin S2 population for energy transfer to chlorophyll-a, and (2) computationally- and experimentally-derived peridinin S2 site energies that support the observed ultrafast peridinin S2 to chlorophyll-a Qx energy transfer.

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

Ultrafast Triplet Pair Separation and Triplet Trapping following Singlet Fission in Amorphous Pentacene Films

In this work, ultrafast infrared and electronic spectroscopy are used to examine the dynamics of triplet pair separation following singlet fission in amorphous and crystalline films of the model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn). Direct probing of correlated triplet pair intermediates through their unique vibrational frequencies, infrared electronic transitions, and indirectly through their visible triplet absorptions reveals that triplet pair separation occurs on similar picosecond timescales in both amorphous and crystalline films despite their markedly different average intermolecular coupling strengths. Although triplet pair separation occurs on similar timescales in both environments, measurements of diffusion-controlled triplet-triplet annihilation reveal that the diffusivity of triplet excited states is an order of magnitude lower in amorphous films. The data reveal the presence of sparse triplet traps in the amorphous environment that inhibit the transport of triplet excitons in comparison to crystalline films. These observations inform recent efforts to develop disordered and polymeric singlet fission sensitizers that contain amorphous regions. In particular, the data suggest that it may be possible to nanostructure amorphous or polymeric singlet fission sensitizers to allow ultrafast triplet pair separation and harvesting in photovoltaic and light emitting applications despite their low triplet exciton diffusivity.

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

Extremely Slow Trap-Mediated Hole Relaxation in Room-Temperature InP/ZnSe/ZnS Quantum Dots

Time-resolved photoluminescence (PL) and transient absorption (TA) spectroscopy have been used to elucidate the hole relaxation dynamics in high-quality InP/ZnSe/ZnS quantum dots (QDs) at room temperature. In QDs having an In/P ratio close to 1:1, hole cooling is fast compared to the ~40 ps time-correlated photon-counting instrument response. However, in QDs that luminesce at wavelengths greater than around 600 nm and have excess indium, a significant fraction of the PL exhibits a slower rise time. In this case, the PL rises over a range of timescales varying from close to the instrument response to approximately 300–400 ps. The time constant of the slowest component increases with increasing InP core size and the fraction of the PL that has the slow rise time increases with excess indium in the particle. In all cases, a slow rise time and any spectral evolution on that timescale are absent in the TA results, indicating that the slow dynamics may be assigned to relaxation in the valence band. QDs emitting at wavelengths below 560 nm show very different dynamics, exhibiting a barely detectable <50 ps rise time. Based on these results and measured elemental compositions, the slow hole relaxation is assigned to the transient population of indium-based traps in the ZnSe shell that are above the valence band edge only for the larger, red-emitting QDs. Here, the relative trap to band edge relaxation rates can be understood in terms of effective mass approximation hole wave function calculations, which show that the relaxation rate is largely determined by the extent to which the hole wave function in the lowest exciton penetrates into the ZnSe shell, overlapping the trapped-hole wave functions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2026

Coherent and Dynamic Small Polaron Delocalization in CuFeO 2

Small polarons remain a bottleneck in realizing efficient transition metal oxide devices. Routes to engineer small polaron coupling to electronic states and lattice modes to control carrier localization remain unclear. Here, we measure small polaron formation in CuFeO 2 using transient extreme ultraviolet reflection spectroscopy and compare to theoretical predictions in realistically parametrized Holstein models, demonstrating that polaron localization depends on coupling to high-frequency versus low-frequency phonon bath components. We measure small polaron formation on a comparable ∼100 fs timescale to other Fe(III) compounds. Dynamic delocalization of the polaron follows formation through a coherent lattice expansion between Fe–O layers and charge-sharing with surrounding Fe(IV) states. Simulations reveal two major factors dictate polaron formation timescales: phonon density and reorganization energy distributions between acoustic and optical modes, matching experimental findings. Our work shows how electronic-structural coupling in a polaron-host material can be leveraged to suppress polaronic effects for various applications.

Hematite↗
DOE OSTI2021

Twist-Angle-Dependent Ultrafast Charge Transfer in MoS 2 -Graphene van der Waals Heterostructures

Vertically stacked transition metal dichalcogenide-graphene heterostructures provide a platform for novel optoelectronic applications with high photoresponse speeds. Photoinduced nonequilibrium carrier and lattice dynamics in such heterostructures underlie these applications but have not been understood. In particular, the dependence of these photoresponses on the twist angle, a key tuning parameter, remains elusive. Here, using ultrafast electron diffraction, we report the simultaneous visualization of charge transfer and electron–phonon coupling in MoS 2 -graphene heterostructures with different stacking configurations. We find that the charge transfer timescale from MoS 2 to graphene varies strongly with twist angle, becoming faster for smaller twist angles, and show that the relaxation timescale is significantly shorter in a heterostructure as compared to a monolayer. These findings illustrate that twist angle constitutes an additional tuning knob for interlayer charge transfer in heterobilayers and deepen our understanding of fundamental photophysical processes in heterostructures, of importance for future applications in optoelectronics and light harvesting.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

In-Operando Study of Shape Retention and Microstructure Development in a Hydrolyzing Sol–Gel Ink during 3D-Printing

3D printing of amorphous and crystalline ceramics is of paramount importance for the fabrication of a wide range of devices with applications across different technology fields. Printed ceramics are remarkably enabled by the sol-gel synthesis method in conjunction with continuous filament direct ink writing. During printing, multiple processes contribute to the evolution of inks including shape retention, chemical conversion, solidification, and microstructure formation. Traditionally, depending on the ink composition and printing environment, several mechanisms have been associated with the shape retention and solidification of 3D printed structures: gelation, rapid solvent evaporation, energy-driven phase transformation, and chemical-driven phase transformation. Understanding the fundamental differences between these mechanisms becomes key since they strongly influence the spatiotemporal evolution of the materials, as the out-of-equilibrium processes inherent to the extrusion, relaxation, and solidification of printed materials have significant effects on the materials properties. Herein, we investigate the shape retention mechanism and the hydrolysis-induced material conversion and microstructure formation during the 3D printing of a water reactive sol-gel ink that transforms into titanium dioxide-based ceramic. This study aims at identifying characteristic mechanisms associated with the material transformation, establishing connections between the microstructure development and the timescales associated with solidification under operando 3D-printing conditions. The investigation of this material's out-of-equilibrium pathways under processing conditions is enabled by time-resolved coherent X-ray scattering, providing simultaneous access to temporospatially resolved microstructural and dynamics information. Furthermore, we explore X-ray speckle tracking as a tool to resolve deformations of the microstructure in a printed filament associated with the deposition of consecutive filaments. Through this work, we aim at providing a fundamental understanding of the relationships behind these transformative processes in 3D printing and their timescales as the basis for achieving unprecedented control over printed materials microstructure.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Effects of Extended Aqueous Processing on Structure, Chemistry, and Performance of Polycrystalline LiNi x Mn y Co z O 2 Cathode Powders

The prospect of aqueous processing of LiNi x Mn y Co z O 2 (NMC) cathodes has significant appeal to battery manufacturers for the reduction in materials cost, toxicological risk, and environmental impact compared to conventional N -methyl-2-pyrrolidone (NMP)-based processing. However, the effects of aqueous processing of NMC powders at industrial timescales are not well studied, with prior studies mostly focusing on relatively brief water washing processes. Here, we investigate the bulk and surface impacts of extended aqueous processing of polycrystalline NMC powders with different compositions. We demonstrate that at timescales of several hours, polycrystalline NMC is susceptible to intergranular fracture, with the severity of fracture scaling with the NMC nickel content. While bulk crystallinity and composition are unchanged, surface sensitive techniques such as X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) indicate that the exposure of water leads to a level of delithiation, nickel reduction, and reconstruction from the layered to rock-salt structure at the surface of individual grains. Dynamic single NMC microparticle compression testing suggests that the resulting mechanical stresses weaken the integrity of the polycrystalline particle and increases susceptibility of intergranular fracture. The initially degraded surfaces along with the increased surface area lead to faster capacity fade and impedance growth during electrochemical cycling. From this work, it is demonstrated that NMC powders require surface or grain boundary modifications to make industrial-scale aqueous cathode processing viable, especially for next-generation nickel-rich NMC chemistries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗