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On Thermodynamic and Kinetic Mechanisms for Stabilizing Surface Solid Solutions

Many processes for energy storage rely on transformations between phases with strong separation tendencies. In these systems, performance limitations can arise from undesirable chemical and mechanical factors associated with the phase separation behavior. Solid solutions represent a desirable alternative, provided the conditions for their formation are known. In the present work, we invoke linear stability theory and diffuse-interface mesoscopic simulations to demonstrate that solid solutions can be stabilized near surface layers of phase-separating systems. Two factors are found to drive surface solid-solution formation: surface relaxation of solution self-strain energy and anisotropy of diffusion mobility. Using a strongly phase-separating LiXFePO4 particle as a model system, we show that the relaxation of the solution self-strain energy competes against the relaxation of the coherency strain energy to stabilize surface solid solutions. Our theoretical understanding also suggests that highly anisotropic diffusion mobility can provide an alternative kinetic route to achieve the same aim, with stabilizing behavior strongly dependent on the specific alignment of the surface orientation. Our findings provide fundamental guidance for manipulating solid-solution behavior in nanoscale structures, in which surface effects become especially significant. Beyond energy storage materials, our findings have important implications for understanding solid-solution formation in other phase-separating systems from metal alloys to ceramics.

25 ENERGY STORAGE↗

Fundamental aspects of deuterium retention in tungsten at high flux plasma exposure

An effect of enhanced trapping of deuterium in tungsten at high flux was discovered. It was shown analytically and confirmed experimentally that the deuterium trapping in a presence of high density of defects in tungsten (W) depends on the ion energy and ion flux. Newly developed analytical model explains experimentally observed discrepancy of deuterium trapping at radiation-induced defects in tungsten at different ion fluxes that significantly improves a prediction of hydrogen isotope accumulation in different plasma devices, including ITER and DEMO. The developed model can be used for many system of hydrogen in a metal in both normal and extreme environments (high fluxes, elevated temperatures, neutron irradiation, etc.). This new model allows, for the first time, to validate density function theory (DFT) predictions of multiple occupation of a defect with deuterium against experimental data that bridge the gap in length and time scale between DFT calculations and experiments. By comparing first-principle calculations based on DFT and semi-empirical “adsorption model,” it was proved that the mechanism of hydrogen isotope trapping in a vacancy cluster is similar to a chemisorption on a surface. Binding energies of deuterium with different types of defects in W were defined. Moreover, the surface barrier of deuterium to be chemisorbed on a clean W surface was found to be less than 1 eV and kinetics of deuterium release is limited by de-trapping from defects rather than to be limited by surface effects.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Automation of Overset Structured Mesh Generation onBoundary Representation Geometries

A scheme is presented for the automatic generation of structured overset meshes ongeometries that are defined by Boundary Representation (BRep) solids. The surface meshsystem consists of face, edge and node meshes corresponding to the three respective basicBRep entity types. A cut-cell method is introduced to improve robustness of the on-geometrydetermination test for a face mesh grid point. A geometric component tagging scheme is utilizedto enhance local grid point distribution on a configuration with a large range of geometricscales. A cap grid topology is automatically utilized around the trailing edge of wing and tailtips to enhance mesh quality and to enable more effective surface coverage. Robustness of thehyperbolic surface marching method is improved by replacing the point projection scheme witha walking scheme. Relaxation of surface grid spacing at concave corners enables automatedhigh quality hyperbolic volume mesh creation. Domain connectivity is automatically performedon the surface mesh system. A variety of test cases are presented including a re-entry capsule,two models of the Juncture Flow Experiment wing-body, five rotorcraft concept vehicles, andvarious components of the High-Lift Common Research Model from the High-Lift PredictionWorkshop 4.

TTT↗

Ocean Surface Flux Algorithm Effects on Tropical Indo-Pacific Intraseasonal Precipitation

Surface latent heat fluxes help maintain tropical intraseasonal precipitation. We develop a latent heat flux diagnostic that depicts how latent heat fluxes vary with the near-surface specific humidity vertical gradient (Δq) and surface wind speed (|V|). Compared to fluxes estimated from |V| and Δq measured at tropical moorings and the Coupled Ocean Atmosphere Response Experiment 3.0 (COARE3.0) algorithm, tropical latent heat fluxes in the National Center for Atmospheric Research CEMS2 and Department of Energy E3SMv1 models are significantly overestimated at |V| and Δq extrema. Madden–Julian oscillation (MJO) sensitivity to surface flux algorithm is tested with offline and inline flux corrections. The offline correction adjusts model output fluxes toward mooring-estimated fluxes; the inline correction replaces the original bulk flux algorithm with the COARE3.0 algorithm in atmosphere-only simulations of each model. Both corrections indicate reduced latent heat flux feedback to intraseasonal precipitation, in better agreement with observations, suggesting that model-simulated fluxes are overly supportive for maintaining MJO convection.

54 ENVIRONMENTAL SCIENCES↗

Rarefied solids

One important limit to creating low density materials is the objects' own weight. As a solid or colloidal matrix becomes more rarefied, gravity acts destructively to compress its suporting skeleton. We describe experimental results and propose a model which matches the low gravity behavior of rarefied or fractal solids. On parabolic airplane flights, we sought to demonstrate a key component of producing higher surface area fractals. Flight paths were selected to give a range of gravity levels: 0.01 g/g(sub 0) (low), 0.16 g(sub 0) (Lunar), 0.33 g/g(sub 0) (Martian), 1 g/g(sub 0) (Earth) and 1.8 g/g(sub 0) (high) (where g(sub 0) = 980 cm/sq s). Results using the model material of hydrophobic silica indicated that stable agglomeration of such tenuous objects can increase markedly in reduced gravity. Optical characterization revealed that fractal dimension changed directly with varying gravity. As measured by fractal dimension, effective surface area and roughness increased by 40% in low gravity. This finding supports the conclusion that relieving internal weight stresses on delicate aggregates can enhance their overall size (by two orders of magnitude) and internal surface area. We conclude that gravitational restructuring limits the overall size and void content of low-density solids. These sparse colloidal regimes may present new and technologically attractive physics, ranging from improved insulators, liquid-like tension in a 'solid' matrix, and characteristically low conductivities for sound and (8 to 14 micrometers wavelength) infrared radiation.

Noever, D. A.↗

Surface Charge of the Calcite (104) Terrace Measured by Rb + Adsorption in Aqueous Solutions Using Resonant Anomalous X-ray Reflectivity

Adsorption of Rb+ on the (104) plane of single crystal calcite was investigated to estimate the charge of the ionic crystal calcite – water interface. The adsorbed Rb+ coverage was quantified as a function of Rb concentration (1 – 100 mM) in calcite-saturated solutions at pH 8.3 by using in-situ resonant anomalous X-ray reflectivity in transmission cell geometry. The Rb+ coverages for all solution conditions were small with the maximum ion coverage (Γmax) of 0.12(4) Rb+/nm2 estimated by the best-fit Langmuir isotherm model. This result provides an estimate of the upper limit to the effective surface charge density of about –0.02 C/m2 considering that any Rb+ adsorption to the terrace plane is likely induced by electrostatic attraction. This charge density is significantly lower (by a factor of ≥10) than those estimated from macroscopic measurements, implying that any excess charge likely originates from surface defects.

adsorption↗

Effects of crystallite size on the structure and magnetism of ferrihydrite

The structure and magnetic properties of nano-sized (1.6 to 4.4 nm) ferrihydrite samples are systematically investigated through a combination of X-ray diffraction (XRD), X-ray pair distribution function (PDF), X-ray absorption spectroscopy (XAS) and magnetic analyses. The XRD, PDF and Fe K-edge XAS data of the ferrihydrite samples are all fitted well with the Michel ferrihydrite model, indicating similar local-, medium- and long-range ordered structures. PDF and XAS fitting results indicate that, with increasing crystallite size, the average coordination numbers of Fe–Fe and the unit cell parameter c increase, while Fe2 and Fe3 vacancies and the unit cell parameter a decrease. Mössbauer results indicate that the surface layer is relatively disordered, which might have been caused by the random distribution of Fe vacancies. These results support Hiemstra's surface-depletion model in terms of the location of disorder and the variations of Fe2 and Fe3 occupancies with size. Magnetic data indicate that the ferrihydrite samples show antiferromagnetism superimposed with a ferromagnetic-like moment at lower temperatures (100 K and 10 K), but ferrihydrite is paramagnetic at room temperature. In addition, both the magnetization and coercivity decrease with increasing ferrihydrite crystallite size due to strong surface effects in fine-grained ferrihydrites. Smaller ferrihydrite samples show less magnetic hyperfine splitting and a lower unblocking temperature (T B ) than larger samples. The dependence of magnetic properties on grain size for nano-sized ferrihydrite provides a practical way to determine the crystallite size of ferrihydrite quantitatively in natural environments or artificial systems.

36 MATERIALS SCIENCE↗

Loop and void damage during heavy ion irradiation on nanocrystalline and coarse grained tungsten: Microstructure, effect of dpa rate, temperature, and grain size

Displacement damage, through heavy ion irradiation was studied on two tungsten grades (coarse grained tungsten (CGW) and nanocrystalline and ultrafine grained tungsten (NCW)) using different displacement per atom rates and different irradiation temperatures (RT and 1050 K). Percentage of <111> and <100> type loops at the irradiation conditions was determined. Irradiation damage in the microstructure was quantified using average loop areas and densities (method A) and loop areal fraction in the grain matrices under 2-beam diffraction conditions (method B). Average values of <111> and <100> loops were calculated from method A. Loop coalescence was shown to occur for CGW at 0.25 dpa. Using both methods of quantifying microstructural damage, no effect of dpa rate was observed and damage in CGW was shown to be the same at RT and 1050 K. Swelling from voids observed at 1050 K was quantified. The loop damage in NCW was compared to CGW at the same diffraction and imaging conditions. NCW was shown to possess enhanced irradiation resistance at RT regarding loop damage and higher swelling resistance at 1050 K compared to CGW. For irradiation at 1050 K, the NCW was shown to have a similar defect densities to the CGW which is attributed to higher surface effects in the CGW, vacancy loop growth to voids and a better sink efficiency in the CGW deduced from the vacancy distribution profiles from Kinetic Monte Carlo simulations. Loop density and swelling was shown to have similar values in grains sizes that range from 80-600 nm. No loop or void denuded zones occurred at any of the irradiation conditions. This work has a collection of experiments and conclusions that are of vital importance to materials and nuclear communities.

36 MATERIALS SCIENCE↗

Continuum kinetic and multi-fluid simulations of classical sheaths

The kinetic study of plasma sheaths is critical, among other things, to understand the deposition of heat on walls, the effect of sputtering, and contamination of the plasma with detrimental impurities. The plasma sheath also provides a boundary condition and can often have a significant global impact on the bulk plasma. In this paper, kinetic studies of classical sheaths are performed with the continuum kinetic code, Gkeyll, which directly solves the Vlasov-Maxwell equations. The code uses a novel version of the finite-element discontinuous Galerkin scheme that conserves energy in the continuous-time limit. The fields are computed using Maxwell equations. Ionization and scattering collisions are included; however, surface effects are neglected. The aim of this work is to introduce the continuum kinetic method and compare its results with those obtained from an already established finite-volume multi-fluid model also implemented in Gkeyll. Novel boundary conditions on the fluids allow the sheath to form without specifying wall fluxes, so the fluids and fields adjust self-consistently at the wall. Our work demonstrates that the kinetic and fluid results are in agreement for the momentum flux, showing that in certain regimes, a multifluid model can be a useful approximation for simulating the plasma boundary. There are differences in the electrostatic potential between the fluid and kinetic results. Further, the direct solutions of the distribution function presented here highlight the non-Maxwellian distribution of electrons in the sheath, emphasizing the need for a kinetic model. The densities, velocities, and the potential show a good agreement between the kinetic and fluid results. But, kinetic physics is highlighted through higher moments such as parallel and perpendicular temperatures which provide significant differences from the fluid results in which the temperature is assumed to be isotropic. Besides decompression cooling, the heat flux is shown to play a role in the temperature differences that are observed, especially inside the collisionless sheath. Published by AIP Publishing.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Thermomechanical peridynamic analysis with irregular non-uniform domain discretization [Thermomechanical peridynamic analysis with non-uniform domain discretization]

Non-uniform discretization of the solution domain in models based on peridynamic theory can improve computational efficiency by allowing for local refinement where needed for accuracy, and helps remove the effect of mesh bias in the simulations. However, the use of non-uniform discretization and a variable horizon requires consideration of possible unbalanced interactions between two material points, adjustment of peridynamic material parameters, and arbitrary shapes of interaction domains. This study presents a modification to the original peridynamic theory in which the strain energy associated with an interaction between two material points is split according to the volumetric ratio arising from the presence of non-uniform discretization and a variable horizon. It also removes the requirement for correction of peridynamic material parameters due to surface effects. Furthermore, the accuracy of this approach is verified against benchmark solutions, and its applicability to engineering problems is demonstrated by considering thermally induced cracking in a nuclear fuel pellet.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Exploratory investigation of the effect of porous surfaces on hypersonic turbulent boundary layers

Four different test surfaces were studied to determine the effect of porous walls on the characteristics of a hypersonic turbulent flat-plate boundary layer. The investigation was an attempt to decrease the surface shear of the boundary layer by transmitting fluctuating pressure energy through the wall and absorbing it in a cavity beneath the wall. Pitot surveys were made at two locations, schlieren photographs of the boundary layer were taken, and hot-wire measurements in the flow above the boundary layer were made to determine whether the surfaces affected the turbulent boundary layer. Neither an increase nor a decrease in surface shear or boundary-layer growth was detected. Tabulations of the pitot data are included.

Watson, R. D.↗

Dielectric properties of crystalline organic molecular films in the limit of zero overlap

We present the calculation of the static dielectric susceptibility tensor and dipole field sums in thin molecular films in the well-defined limit of zero intermolecular overlap. Microelectrostatic and charge redistribution approaches are applied to study the evolution of dielectric properties from one to a few molecular layers in films of different conjugated molecules with organic electronics applications. Because of the conditional convergence of dipolar interactions, dipole fields depend on the shape of the sample and different values are found in the middle layer of a thick film and in the bulk. The shape dependence is eliminated when depolarization is taken into account, and the dielectric tensor of molecular films converges to the bulk limit within a few molecular layers. We quantify the magnitude of surface effects and interpret general trends among different systems in terms of molecular properties, such as shape, polarizability anisotropy, and supramolecular organization. A connection between atomistic models for molecular dielectrics and simpler theories for polarizable atomic lattices is also provided.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Effect of Gamma Radiation Exposure on Active Silicon Photonic Device Performance Metrics

In this study, we test Si vertical junction disk modulators and waveguide-integrated Ge PIN photodiodes to see how the key performance metrics are affected by 60Co gamma radiation (total ionizing dose), a common proxy for simulating a mix of high energy ion particle flux. It is found that reverse bias dark current increases significantly for both devices after 1 Mrad(Si) exposure. Whereas the bandwidth of the Si disk modulator decreases by 6.5 % after 1 Mrad(Si) dose, the bandwidth of the Ge PIN photodiode appears to be unaffected. The increased sensitivity of the Si disk modulator bandwidth to gamma radiation is hypothesized to be caused by a decrease in the carrier concentration of the junction with a resulting increase in p-n junction RC time constant. The Ge PIN photodiode is relatively insensitive to the surface effects because the absorption happens away from the SiO2-Ge interface and the gamma radiation has a minimal effect on carrier mobility.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Revealing the Transient Formation Dynamics and Optoelectronic Properties of 2D Ruddlesden–Popper Phases on 3D Perovskites

Using in situ photoluminescence measurements during the spin-coating and annealing steps, this study probes the formation of 2D layers on 3D triple cation perovskite films comparing phenylethylammonium and 2-thiophenemethylammonium iodide bulky cations. This study elucidates the formation mechanisms of the surface layers for both cases and reveals two regimes during 2D layer formation: a kinetic-driven and a thermodynamic-driven process. These driving forces result in different compositions of the 2D/3D interface for each treatment, namely, different ratios of pure 2D (n = 1) and quasi-2D (n > 1) structures. Further, this study shows that a higher ratio of quasi-2D phases is more beneficial for device performance, as pure-2D layers may hamper current extraction. Due to a more evenly distributed formation energy profile among 2D and quasi-2D phases, highly concentrated 2-thiophenemethylammonium iodide appears to be more suited for effective surface passivation than its phenylethylammonium analog.

36 MATERIALS SCIENCE↗

Concept of Lattice Mismatch and Emergence of Surface States in Two-dimensional Hybrid Perovskite Quantum Wells

We present that surface states are ubiquitous to semiconductors and significantly impact the physical properties and, consequently, the performance of optoelectronic devices. Moreover, surface effects are strongly amplified in lower dimensional systems such as quantum wells and nanostructures. Layered halide perovskites (LHPs) are two-dimensional solution-processed natural quantum wells where optoelectronic properties can be tuned by varying the perovskite layer thickness n, i.e., the number of octahedra spanning the layer. They are efficient semiconductors with technologically relevant stability. Here, a generic elastic model and electronic structure modeling are applied to LHPs heterostructures with various layer thickness. We show that the relaxation of the interface strain is triggered by perovskite layers above a critical thickness. This leads to the release of the mechanical energy arising from the lattice mismatch, which nucleates the surface reorganization and may potentially induce the formation of previously observed lower energy edge states. Finally, these states, which are absent in three-dimensional perovskites are anticipated to play a crucial role in the design of LHPs for optoelectronic systems.

36 MATERIALS SCIENCE↗

Unraveling the Formation Mechanism of a Hybrid Zr-Based Chemical Conversion Coating with Organic and Copper Compounds for Corrosion Inhibition

Environmental-friendly chromate-free, zirconium (Zr)-based conversion coating is a promising green technology for corrosion protection. Additives in the surface treatment provides critical functionalities and performance improvements; however, mechanistic understanding as of how the additives influence the coatings remains unclear. In this study, a new organic-inorganic hybrid Zrbased conversion coating which combines copper (Cu) compounds and polyamidoamine (PAMAM), taking advantages of a complementary nature of organic and inorganic additives. Here, a multimodal approach combining electron and X-ray characterization is applied to study the interaction of Cu 2+ and PAMAM and the resulting impacts on the coating formation. Adding PAMAM changed the surface morphology, thickness, distribution of Cu in the cluster and void formation of the coatings. High PAMAM (100-200 pm) leads to little conversion coating formation, and low PAMAM (0-25 ppm) shows voids formation under the coatings. Moreover, PAMAM incorporates in the coating in a form of PAMAM-Cu complex with a higher concentration towards the surface, provides an organic layer at the surface of the coating. X-ray absorption near-edge structure (XANES) spectroscopy shows a difference between the conventional and hybrid coating treatments in an alkaline solution to simulate the E-coat process, suggesting the contribution of PAMAM in the enhanced chemical stability in an alkaline environment. Therefore, an intermediate range of addition of PAMAM (50 ppm) is optimal to 1) avoid excessive voids formation, 2) promote some Cu cluster formation and thus enhancing the Zr-based coating formation and 3) incorporate organic components into the coating to improve the adhesion of the subsequent coatings. Overall, this work furthers our knowledge on the formation mechanism of an effective and environmentally friendly hybrid conversion coating for corrosion inhibition, demonstrating a critical processing-structureproperty relationship. This study will benefit future development of green and effective surface treatment technology.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Tuning the electronic properties at the surface of BaBiO{sub 3} thin films

The presence of 2D electron gases at surfaces or interfaces in oxide thin films remains a hot topic in condensed matter physics. In particular, BaBiO{sub 3} appears as a very interesting system as it was theoretically proposed that its (001) surface should become metallic if a Bi-termination is achieved (Vildosola et al., PRL 110, 206805 (2013)). Here we report on the preparation by pulsed laser deposition and characterization of BaBiO{sub 3} thin films on silicon. We show that the texture of the films can be tuned by controlling the growth conditions, being possible to stabilize strongly (100)-textured films. We find significant differences on the spectroscopic and transport properties between (100)-textured and non-textured films. We rationalize these experimental results by performing first principles calculations, which indicate the existence of electron doping at the (100) surface. This stabilizes Bi ions in a 3+ state, shortens Bi-O bonds and reduces the electronic band gap, increasing the surface conductivity. Our results emphasize the importance of surface effects on the electronic properties of perovskites, and provide strategies to design novel oxide heterostructures with potential interface-related 2D electron gases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Causes of and Solutions to Wind Speed Bias in NREL's 2020 Offshore Wind Resource Assessment for the California Pacific Outer Continental Shelf

This report provides the results of a detailed analysis into the causes of high wind speed bias in the 20-year wind resource data set for offshore California the National Renewable Energy Laboratory (NREL) released in 2020, herein called CA20. The data set was developed using the state-of-the-art Weather Research and Forecasting (WRF) model. Notably, no floating lidars were available at the time in offshore California to validate offshore hub-height wind speeds. In late 2020, the Pacific Northwest National Laboratory (PNNL) deployed two floating lidars in the California outer continental shelf (OCS), near the Bureau of Ocean Energy Management (BOEM) call areas of Humboldt and Morro Bay. Using these observations through 2021, NREL found considerable bias in modeled hub-height winds at both locations: up to +2 m/s at Humboldt over a 6-month period, and up to +1 m/s at Morro Bay over a one-year period. Upon the discovery of this bias, the Department of Energy (DOE) and BOEM funded NREL and PNNL to investigate the causes of, impacts of, and solutions to the bias in the CA20 data set. This report summarizes the findings of this research. We first investigated whether different WRF model setups could lead to reduced bias. We found that the choice of planetary boundary layer (PBL) scheme - which controls the vertical turbulent mixing of momentum, heat, and moisture in the lowermost part of the atmosphere - greatly affected hub-height wind speeds in the region. Specifically, switching from the Mellor-Yamada-Nakanishi-Niino (MYNN) scheme used in CA20 (and widely used across a range of operational and research weather models) to the less common Yonsei University (YSU) scheme nearly eliminated the bias at both the Humboldt and Morro Bay lidar locations. The large discrepancy between the MYNN- and YSU-modeled hub-height winds pointed towards the role of atmospheric stability. In general, PBL schemes agree well in conditions of high turbulence and mixing, normally referred to as "unstable" conditions. By contrast, PBL schemes start to diverge in "stable" conditions, where turbulence is low and thermal stratification (i.e., higher temperature air sitting on top of colder air) greatly suppresses vertical mixing. Under such conditions, winds aloft can decouple from surface effects and greatly accelerate, causing high wind speeds at hub-height and frequent low-level jets (LLJs). We determined that these stable conditions are in fact dominant in offshore California. The region is characterized by moderate-to-extreme stable stratification with a LLJ on average around 200 meters above sea-level. To our knowledge, no wind energy area globally has as strongly stable stratification as offshore California. Under these extreme conditions, we determined that the MYNN scheme models higher stability than YSU, resulting in less vertical turbulent mixing than YSU, allowing for the acceleration of hub-height winds, more intense LLJs, and higher-amplitude inertial oscillations. Using surface observations, we found that MYNN overestimates near-surface stability, whereas YSU tends to model stability better. We then considered several short-term case studies to assess additional meteorological drivers of the bias at Humboldt. We found that during synoptic scale northerly flows driven by the North Pacific High and inland thermal low, a coastal warm bias in the MYNN case studies contributes to the modeled wind speed bias by altering the boundary layer thermodynamics via a thermal wind mechanism. Given the strong performance of the YSU-based runs in offshore California, NREL has produced and published an updated version of the CA20 data set with YSU as the PBL scheme. This updated data set is now part of NREL's 2023 National Offshore Wind (NOW-23) data set, which covers all the U.S. offshore waters. The development and final validation of the NOW-23 data set in offshore California is documented in this report.

17 WIND ENERGY↗