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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Rejuvenation as the origin of planar defects in the CrCoNi medium entropy alloy

Abstract High or medium- entropy alloys (HEAs/MEAs) are multi-principal element alloys with equal atomic elemental composition, some of which have shown record-breaking mechanical performance. However, the link between short-range order (SRO) and the exceptional mechanical properties of these alloys has remained elusive. The local destruction of SRO by dislocation glide has been predicted to lead to a rejuvenated state with increased entropy and free energy, creating softer zones within the matrix and planar fault boundaries that enhance the ductility, but this has not been verified. Here, we integrate in situ nanomechanical testing with energy-filtered four-dimensional scanning transmission electron microscopy (4D-STEM) and directly observe the rejuvenation during cyclic mechanical loading in single crystal CrCoNi at room temperature. Surprisingly, stacking faults (SFs) and twin boundaries (TBs) are reversible in initial cycles but become irreversible after a thousand cycles, indicating SF energy reduction and rejuvenation. Molecular dynamics (MD) simulation further reveals that the local breakdown of SRO in the MEA triggers these SF reversibility changes. As a result, the deformation features in HEAs/MEAs remain planar and highly localized to the rejuvenated planes, leading to the superior damage tolerance characteristic in this class of alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2022

$T\overline{T}$-deformed free energy of the Airy model

Sharpening the correspondence of Jackiw-Teitelboim (JT) gravity and its dual matrix model description at a finite radial cutoff λ through the $T\overline{T}$ deformation is of interest. To proceed, we simplify the problem by considering the Airy model and deform Airy correlators in the same way as in $T\overline{T}$ -deformed JT gravity. We use those correlators to compute the annealed and quenched free energies for both λ > 0 and λ < 0 from an integral representation of the replica trick. At the leading order in λ and low temperatures, we confirm that the genus-zero quenched free energy monotonically decreases as a function of temperature when perturbation theory is valid. We then study the all-genus quenched free energy at low temperatures, where we discover and discuss subtleties due to non-perturbative effects in the Airy model, as well as the contributions from the non-perturbative branch under the $T\overline{T}$ deformation.

2D gravity↗
DOE OSTI2024

Bubble-Free Frontal Polymerization of Acrylates via Redox-Initiated Free Radical Polymerization

Thermal frontal polymerization (FP) of acrylate monomers mixed with conventional peroxide initiators leads to significant bubble formation at the polymerizing front, limiting their practical applications. Redox initiators present a promising alternative to peroxide initiators, as they prevent the formation of gaseous byproducts during initiator decomposition and lower the front temperature, thereby enabling bubble-free FP. In this study, we investigate the FP of acrylate monomers of varying functionalities, including methyl methacrylate (MMA), 1,6-hexanediol diacrylate (HDDA), and trimethylolpropane triacrylate (TMPTA), using N,N -dimethylaniline/benzoyl peroxide (DMA/BPO) redox couple at room temperature and compare their front behavior, pot life, and bubble formation with those of same resin systems mixed with a conventional peroxide initiator, Luperox 231. The use of redox couples in FP of acrylates shows promise for rapid, energy-efficient manufacturing of polyacrylates and can enable new applications such as 3D printing and composite manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Intrinsic (Trap‐Free) Transistors Based on Epitaxial Single‐Crystal Perovskites

Abstract The first experimental realization of the intrinsic (not dominated by defects) charge conduction regime in lead‐halide perovskite field‐effect transistors (FETs) is reported. The advance is enabled by: i) a new vapor‐phase epitaxy technique that results in large‐area single‐crystalline cesium lead bromide (CsPbBr 3 ) films with excellent structural and surface properties, including atomically flat surface morphology, essentially free from defects and traps at the level relevant to device operation; ii) an extensive materials analysis of these films using a variety of thin‐film and surface probes certifying the chemical and structural quality of the material; and iii) the fabrication of nearly ideal (trap‐free) FETs with characteristics superior to any reported to date. These devices allow the investigation of the intrinsic FET and (gated) Hall‐effect carrier mobilities as functions of temperature. The intrinsic mobility is found to increase on cooling from ≈30 cm 2 V −1 s −1 at room temperature to ≈250 cm 2 V −1 s −1 at 50 K, revealing a band transport limited by phonon scattering. Establishing the intrinsic (phonon‐limited) mobility provides a solid test for theoretical descriptions of carrier transport in perovskites, reveals basic limits to the technology, and points to a path for future high‐performance perovskite electronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Interpreting the Diurnal Cycle of Clouds and Precipitation in the ARM GoAmazon Observations: Shallow to Deep Convection Transition

The Green Ocean Amazon (GoAmazon) 2014/5 field campaign data are used to study the diurnal cycle of clouds and precipitation. Through a careful classification of days with shallow cumulus, congestus and deep convection, we investigate the major differences among locally generated convection regimes and the most important environmental factors governing the shallow-to-deep convection transition. On shallow cumulus days, a greater sensible heat flux drives deeper boundary layer growth, which entrains drier free-tropospheric air and lowers the relative humidity, thus leading to a significantly higher cloud base than those on days with deeper convection. Congestus and deep convection regimes exhibit distinct cloud top height distributions with noticeable differences in the vertical wind shear in the mid-troposphere, suggesting an important role of wind shear in limiting the vertical extent of convection. On deep convection days, with preexisting nocturnal convection or cold-pools from external disturbances, the timing of peak surface precipitation (12:00–13:00 LST) tends to be in-phase with the diurnal variation in surface fluxes. However, it takes longer for local deep convection to develop without these disturbances. A plume model with thermodynamic and dynamical constraints is developed to explore the relative importance of various convection-controlling factors. Initial cloud-base vertical velocity and buoyancy are important in helping parcels ascend to the level of free convection (LFC). After parcels reach the LFC, entrainment of environmental air and lower free troposphere humidity become crucial in determining cloud top. Entrainment rate differentiates among convection regimes, which may be tied to the cloud size distribution at cloud base.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Flavor in SU(5)$SU(5)$ Finite Grand Unified Models

Abstract Four supersymmetric models which exhibit and/or symmetries are studied, that are finite to two or all loops, and their corresponding mass matrices. The first is an all‐loop finite model based on an flavor symmetry, which leads to phenomenologically nonviable mass matrices. The remaining models, based on cyclic symmetries, show various mass textures, some of which are phenomenologically promising. For the two‐loop finite models, the parametric solutions to the finiteness conditions determine completely some of the Yukawa couplings, and lead to a restricted range of values for other ones at the GUT scale, with a considerable reduction in the number of free parameters. One particular solution of the two‐loop models shows an enhanced symmetry, leading to an all‐loop finite model, which has a significant parameter reduction and could in principle reproduce the observed quark masses and mixing pattern. In this case the finiteness conditions determine the absolute value of all the Yukawa couplings at the unification scale. Finally, the minimum number of phases in the mass matrices and their position are determined, a task not previously done in Finite Unified Theories, which contributes towards the reduction of parameters and a better understanding of the Yukawa couplings.

Estrada Ramos, Luis Odín↗
DOE OSTI2020

Interacting radiation after Planck and its implications for the Hubble tension

Standard cosmology predicts that prior to matter-radiation equality about 41% of the energy density was in free-streaming neutrinos. In many beyond Standard Model scenarios, however, the amount and free-streaming nature of this component is modified. For example, this occurs in models with new neutrino self-interactions or an additional dark sector with interacting light particles. Here, we consider several extensions of the standard cosmology that include a non-free-streaming radiation component as motivated by such particle physics models and use the final Planck data release to constrain them. This release contains significant improvements in the polarization likelihood which plays an important role in distinguishing free-streaming from interacting radiation species. Fixing the total amount of energy in radiation to match the expectation from standard neutrino decoupling we find that the fraction of free-streaming radiation must be ffs > 0.8 at 95% CL (combining temperature, polarization and baryon acoustic oscillation data). Allowing for arbitrary contributions of free-streaming and interacting radiation, the effective number of new non-free-streaming degrees of freedom is constrained to be Nfld < 0.6 at 95% CL. Cosmologies with additional radiation are also known to ease the discrepancy between the local measurement and CMB inference of the current expansion rate H0. We show that including a non-free-streaming radiation component allows for a larger amount of total energy density in radiation, leading to a mild improvement of the fit to cosmological data compared to previously discussed models with only a free-streaming component.

particle physics - cosmology connection↗
DOE OSTI2024

Electromagnetic Design Optimization Integrated with Mechanical Stress Analysis of PM-Assisted Synchronous Reluctance Machine Topologies Enabled with a Blend of Magnets

Permanent Magnet-Assisted Synchronous Reluctance Machines (PMASynRM) provide a low-cost alternative to Surface PM Machines due to the use of relatively lower grades of rare-earth (RE) or RE-free magnets, as the performance degradation due to weaker magnets is compensated by the presence of reluctance torque. However, the weaker magnets suffer from a high risk of demagnetization, leading to unreliable motor operation. Using a blend of RE and RE-free magnets has the potential to overcome this issue. This paper proposes to blend different grades of various rare-earth (RE) and rare-earth-free (RE-free) magnets in six different combinations and utilizes them in two-layer and three-layer U-shaped PMASynRM topologies with both eight-pole and six-pole variations. The rotor of the various designs is then optimized using a differential evolution (DE) based optimization algorithm to obtain low-cost designs with reduced RE magnet volume and minimum demagnetization risk. The optimization of each design is also integrated with the evaluation of mechanical stresses in the rotor laminations so as to maintain the stresses below the material yield strength. Furthermore, the various performance metrics, such as toque–speed/power–speed characteristics, demagnetization, and efficiency maps, are evaluated for each of the optimized and mechanically feasible designs. A quantitative comparison of the various optimized designs is also obtained to highlight the various trade-offs. The results indicate the feasibility of meeting the baseline torque requirement across the entire speed range, even with a 100% reduction in RE magnet volume and less than 5% demagnetization risk, while achieving a cost reduction exceeding 50%. Moreover, the two-layer, eight-pole designs exhibit relatively higher performance, whereas the three-layer, eight-pole designs are found to be the most economical option.

design optimization↗
DOE OSTI2023

Unveiling the Role of Compositional Drifts on the Tack of Pressure‐Sensitive‐Adhesives

Abstract Pressure‐sensitive‐adhesives (PSAs) are pervasive in electronic, automobile, packaging, and biomedical applications due to their ability to stick to numerous surfaces without undergoing chemical reactions. These materials are typically synthesized by the free radical copolymerization of alkyl acrylates and acrylic acid, leading to an ensemble of polymer chains with varying composition and molecular weight. Here, reversible addition−fragmentation chain‐transfer (RAFT) copolymerizations in a semi‐batch reactor are used to tailor the molecular architecture and bulk mechanical properties of acrylic copolymers. In the absence of cross‐links, the localization of acrylic acid toward the chain ends leads to microphase separation, creep resistance, and enhanced tack. However, in the presence of Al(acac) 3 crosslinker, the creep resistance remains unchanged and mostly the large‐strain mechanical properties are affected. This behavior is attributed to microphase separation, but also to a change in the energy required to break physical associations, and untangle and elongate associative polymers to large deformations.

Polymer Science↗
DOE OSTI2025

A model to assess Zircaloy’s mechanical property changes following a transient beyond critical heat flux

Maintaining the integrity of nuclear fuel rods is essential for ensuring public health and safety in nuclear power generation. During reactor operation, this integrity is confirmed by demonstrating compliance with established regulatory acceptance criteria. For moderate-frequency events, such as limiting transients and anticipated operational occurrences (AOOs), the current fuel integrity criterion is based on preventing boiling transition. This criterion assumes that prevention of boiling transition will prevent excessive cladding heating and, thus, fuel failure during normal operations. While conservative, this approach places significant constraints on core design, fuel cycle economics, and a plant’s ability to perform major power uprates, leading to suboptimal fuel utilization and inefficient carbon-free energy production. A more efficient approach could be achieved by revising the failure criterion to a material-specific limit rather than strictly preventing the boiling transition, since boiling transition per se is not a cause of fuel cladding failure. Here, as a result, a new licensing framework based on material properties, termed time-at-temperature (t@T), is needed. This approach would allow for brief periods of post–critical heat flux operation during an AOO without compromising safety. Implementing the t@T licensing strategy requires a robust technical foundation in material properties, which must be established through comprehensive data collection on both unirradiated and irradiated fuel and cladding materials. This foundation would enable the development of a safety basis that ensures safe operation while providing greater flexibility and efficiency for reactor operation. This paper documents a thorough review of the available data to establish a baseline knowledge that can inform the development of cladding mechanical models, as well as identify experimental data gaps that need to be addressed in future research. Machine learning and data informatics were utilized to extract the importance of parameters on the t@T parameter. Industry tools were used to perform baseline analyses to define the relevant transient conditions for data analysis. The subsequent review successfully identified applicable experimental data, as well as sufficient data to evaluate changes in cladding mechanical properties following an AOO transient. Rather than developing new models, this work coupled existing irradiation annealing and recrystallization models to calculate changes in hardness, yield stress, and ultimate tensile stress following an AOO event. The findings from this review were summarized to highlight the experimental data needs required to fill remaining gaps and support the development of future t@T licensing methodologies.

Cladding performance↗
DOE OSTI2021

Alkylation of monomeric, dimeric, and polymeric lignin models through carbon-hydrogen activation using Ru-catalyzed Murai reaction

In this study, we have assessed directed carbon-hydrogen activation (CHA) for alkylation of monomeric, dimeric, and polymeric lignin models using Murai's catalyst [RuH 2 (CO)(PPh 3 ) 3 ]. Based on related work from our laboratory showing that isolated organosolv lignin bears benzylic directing groups ideal for CHA reactions, this approach could offer new methodology for the valorization of biorefinery lignin. Monomeric and dimeric models bearing a keto group at the benzylic position undergo Ru-catalyzed alkylation in good to excellent yield. Similarly, models bearing a benzylic OH group also undergo alkylation via a tandem oxidation/alkylation process enabled by the Ru catalyst. Polymeric models show low levels of functionalization as a result of the poor solubility of the starting polymer. With unsymmetrical models, functionalization occurs first at the least sterically hindered ortho-site, but a subsequent alkylation, leading to disubstituted products can occur at the more sterically hindered site, leading to hexasubstituted arenes. The reaction shows sensitivity to free phenolic OH groups, which appears to reduce the yield in some reactions, and is also a contributing factor to the low yields observed with polymeric lignin models. Finally, combining CHA methodology with lignin isolation technology able to introduce appropriate directing groups for catalytic functionalization will form the basis for improved conversion of lignin to high value chemical products.

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

Controlling Preferred Grain Orientation in Vapor-Deposited Metal-Halide Perovskite Thin Films

Metal-halide perovskites are promising semiconductor materials for light-absorber layers in solar cells due to their optimized band gap, defect tolerance, and relative ease of synthesis. In this work, we demonstrate the viability of vapor transport deposition (VTD), a solvent-free processing method, to realize polycrystalline films of both lead iodide (PbI 2 ) and methylammonium lead iodide (MAPbI 3 ) perovskites showing preferential crystallographic orientation. Notable is the difference in perovskite film texturing observed for sequentially and co-deposited VTD films of MAPbI 3 , as well as the lack of strong preferential orientation in solution-processed MAPbI 3 films. While sequential deposition of the perovskite precursors PbI 2 and methylammonium iodide (MAI) leads to a MAPbI 3 film with a limited preferential grain orientation, co-deposited MAPbI 3 films mirror the orientation of excess PbI 2 present in the film. The latter is confirmed by the similar dependence of preferential orientation for PbI 2 and co-deposited MAPbI 3 on underlayer roughness, as well as the emergence of preferential orientation in MAPbI 3 only when excess PbI 2 is present. Both MAPbI 3 and PbI 2 films show a strong preferred lattice orientation on smooth substrates, while on rougher substrates, this orientation is disrupted. Furthermore, these results are interpreted as excess PbI 2 frustrating the diffusion of MAI in the film, which would otherwise disrupt the preferred orientation, pointing to a notable difference in lattice orientation arising from processing technique and conditions.

Deposition↗
DOE OSTI2024

Microscopic Origin of Twist-Dependent Electron Transfer Rate in Bilayer Graphene

Using molecular simulation and continuum dielectric theory, we consider how electrochemical kinetics are modulated by the twist angle in bilayer graphene electrodes. By establishing a connection between the twist angle and the screening length of charge carriers within the electrode, we investigate how tunable metallicity modifies the statistics of the electron transfer energy gap. Constant potential molecular simulations show that the activation free energy for electron transfer increases with screening length, leading to a non-monotonic dependence on the twist angle. Here, the twist angle alters the density of states, tuning the number of thermally accessible channels for electron transfer and the reorganization energy by affecting the stability of the vertically excited state through attenuated image charge interactions. Understanding these effects allows us to express the Marcus rate of interfacial electron transfer as a function of the twist angle in a manner consistent with experimental observations.

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

Mechanistic Similarities and Differences for Hydrogenation of Aromatic Heterocycles and Aliphatic Carbonyls on Sulfided Ru Nanoparticles

This study establishes the contrasting reactivity trends for the hydrogenation of aromatic hydrocarbons (AHCs = C n H m X, X = N, S, O, and C) and aliphatic carbonyls [R a C(O)R b ; R a = alkyl group, R b = CH 3 or H] on sulfided Ru clusters arising from the difference in the elementary proton and hydride attack catalytic sequence. Both reactions require sequential additions of a proton from either Ru n+ –(SH 2 ) or S 2 –(H δ+ ) species and a hydride from Ru n+ –(H δ– ) species to the unsaturated C=X bonds. For the five-membered-ring aromatic heterocycles (AHCs = pyrrole, thiophene, and furan), an initial proton addition limits the catalytic turnovers; thus, their hydrogenation reactivity increases with increasing gas-phase proton affinities of the AHCs. Pyridine as the more basic six-membered N-AHC is more susceptible to protonation; therefore, it is more reactive, and its initial proton addition is quasi-equilibrated, followed by the kinetically relevant hydride addition. Conversely, aliphatic carbonyls prefer to undergo hydrogen additions in a reverse sequence, where a Ru n+ –(H δ– ) hydride initially attacks the electron-deficient carbonyl C atom as the kinetically relevant step before a subsequent rapid S 2 –(H δ+ ) proton addition on the electron-rich O atom, as confirmed by isotopic exchange studies with butanal-D 2 and 1-butanol-D 2 mixtures and density functional theory calculations on S-deficient RuS 2 (100) surfaces. For these reasons, their hydrogenation reactivity increases with increasing gas-phase hydride affinities of the carbonyls. On metallic Ru surfaces without sulfur, hydrogen adatoms (H*) are the only reactive hydrogen species; the reactivity of their attack on aromatic heterocycles increases with increasing reactant proton affinities much more sensitively than that on sulfided Ru surfaces. This work illustrates the distinct catalytic roles of the diverse hydrogen species in hydrogenation—the interplay between proton and hydride additions has marked catalytic consequences in shaping the free energy landscape of the reactions, which in turn leads to the observed kinetic dependences, kinetic parameters, reactivity trends, and scaling relations between the measured barriers and the appropriate kinetic descriptors, that is, proton affinity of AHCs and hydride affinity of carbonyls in hydrogenation catalysis. Here, these mechanistic similarities and differences provide explanations of the observed reactivity trends and thus have profound implications for industrial hydrogenation and hydrotreating catalysis.

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

The Dependence of Climate Sensitivity on the Meridional Distribution of Radiative Forcing

Abstract This study investigates how climate sensitivity depends upon the spatial pattern of radiative forcing. Sensitivity experiments using a coupled ocean‐atmosphere model were conducted by adding anomalous incoming solar radiation over the entire globe, Northern Hemisphere mid‐latitudes, Southern Ocean, and tropics. The varied forcing patterns led to highly divergent climate sensitivities. Specifically, the climate is nearly twice as sensitive to Southern Ocean forcing as tropical forcing. Strong coupling between the surface and free troposphere in the tropics increases the inversion strength, leading to smaller cloud feedback in the tropical forcing experiments. In contrast, the extratropics exhibit weaker coupling, a decrease or near‐zero change in the inversion strength, and strong positive cloud feedback. These results contrast with the conventional SST‐pattern effect in which tropical surface temperature changes regulate climate sensitivity. They also have important implications for other potentially asymmetric forcings, such as those from geoengineering, volcanic eruptions, and paleoclimatic changes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Ion diffusion retarded by diverging chemical susceptibility

Abstract For first-order phase transitions, the second derivatives of Gibbs free energy (specific heat and compressibility) diverge at the transition point, resulting in an effect known as super-elasticity along the pressure axis, or super-thermicity along the temperature axis. Here we report a chemical analogy of these singularity effects along the atomic doping axis, where the second derivative of Gibbs free energy (chemical susceptibility) diverges at the transition point, leading to an anomalously high energy barrier for dopant diffusion in co-existing phases, an effect we coin as super-susceptibility. The effect is realized in hydrogen diffusion in vanadium dioxide (VO 2 ) with a metal-insulator transition (MIT). We show that hydrogen faces three times higher energy barrier and over one order of magnitude lower diffusivity when it diffuses across a metal-insulator domain wall in VO 2 . The additional energy barrier is attributed to a volumetric energy penalty that the diffusers need to pay for the reduction of latent heat. The super-susceptibility and resultant retarded atomic diffusion are expected to exist universally in all phase transformations where the transformation temperature is coupled to chemical composition, and inspires new ways to engineer dopant diffusion in phase-coexisting material systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Sparsity-Independent Lyapunov Exponent in the Sachdev-Ye-Kitaev Model

The saturation of a recently proposed universal bound on the Lyapunov exponent has been conjectured to signal the existence of a gravity dual. This saturation occurs in the low-temperature limit of the dense Sachdev-Ye-Kitaev (SYK) model, N Majorana fermions with q body ( q > 2 ) infinite-range interactions. We calculate certain out-of-time-order correlators (OTOCs) for N ≤ 64 fermions for a highly sparse SYK model and find no significant dependence of the Lyapunov exponent on sparsity up to near the percolation limit where the Hamiltonian breaks up into blocks. This provides strong support to the saturation of the Lyapunov exponent in the low-temperature limit of the sparse SYK. A key ingredient to reaching N = 64 is the development of a novel quantum spin model simulation library that implements highly optimized matrix-free Krylov subspace methods on graphical processing units. This leads to a significantly lower simulation time as well as vastly reduced memory usage over previous approaches, while using modest computational resources. Strong sparsity-driven statistical fluctuations require both the use of a much larger number of disorder realizations with respect to the dense limit and a careful finite size scaling analysis. The saturation of the bound in the sparse SYK points to the existence of a gravity analog that would enlarge substantially the number of field theories with this feature. Published by the American Physical Society 2024

Physics↗
DOE OSTI2025

Origin of the Low-Energy Enhancement of the γ-Ray Strength Function

The low-energy enhancement (LEE) in γ-ray strength functions has been experimentally identified in a large number of nuclei during the past two decades; however, the origin of the enhancement is not fully understood. Building on previous theoretical work, we investigate the LEE and its relation to the scissors mode (SM) with an independent theoretical approach. We apply a novel angular-momentum-projected shell-model method that explicitly endows degrees of freedom to describe the scissors motion. Taking the recently measured γ-ray strength functions in Neodymium isotopes as examples, we find that the LEE arises from a quasi-free scissors motion appearing only in weakly-deformed nuclei, which can be viewed as an approximate free-rotation of neutrons with respect to protons. This leads us to propose a new type of collective motion, scissors rotation, to contrast the scissors vibration widely known in well-deformed nuclei. The observed LEE is naturally interpreted as the first evidence for this collective excitation mode.

Collective models↗