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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 217 records · Page 12

Robust Self-Healing Adhesives Based on Dynamic Urethane Exchange Reactions

Thermoset polyurethanes (PUs) have been successfully reprocessed as covalent adaptable networks (CANs) by catalyzing carbamate exchange. Here we extend bond exchange beyond the internal network cross-links to create a dynamic urethane adhesive. Interfacing PU CANs to substrates with nucleophilic functional groups creates adhesives capable of reversible transcarbamoylation with the substrate, which has not been demonstrated previously by CAN adhesives. Two types of thermoset PU films were synthesized, one containing the green carbamate exchange catalyst Zr(tmhd)4 and the other containing no catalyst. Although otherwise identical in chemical and network properties, as indicated by FT-IR spectroscopy and dynamic mechanical thermal analysis (DMTA), the film containing catalyst showed dynamic bond exchange behavior through stress relaxation analysis. When evaluated as an adhesive, the CAN film exhibited self-healing properties and retained its adhesive strength for five cycles, which is attributed to reversible covalent bonding to the glass substrate. Furthermore, this work expands industrially relevant CANs to structural adhesives and demonstrates their potential value in an application that presently employs PUs as single-use materials.

adhesive↗

The allosteric mechanism leading to an open-groove lipid conductive state of the TMEM16F scramblase

TMEM16F is a Ca 2+ -activated phospholipid scramblase in the TMEM16 family of membrane proteins. Unlike other TMEM16s exhibiting a membrane-exposed hydrophilic groove that serves as a translocation pathway for lipids, the experimentally determined structures of TMEM16F shows the groove in a closed conformation even under conditions of maximal scramblase activity. It is currently unknown if/how TMEM16F groove can open for lipid scrambling. Here we describe the analysis of ~400 µs all-atom molecular dynamics (MD) simulations of the TMEM16F revealing an allosteric mechanism leading to an open-groove, lipid scrambling competent state of the protein. The groove opens into a continuous hydrophilic conduit that is highly similar in structure to that seen in other activated scramblases. The allosteric pathway connects this opening to an observed destabilization of the Ca 2+ ion bound at the distal site near the dimer interface, to the dynamics of specific protein regions that produces the open-groove state to scramble phospholipids.

59 BASIC BIOLOGICAL SCIENCES↗

In-situ/operando X-ray absorption spectroscopic investigation of the electrode/electrolyte interface on the molecular scale

A method for performing X-ray absorption spectroscopy (XAS) in the soft X-ray region was developed to investigate the surface-sensitive electron signal of electrode/electrolyte interfaces in common multivalent based organic solvents under in situ/operando conditions. Our approach enables us to probe the molecular-scale structure of electrode interfaces by measuring total electron yield and is suitable for redox systems exhibiting low intrinsic electrochemical current. In-situ F K-edge XAS measurements in a 0.5 M Magnesium bis(trifluoromethanesulfonimide)/2-Methyltetrahydrofuran (Mg(TFSI) 2 /2-MeTHF) electrolyte were carried out to determine the evolution of interfacial species during the electrochemical charging/discharging process. Time-dependent density-functional theory (TD-DFT) simulation indicate that the F K-edge evolution is the result of interfacial chemical environment change driven by electrochemical potential. In addition, we performed the “operando XAS” which runs the CV and collects spectra simultaneously. Furthermore, by using this method, the non-equilibrium state of condensed matter interfaces and interfacial dynamical transient process can be revealed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving Efficiency and Stability of Perovskite Solar Cells Enabled by A Near-Infrared-Absorbing Moisture Barrier

Simultaneously improving device efficiency and stability is the most important issue in perovskite solar cell (PSC) research. Here, we strategically introduce a multi-functional interface layer (MFIL) with integrated roles of: (1) electron transport, (2) moisture barrier, (3) near-infrared photocurrent enhancement, (4) trap passivation, and (5) ion migration suppression to enhance the device performance. The narrow-band-gap non-fullerene acceptor, Y6, was screened out to replace the most commonly used PCBM in the inverted PSCs. A significantly improved power conversion efficiency of 21.0% was achieved, along with a remarkable stability (up to 1,700 h) without encapsulation under various external stimuli (light, heat, and moisture). Furthermore, systematic studies of the molecular orientation or passivation and the charge carrier dynamics at the interface between perovskite and MFIL were presented. These results offer deep insights for designing advanced interlayers and establish the correlations between molecular orientation, interface molecular bonding, trap state density, non-radiation recombination, and the device performance.

14 SOLAR ENERGY↗

Damage initiation and evolution in Al-Si layered microstructures under shock loading conditions at atomic scales

Designing materials with microstructural features like multiphase interfaces have shown significant promise for usage in the next generation defense and nuclear applications. The dynamic response of these interfaces in extreme environments is observed to vary with the deformability of individual phases, which could subsequently alter the favored damage nucleation sites related to spall failure. Here, we investigate the role of spacing of interfaces in a nanocrystalline layered Aluminum-Silicon system on the shock wave propagation behavior, and microstructural and defect evolution using classical molecular dynamics simulations. The simulations are carried out with different hypothetical Al/Si microstructures including variations in the distribution of Si grains as layers in a nanocrystalline Al matrix. The molecular dynamics simulations suggest that spall failure is preferentially initiated at Al/Si interfaces. In addition, for the same system volume and same concentration of Si, a higher number of layers is marked by an increase in shock wave velocity and reduced resistance to spall failure.

36 MATERIALS SCIENCE↗

Quantifying the Impact of Electric Fields on the Local Structure and Migration of Potassium Ions at the Orthoclase (001) Surface

Developing an understanding of the response of mineral/water interfaces to applied electric fields is central to detecting and interpreting signatures of interfacial processes in the subsurface. Here we focus density functional theory calculations on understanding K + cation binding and diffusion across the (001) surface of orthoclase feldspar under various applied electric fields with and without surface hydration. The calculations reveal how water ligands labilize surface K + cations for diffusion while also increasing their sensitivity to electric field effects on the binding energy at different surface sites. The calculations also show how the direction and strength of the electric field systematically affect surface cation mobility, sorption, and hydration behavior. Specifically, electric fields directed toward the surface increase the potassium binding energies, facilitate K + diffusion across multiple binding sites, and increase the propensity of surface K + ions to lose their hydration shells. Furthermore, the findings help fill a major knowledge gap into the impact of electric fields on mineral/water interface structure and dynamics more generally, featuring in this case a commonly found type of feldspar involved in a multitude of atmospheric and geochemical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural and dynamic changes in P-Rex1 upon activation by PIP 3 and inhibition by IP 4

PIP 3 -dependent Rac exchanger 1 (P-Rex1) is abundantly expressed in neutrophils and plays central roles in chemotaxis and cancer metastasis by serving as a guanine-nucleotide exchange factor (GEF) for Rac. The enzyme is synergistically activated by PIP 3 and heterotrimeric Gβγ subunits, but mechanistic details remain poorly understood. While investigating the regulation of P-Rex1 by PIP 3 , we discovered that Ins(1,3,4,5)P 4 (IP 4 ) inhibits P-Rex1 activity and induces large decreases in backbone dynamics in diverse regions of the protein. Cryo-electron microscopy analysis of the P-Rex1·IP 4 complex revealed a conformation wherein the pleckstrin homology (PH) domain occludes the active site of the Dbl homology (DH) domain. This configuration is stabilized by interactions between the first DEP domain (DEP1) and the DH domain and between the PH domain and a 4-helix bundle (4HB) subdomain that extends from the C-terminal domain of P-Rex1. Disruption of the DH–DEP1 interface in a DH/PH-DEP1 fragment enhanced activity and led to a more extended conformation in solution, whereas mutations that constrain the occluded conformation led to decreased GEF activity. Variants of full-length P-Rex1 in which the DH–DEP1 and PH–4HB interfaces were disturbed exhibited enhanced activity during chemokineinduced cell migration, confirming that the observed structure represents the autoinhibited state in living cells. Interactions with PIP 3 -containing liposomes led to disruption of these interfaces and increased dynamics protein-wide. Our results further suggest that inositol phosphates such as IP 4 help to inhibit basal P-Rex1 activity in neutrophils, similar to their inhibitory effects on phosphatidylinositol-3-kinase.

59 BASIC BIOLOGICAL SCIENCES↗

Panoramic Mapping of Phonon Transport from Ultrafast Electron Diffraction and Scientific Machine Learning

Abstract One central challenge in understanding phonon thermal transport is a lack of experimental tools to investigate frequency‐resolved phonon transport. Although recent advances in computation lead to frequency‐resolved information, it is hindered by unknown defects in bulk regions and at interfaces. Here, a framework that can uncover microscopic phonon transport information in heterostructures is presented, integrating state‐of‐the‐art ultrafast electron diffraction (UED) with advanced scientific machine learning (SciML). Taking advantage of the dual temporal and reciprocal‐space resolution in UED, and the ability of SciML to solve inverse problems involving coupled Boltzmann transport equations, the frequency‐dependent interfacial transmittance and frequency‐dependent relaxation times of the heterostructure from the diffraction patterns are reliably recovered. The framework is applied to experimental Au/Si UED data, and a transport pattern beyond the diffuse mismatch model is revealed, which further enables a direct reconstruction of real‐space, real‐time, frequency‐resolved phonon dynamics across the interface. The work provides a new pathway to probe interfacial phonon transport mechanisms with unprecedented details.

36 MATERIALS SCIENCE↗

Unraveling disadhesion mechanism of epoxy/CSH interface under aggressive conditions

Almost all FRP-reinforced concrete exposed to the marine environment are susceptible to durability deficiencies due to failure of the FRP/epoxy/concrete interface, especially the vulnerable epoxy/concrete interface, which is frequently attacked by water and ions. Herein, molecular dynamics simulations of epoxy/CSH interface under different environmental exposures are utilized to specifically elucidate the degradation principles of water and ions on the bonding properties and mechanical responses of the epoxy/concrete interface. The environmental sequences associated with the interfacial bonding degradation are arranged as Na{sub 2}SO{sub 4} + NaCl>NaCl>Na{sub 2}SO{sub 4} > Water>Dry. Remarkably, water molecules weaken the interaction between the epoxy and CSH by robbing interfacial H- and Ca-O bonds, thereby reducing the energy barrier to interfacial peel and shear failure. The weakening effects are exacerbated by the presence of aggressive ions, as Na{sup +} ions attracted to the CSH surface accumulate more water molecules in the interfacial region by forming hydrated ions clusters, which ultimately accelerates the epoxy/CSH interfacial degradation.

36 MATERIALS SCIENCE↗

Hydrodynamic instabilities and heat transfer characteristics in the duct flow of a fluid in the supercritical thermodynamic regime

The behavior of fluids at supercritical thermodynamic conditions is inherently complex due to large variations in thermodynamic and transport properties. Recent numerical and experimental investigations illustrate ongoing interest for these fluids, especially supercritical CO 2 and supercritical water, for a variety of applications. For example, supercritical water reactors (SCWR) operate in this extreme condition of high-pressure and temperature, resulting in highly dynamic flow fields and unexpected heat transfer regimes. The potential heat transfer benefits in this regime are directly associated with the extreme variations in thermodynamic and transport properties, which occur at, and above, the critical point. This work characterizes the hydrodynamic instabilities that arise for fluids at supercritical thermodynamic conditions when buoyancy forces are significant. Two specific configurations are considered, a natural convection cavity flow, and a mixed convection, heated, horizontal channel flow. Natural convection flow in a cavity is a classical configuration with expected behavior below the critical point. This configuration aids in characterizing the effect of the variable properties in the supercritical thermodynamic regime. Further, limited studies in the existing literature have been conducted for low-Reynolds and intermediate-Rayleigh numbers, mixed-convection channel flows for supercritical water, which is the focus of the channel flow configuration. To investigate the thermally driven hydrodynamic instabilities in this regime, a high-order fully-implicit numerical method is used. Such strong variations in thermophysical properties (in particular, density) are difficult to simulate and an altogether compressible framework is needed. Therefore, the compressible Navier-Stokes equations are solved without any additional assumptions. The fully implicit, high-order in space and time, reconstructed discontinuous Galerkin method as implemented within the multi-physics code called ALE3D (Arbitrary Lagrangian and Eulerian in 2D and 3D), developed at Lawrence Livermore National Laboratory (LLNL), is used. This fully implicit, L-stable method accurately captures the compressible nature of the ow in the limit of very low Mach number. It has been widely accepted that above the critical point, only one phase is observed. However, recent research has indicated the existence of the distinct gas-like and liquid-like regions separated by the Widom line, the locus of the maxima of the specific heat. Along the Widom line, density decreases 6-fold, viscosity drops by a factor of 2, while specific heat spikes by an order of magnitude. These variations, specifically in density and viscosity, produce a thick pseudo-interface and flow dynamics behavior akin to film boiling. A pseudo-film at the heated wall of the cavity and the horizontal channel is observed where buoyancy forces induce mixing through the specific configurations. Further the local Rayleigh and Richardson numbers provide maps of the flow field and the buoyancy forces driving the microscopic mixing. In the first chapter, I describe a background of supercritical fluid and the various applications. The second chapter focuses on the mathematical model and numerical method used for simulations, where a description of the equation of state for supercritical water is described. The third chapter focuses on the natural convection cavity with a heated bottom wall. In this cavity a gas-like and a liquid-like flow within the supercritical thermodynamic regime are observed. The fourth chapter focuses on a forced convection, horizontal channel, distinguishing between the gas-like, liquid-like, and mixed flow regimes. Mixed convection flow, with the addition of gravitational forces in the horizontal channel show the influence of variable properties on the hydrodynamic development, heat transfer, and rising instabilities. The last chapter of this research focuses on characterizing the unstable hydrodynamics through time-averaging processes and analysis of the movement of energy through the developing plumes.

42 ENGINEERING↗

Water dissociation at the water–rutile TiO 2 (110) interface from ab initio-based deep neural network simulations

The interaction of water with TiO 2 surfaces is of crucial importance in various scientific fields and applications, from photocatalysis for hydrogen production and the photooxidation of organic pollutants to self-cleaning surfaces and bio-medical devices. In particular, the equilibrium fraction of water dissociation at the TiO 2 –water interface has a critical role in the surface chemistry of TiO 2 , but is difficult to determine both experimentally and computationally. Among TiO 2 surfaces, rutile TiO 2 (110) is of special interest as the most abundant surface of TiO 2 ’s stable rutile phase. While surface-science studies have provided detailed information on the interaction of rutile TiO 2 (110) with gas-phase water, much less is known about the TiO 2 (110)–water interface, which is more relevant to many applications. In this work, we characterize the structure of the aqueous TiO 2 (110) interface using nanosecond timescale molecular dynamics simulations with ab initio-based deep neural network potentials that accurately describe water/TiO 2 (110) interactions over a wide range of water coverages. Simulations on TiO 2 (110) slab models of increasing thickness provide insight into the dynamic equilibrium between molecular and dissociated adsorbed water at the interface and allow us to obtain a reliable estimate of the equilibrium fraction of water dissociation. We find a dissociation fraction of 22 ± 6% with an associated average hydroxyl lifetime of 7.6 ± 1.8 ns. These quantities are both much larger than corresponding estimates for the aqueous anatase TiO 2 (101) interface, consistent with the higher water photooxidation activity that is observed for rutile relative to anatase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Examining polymer‐protein biophysical interactions with small‐angle x‐ray scattering and quartz crystal microbalance with dissipation

Abstract Polymer‐protein hybrids can be deployed to improve protein solubility and stability in denaturing environments. While previous work used robotics and active machine learning to inform new designs, further biophysical information is required to ascertain structure–function behavior. Here, we show the value of tandem small‐angle x‐ray scattering (SAXS) and quartz crystal microbalance with dissipation (QCMD) experiments to reveal detailed polymer‐protein interactions with horseradish peroxidase (HRP) as a test case. Of particular interest was the process of polymer‐protein complex formation under thermal stress whereby SAXS monitors formation in solution while QCMD follows these dynamics at an interface. The radius of gyration ( R g ) of the protein as measured by SAXS does not change significantly in the presence of polymer under denaturing conditions, but thickness and dissipation changes were observed in QCMD data. SAXS data with and without thermal stress were utilized to create bead models of the potential complexes and denatured enzyme, and each model fit provided insight into the degree of interactions. Additionally, QCMD data demonstrated that HRP deforms by spreading upon surface adsorption at low concentration as shown by longer adsorption times and smaller frequency shifts. In contrast, thermally stressed and highly inactive HRP had faster adsorption kinetics. The combination of SAXS and QCMD serves as a framework for biophysical characterization of interactions between proteins and polymers which could be useful in designing polymer‐protein hybrids.

60 APPLIED LIFE SCIENCES↗

Support Effect and Surface Reconstruction in In 2 O 3 / m- ZrO 2 Catalyzed CO 2 Hydrogenation

Here, we investigate the chemical and structural dynamics at the interface of In 2 O 3 /m-ZrO 2 and their consequences on the CO 2 hydrogenation reaction (CO 2 HR) under reaction conditions. While acting to enrich CO 2 , monoclinic zirconia (m-ZrO 2 ) was also found to serve as a chemical and structural modifier of In 2 O 3 that directly governs the outcome of the CO 2 HR. These modifying effects include the following: (1) Under reaction conditions (above 623 K), partially reduced In 2 O 3 , i.e., InO x (0 < x < 1.5), was found to migrate in and out of the subsurface of m-ZrO 2 in a semireversible manner, where m-ZrO 2 accommodates and stabilizes InO x by serving as a reservoir. The decreased concentration of surface InO x under elevated temperatures coincides with significantly decreased selectivity toward methanol and a sharp increase of the reverse water–gas shift reaction. The reconstruction-induced variation of InO x concentration appears to be one of the most important factors contributing to the altered catalytic performance of CO 2 HR at different reaction conditions. (2) The strong interactions and reactions between m-ZrO 2 and In 2 O 3 result in the activation of a pool of In–O bonds at the In 2 O 3 /m-ZrO 2 interface to form oxygen vacancies. On the other hand, the high dispersity of In 2 O 3 nanostructures onto m-ZrO 2 prevents their over-reduction under catalytically relevant conditions (up to 673 K), when bare In 2 O 3 is unavoidably reduced into the metallic phase (In 0 ). The relationship between the extent of reduction of In 2 O 3 and catalytic performance (CO 2 conversion, CH 3 OH selectivity, or yield of CH 3 OH) suggests the presence of an optimum coverage of surface InO x and oxygen vacancies under reaction conditions. The conventional model that links catalytic performance solely to the coverage of oxygen vacancies appears invalid in the present case. In situ analysis also allows the observation of surface reaction intermediates and their interconversions, including the reduction of CO 3 * into formate, a precursor for the formation of methanol and CO. The combinative ex situ and in situ study sheds light on the reaction mechanism of the CO 2 HR on In 2 O 3 /m-ZrO 2 -based catalysts. Our findings on the large-scale surface reconstructions, support effect, and the reaction mechanism of In 2 O 3 /m-ZrO 2 for CO 2 HR may apply to other related metal oxide catalyzed CO 2 reduction reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Role of Subsurface Flow on Evapotranspiration: A Global Sensitivity Analysis

Abstract Water resources are impacted by water‐energy balance fluxes at the land surface, most notably evapotranspiration ( ET ), the largest component of surface energy balance. While integrated hydrologic models show promise in quantifying the nonlinear dynamics at this interface, the model results are plagued by parametric uncertainties. Given the high computational demand of running multiple parameter spaces of these models, little is known about how these uncertainties propagate into land surface processes. In this work, we perform a global sensitivity analysis by computing Sobol and AMAE indices using a surrogate model constructed with a polynomial chaos expansion to assess the impacts of the subsurface physical properties on ET . We do so by modeling a semisynthetic test case. Our results show that the effects of vertical hydraulic conductivity, porosity, and the water retention curve parameter Van Genuchten α mainly control ET . However, we note that while evaporation ( E ) shows behavior similar to the ET with high sensitivity to the parameters controlling the flow in the unsaturated zone, transpiration ( T ) is very sensitive to the saturated zone parameters and groundwater flow, especially during periods without rain. Our results also show that heterogeneities in land cover impact the flow in the saturated zone. Furthermore, our work demonstrates that reduced‐order models can be developed to make integrated models more accessible for rigorous sensitivity analyses and calibration purposes.

Maina, Fadji Zaouna↗

Unveiling the role of structural vacancies in Mn-based Prussian blue analogues for energy storage applications

Prussian blue analogues (PBAs) are promising cathode materials for monovalent- and multivalent-ion batteries due to their large framework structures. Nevertheless, the influence of lattice vacancies on their electrochemical performance has not been thoroughly clarified, hindering the further development of PBAs. Here we identify two types of functional vacancies, i.e., structural vacancies (SVs) and incidental vacancies (IVs), in manganese hexacyanoferrate (MnHCF) through synchrotron-based X-ray absorption spectroscopy and density functional theory calculations. Unlike structurally disordered IVs, the introduction of structurally ordered SVs promotes ion transport and reduces the interaction between host ions and the framework, enabling improved cycling and rate performance. The controllable adjustment of SVs in K-rich MnHCF is achieved through a co-reactant method. Furthermore, the partial introduction of SVs in K-rich MnHCF is demonstrated to favor both a milder structural evolution by alleviating the Jahn–Teller distortion of Mn 3+ and a stable dynamic process of interface reaction. As a result, this study unveils the potential importance of incorporating structural vacancies into MnHCF for advanced energy storage applications.

Gao, Chongwei↗

From force chains to nonclassical nonlinear dynamics in cemented granular materials

In this letter, we present evidence for a mechanism responsible for the nonclassical nonlinear dynamics observed in many cemented granular materials that are generally classified as mesoscopic nonlinear elastic materials. We demonstrate numerically that force chains are created within the complex grain-pore network of these materials when subjected to dynamic loading. The interface properties between grains along with the sharp and localized increase of the stress occurring at the grain-grain contacts leads to a reversible decrease of the elastic properties at macroscopic scale and peculiar effects on the propagation of elastic waves when grain boundary properties are appropriately considered. These effects are observed for relatively small amplitudes of the elastic waves, i.e., within tens of microstrain, and relatively large wavelengths, i.e., orders of magnitude larger than the material constituents. The mechanics are investigated numerically using the hybrid finite-discrete-element method and match those observed experimentally using nonlinear resonant ultrasound spectroscopy.

36 MATERIALS SCIENCE↗

Enhancing Adaptive Physics Refinement Simulations Through the Addition of Realistic Red Blood Cell Counts

Simulations of cancer cell transport require accurately modeling mm-scale and longer trajectories through a circulatory system containing trillions of deformable red blood cells, whose intercellular interactions require submicron fidelity. Using a hybrid CPU-GPU approach, we extend the advanced physics refinement (APR) method to couple a finely-resolved region of explicitly-modeled red blood cells to a coarsely-resolved bulk fluid domain. We further develop algorithms that: capture the dynamics at the interface of differing viscosities, maintain hematocrit within the cell-filled volume, and move the finely-resolved region and encapsulated cells while tracking an individual cancer cell. Comparison to a fully-resolved fluid-structure interaction model is presented for verification. Finally, we use the advanced APR method to simulate cancer cell transport over a mm-scale distance while maintaining a local region of RBCs, using a fraction of the computational power required to run a fully-resolved model.

Roychowdhury, Sayan↗

ACCERT

The main function of ACCERT (The Algorithm for the Capital Cost Estimation of Reactor Technologies) is to provide an item-by-item estimate of the cost of a facility, at present a nuclear reactor complex, primarily nuclear power stations. The core of ACCERT is the large number of algorithms that have been developed and will continue to be developed. ACCERT is also a general methodology for identifying and organizing the individual items that are estimated using the ACCERT algorithms. ACCERT also summarize status and results; to save results and pull information from previous analyses; and to provide an interactive dynamic graphical user interface for a wide range of functions and visualizations.

Zhou, Jia [Argonne National Laboratory (ANL), Argo↗