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At least 541 records · Page 30

Plasma kinetic effects on interfacial mix and burn rates in multispatial dimensions

The physics of mixing in plasmas is of great significance to inertial confinement fusion and high energy density laboratory experiments. Two- and three-dimensional (2D and 3D) particle-in-cell simulations with a binary collision model are used to explore kinetic effects arising during the mixing of plasma media. The applicability of the one-dimensional (1D) ambipolarity condition is evaluated in 2D and 3D simulations of a plasma interface with a sinusoidal perturbation. The 1D ambipolarity condition is found to remain valid in 2D and 3D, as electrons and ions flow together required for $J$ = 0. Simulations of perturbed interfaces show that diffusion-induced total pressure imbalance and hydroflows flatten fine interface structures and drive rapid atomic mix. The atomic mix rate from a structured interface is faster than the ~$\sqrt{\bar{t}}$ scaling obtained from 1D theory in the small-Knudsen-number limit. Plasma kinetic effects inhibit the growth of the Rayleigh-Taylor instability at small wavelengths and result in a nonmonotonic growth rate scaling with wavenumber k with a maximum at a low k value, much different from $\sqrt{Agk}$ (where A is the Atwood number and g is the gravitational constant) as expected in the absence of plasma kinetic effects. Simulations under plasma conditions relevant to MARBLE separated-reactant experiments on Omega and the NIF show kinetic modification of DT fusion reaction rates. With non-Maxwellian distributions and relative drifts between D and T ions, DT reactivity is higher than that inferred from rates using stationary Maxwellian distributions. Reactivity is additionally revealed to be reduced in the presence of finite-Knudsen-layer losses.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Chemical transformations and transport phenomena at interfaces

Abstract Interfaces, the boundary that separates two or more chemical compositions and/or phases of matter, alters basic chemical and physical properties including the thermodynamics of selectivity, transition states, and pathways of chemical reactions, nucleation events and phase growth, and kinetic barriers and mechanisms for mass transport and heat transport. While progress has been made in advancing more interface‐sensitive experimental approaches, their interpretation requires new theoretical methods and models that in turn can further elaborate on the microscopic physics that make interfacial chemistry so unique compared to the bulk phase. In this review, we describe some of the most recent theoretical efforts in modeling interfaces, and what has been learned about the transport and chemical transformations that occur at the air–liquid and solid–liquid interfaces. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Structure and Mechanism > Computational Materials Science Software > Quantum Chemistry Software > Simulation Methods

Hao, Hongxia↗

Roadmap on advanced and / real-time characterisation of solid state materials and devices for energy applications

A strong societal and political drive is motivating the development and optimization of novel energy conversion and storage systems for decarbonization. The successful implementation of solid state devices such as fuel cells and secondary batteries depends, however, on achieving ambitious targets in terms of performance, reliability and cost competitiveness. Research and technology are addressing these needs through a holistic approach including exploration of new materials and nanoarchitectures, as well as system engineering. These significant efforts require the support of appropriate characterization tools capable of assessing nanometer-scale phenomena such as concentration profiles of ionic and electronic charges, local chemical compositions and their evolution over time across interfaces. This roadmap provides an overview of selected advanced characterization techniques for energy materials and devices. Specific focus is put on in situ/operando methods for probing electrochemical phenomena in real-time under realistic working conditions. Experts in the field provide an extensive review of the current state of the art in 2025 and the current and future challenges for the characterization of local chemistry and kinetics in the bulk of the material, in nanoarchitectures (e.g. thin films) and at the interfaces (e.g. grain boundaries, phase contacts, solid/liquid and solid/gas interfaces) . The aim is to provide a detailed guide to the techniques, describing opportunities and bottlenecks for their practical deployment and examples of successful applications.

25 ENERGY STORAGE↗

Modeling investigation of the stability and irradiation-induced evolution of nanoscale precipitates in advanced structural materials

Materials used in extremely hostile environment such as nuclear reactors are subject to a high flux of neutron irradiation, and thus vast concentrations of vacancy and interstitial point defects are produced because of collisions of energetic neutrons with host lattice atoms. The fate of these defects depends on various reaction mechanisms which occur immediately following the displacement cascade evolution and during the longer-time kinetically dominated evolution such as annihilation, recombination, clustering or trapping at sinks of vacancies, interstitials and their clusters. The long-range diffusional transport and evolution of point defects and self-defect clusters drive a microstructural and microchemical evolution that are known to produce degradation of mechanical properties including the creep rate, yield strength, ductility, or fracture toughness, and correspondingly affect material serviceability and lifetimes in nuclear applications. Therefore, a detailed understanding of microstructural evolution in materials at different time and length scales is of significant importance. The primary objective of this work is to utilize a hierarchical computational modeling approach i) to evaluate the potential for nanoscale precipitates to enhance point defect recombination rates and thereby the self-healing ability of advanced structural materials, and ii) to evaluate the stability and irradiation-induced evolution of such nanoscale precipitates resulting from enhanced point defect transport to and annihilation at precipitate interfaces. This project will utilize, and as necessary develop, computational materials modeling techniques within a hierarchical computational modeling approach, principally including molecular dynamics, kinetic Monte Carlo and spatially-dependent cluster dynamics modeling, to identify and understand the most important physical processes relevant to promoting the “selfhealing” or radiation resistance in advanced materials containing nanoscale precipitates. In particular, the interfacial structure of embedded nanoscale precipitates will be evaluated by electronic- and atomic-scale modeling methods, and the efficiency of the validated interfaces for trapping point defects will next be evaluated by atomic-scale modeling (e.g., determining the sink strength of the precipitates), addressing key questions related to the optimal interface characteristics to attract point defects and enhance their recombination. Kinetic models will also be developed to simulate microstructural evolution of the nanoscale features and irradiation produced defect clusters, and compared with observed microstructural changes.

36 MATERIALS SCIENCE↗

Interfaces between hexagonal and cubic oxides and their structure alternatives

Multi-layer structure of functional materials often involves the integration of different crystalline phases. The film growth orientation thus frequently exhibits a transformation, owing to multiple possibilities caused by incompatible in-plane structural symmetry. Nevertheless, the detailed mechanism of the transformation has not yet been fully explored. Here we thoroughly probe the heteroepitaxially grown hexagonal zinc oxide (ZnO) films on cubic (001)-magnesium oxide (MgO) substrates using advanced scanning transition electron microscopy, X-ray diffraction and first principles calculations, revealing two distinct interface models of (001) ZnO/(001) MgO and (100) ZnO/(001) MgO. Here we have found that the structure alternatives are controlled thermodynamically by the nucleation, while kinetically by the enhanced Zn adsorption and O diffusion upon the phase transformation. Finally, this work not only provides a guideline for the interface fabrication with distinct crystalline phases but also shows how polar and non-polar hexagonal ZnO films might be manipulated on the same cubic substrate.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Precipitate growth kinetics under inhomogeneous concentration fields using a phase-field model

We investigate precipitation dynamics in the presence of a local solute gradient using phase-field simulations. During the homogenization heat treatment of the solidified Inconel 718 alloy, high Nb concentration within the Laves phases or at the core of the secondary arms results in Nb diffusion into the γ matrix. The volume fraction and spatial distribution of precipitation during subsequent annealing can be controlled by tailoring the Nb concentration gradient in the matrix during homogenization. We use a surrogate Ni-Fe-Nb alloy for Inconel 718 to explore the growth dynamics of δ precipitates related to the local Nb concentration levels. The simulations indicate that in the presence of a Nb concentration gradient the growth rate of δ precipitates is higher than in a matrix of uniform average Nb concentration. The higher growth rate is a result of the higher local thermodynamic driving force at the interface between the solute-rich matrix and the δ interface. Here, we propose a phenomenological model to describe the diffusion-controlled growth kinetics of the δ phase under a solute concentration gradient.

36 MATERIALS SCIENCE↗

Thin Interface Asymptotics for an Energy/Entropy Approach to Phase-Field Models with Unequal Conductivities

Karma and Rapped recently developed a new sharp interface asymptotic analysis of the phase-field equations that is especially appropriate for modeling dendritic growth at low undercoolings. Their approach relieves a stringent restriction on the interface thickness that applies in the conventional asymptotic analysis, and has the added advantage that interfacial kinetic effects can also be eliminated. However, their analysis focussed on the case of equal thermal conductivities in the solid and liquid phases; when applied to a standard phase-field model with unequal conductivities, anomalous terms arise in the limiting forms of the boundary conditions for the interfacial temperature that are not present in conventional sharp-interface solidification models, as discussed further by Almgren. In this paper we apply their asymptotic methodology to a generalized phase-field model which is derived using a thermodynamically consistent approach that is based on independent entropy and internal energy gradient functionals that include double wells in both the entropy and internal energy densities. The additional degrees of freedom associated with the generalized phased-field equations can be chosen to eliminate the anomalous terms that arise for unequal conductivities.

McFadden, G. B.↗

Interstellar hydrogen fluxes measured by IBEX-LO in 2009: Numerical modeling and comparison with the data

In this paper, we perform numerical modeling of the interstellar hydrogen fluxes measured by IBEX-Lo during orbit 23 (spring 2009) using a state-of-the-art kinetic model of the interstellar neutral hydrogen distribution in the heliosphere. This model takes into account the temporal and heliolatitudinal variations of the solar parameters as well as the non-Maxwellian kinetic properties of the hydrogen distribution due to charge exchange in the heliospheric interface. We found that there is a qualitative difference between the IBEX-Lo data and the modeling results obtained with the three-dimensional, time-dependent model. Namely, the model predicts a larger count rate in energy bin 2 (20–41 eV) than in energy bin 1 (11–21 eV), while the data shows the opposite case. We perform study of the model parameter effects on the IBEX-Lo fluxes and the ratio of fluxes in two energy channels. We show that the most important parameter, which has a major influence on the ratio of the fluxes in the two energy bins, is the solar radiation pressure. The parameter fitting procedure shows that the best agreement between the model result and the data occurs when the ratio of the solar radiation pressure to the solar gravitation, μ{sub 0}, is 1.26{sub −0.076}{sup +0.06}, and the total ionization rate of hydrogen at 1 AU is β{sub E,0}=3.7{sub −0.35}{sup +0.39}×10{sup −7} s{sup −1}. We have found that the value of μ{sub 0} is much larger than μ{sub 0} = 0.89, which is the value derived from the integrated solar Lyα flux data for the period of time studied. We discuss possible reasons for the differences.

79 ASTRONOMY AND ASTROPHYSICS↗

Temperature effects on the atomic structure and kinetics in single crystal electrochemistry

The influence of temperature on the atomic structure at the electrochemical interface has been studied using in-situ surface x-ray scattering (SXS) during the formation of metal monolayers on a Au(111) electrode. For the surface reconstruction of Au(111), higher temperatures increase the mobility of surface atoms in the unreconstructed phase which then determines the surface ordering during the formation of the reconstruction. For the underpotential deposition (UPD) systems, the surface diffusion of the depositing metal adatoms is significantly reduced at low temperatures which results in the frustration of ordered structures in the case of Cu UPD, occurring on a Br-modified surface, and in the formation of a disordered Ag monolayer during Ag UPD. The results indicate that temperature changes affect the mass transport and diffusion of metal adatoms on the electrode surface. This demonstrates the importance of including temperature as a variable in studying surface structure and reactions at the electrochemical interface.

Gründer, Yvonne↗

On the Importance of the Associative Carboxyl Mechanism for the Water-Gas Shift Reaction at Pt/CeO 2 Interface Sites

Periodic density functional theory calculations and microkinetic modeling are used to investigate the associative carboxyl pathways of the water-gas shift (WGS) reaction at the Pt/CeO 2 (111) interface. Analysis of a microkinetic model based on parameters obtained from first principles suggests that the turnover frequencies for the CO-assisted associative carboxyl mechanism are comparable to experimental results. However, this microkinetic model containing various associative carboxyl pathways at interface sites cannot explain the experimentally observed activation barriers and reaction orders of Pt/CeO 2 catalysts. Considering furthermore that a model of an associative carboxyl mechanism with redox regeneration, also derived from first principles and recently published by us, accurately predicts all kinetic parameters while displaying a 2 orders of magnitude higher turnover frequency, we conclude that at Pt/CeO 2 interface sites, the WGS reaction follows a bifunctional Mars-van Krevelen mechanism in which support oxygen vacancies facilitate water dissociation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding palladium–tellurium cluster formation on WTe2: From a kinetically hindered distribution to thermodynamically controlled monodispersity

Abstract A fundamental understanding of the transition metal dichalcogenide (TMDC)–metal interface is critical for their utilization in a broad range of applications. We investigate how the deposition of palladium (Pd), as a model metal, on WTe2(001), leads to the assembly of Pd into clusters and nanoparticles. Using X-ray photoemission spectroscopy, scanning tunneling microscopy imaging, and ab initio simulations, we find that Pd nucleation is driven by the interaction with and the availability of mobile excess tellurium (Te) leading to the formation of Pd-Te clusters at room temperature. Surprisingly, the nucleation of Pd-Te clusters is not affected by intrinsic surface defects, even at elevated temperatures. Upon annealing, the Pd-Te nanoclusters adopt an identical nanostructure and are stable up to ∼523 K. Density functional theory calculations provide a foundation for our understanding of the mobility of Pd and Te atoms, preferential nucleation of Pd-Te clusters, and the origin of their annealing-induced monodispersity. These results highlight the role the excess chalcogenide atoms may play in the metal deposition process. More broadly, the discoveries of synthetic pathways yielding thermally robust monodispersed nanostructures on TMDCs are critical to the manufacturing of novel quantum and microelectronics devices and catalytically active nano-alloy centers.

36 MATERIALS SCIENCE↗

Geochemical rate processes at mineral-water interfaces: Linking molecular-scale surface properties to macroscopic observables

The project emphasis at WSU is on the understanding of the principal influences on surface chemistry, morphology, and kinetics of reactions of minerals in aqueous solutions. This emphasis, in the last project period has guided our efforts to the study of morphological relaxation in response to solution perturbations as well as to develop a methodology for creating on-demand etch pits for the purposes of generating specific step orientations on calcite surfaces. In the response of any mineral-water interface to changes in environmental conditions, dissolution and mineralization rates undergo rapid changes because the reaction rates at step edges are governed directly by these conditions. Our previous investigations of mineral dissolution have revealed that the topographic relaxation time under near equilibrium conditions can be much longer than the characteristic times of experimental investigations. The investigations described below are directed towards evaluating the effects of sample history, miscut and pretreatment on the observed dissolution behavior of our target mineral-water interface systems. In addition, we have developed a simple method for generating on-demand etch pits for the purposes of studying kinetically unstable step orientations.

Higgins, Steven R.↗

Oxidation behaviour of ferritic stainless steel grade Crofer 22 APU at 700 °C in flowing Ar−75%CO{sub 2}−12%H{sub 2}O

The oxidation of Ferritic Stainless Steel (FSS) grade Crofer 22 APU has been investigated. FSS alloys were exposed to isothermal conditions in a horizontal tube furnace at a 700 °C in flowing Ar−75%CO{sub 2}−12%H{sub 2}O at a pressure of approximately 1 atm. The results showed that the growth of non protective Fe{sub 2}O{sub 3} and spinel was observed after 50 h exposure in the presence of 12% H{sub 2}O. The weight was increased significantly with time of exposure. The formation of different oxides is presented on the interface of the specimen such as MnCr{sub 2}O{sub 4}, Fe{sub 3}O{sub 4} and Fe{sub 2}O{sub 3} were revealed by X-ray diffraction and supported by EDAX analysis. FSS did not form a protective Cr{sub 2}O{sub 3} layer due to water vapour accelerates the kinetics oxidation. Data of microstructure observation is presented and discussed in this paper in term of water vapour effects.

36 MATERIALS SCIENCE↗

A Level Set Evaporation Model for Heterogeneous Atom Probe Tip

With the development of local electrode atom probe tomography (LEAP), the materials systems feasible for atomic structure determination has expanded from predominantly metals to include heterogeneous materials with complex structure and compositions. This makes the 3D atomic structure determination possible for most energy materials in battery, fuel cell, semiconductor, and nuclear applications. Atom probe tomography (APT) has been utilized to study multiphase materials with segregation and interface problems. The unique and quantitative information retrieved from APT can provide a foundation for the study of kinetic pathways, nanoscale composition mapping, multilayer interfacial segregation, dislocations and grain boundaries. However, a new challenge surfaces when the materials systems expand into heterogeneous materials: the traditional structure reconstruction introduces false magnification and large artifacts due to the underlying assumption of uniform and isotropic evaporation.

Atom probe, heterogeneous structure, evporation mo↗

High performance La 2 NiO 4+δ -infiltrated (La 0.6 Sr 0.4 ) 0.995 Co 0.2 Fe 0.8 O 3–δ cathode for solid oxide fuel cells

In this paper, we reported our effort on improving electrochemical performance of (La 0.6 Sr 0.4 ) 0.995 Co 0.2 Fe 0.8 O 3–δ (LSCF) cathode in solid oxide fuel cell (SOFC) by infiltration of La 2 NiO 4+δ (LNO). It is found that a porous LSCF backbone coated with LNO nanoparticles is an attractive way to acquire a noticeable decrease in the polarization resistance and activation energy of LSCF cathode, thereby showing high surface activity and enhanced oxygen transport capability. The key contributions of the LNO nanoparticles also lead to a 67% increase in peak power density and operation stability at a constant current density of 250 mA cm –2 with a low degradation rate of 0.39% for about 500 h at 750 °C. Although extended durability of LNO-infiltrated LSCF might be concerned, based on coarsening of the LNO nanoparticles, a greatly increased power density and voltage output after a cell operation of 500 h engenders substantial confidence in the beneficial effect of LNO-infiltrated LSCF materials on cell properties. In conclusion, the enhancement of ORR kinetics could be ascribed to the increase of active surface area and active reaction regions from the heterostructured LSCF/LNO interface architecture, and/or favorable cation diffusion from LSCF to LNO.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Kinetic Alfven waves as a source of plasma transport at the dayside magnetopause

As the shocked solar wind with variable plasma density and magnetic field impinges on the dayside magnetopause, it is likely to generate large-scale Alfven waves at the solar wind magnetosphere interface. However, large gradients in the density and magnetic field at the magnetopause boundary effectively couple large-scale Alfven waves with kinetic Alfven waves may play an important role in plasma transport at the dayside magnetopause and in electron acceleration along field lines. The transport can occur because, unlike the magnetohydrodynamic (MHD) shear Alfven wave, the kinetic Alfven wave has an associated parallel electric field which breaks down the 'frozen-in' condition and decouples the plasma from field lines. We calculate the average deviation of the plasma from the field line from which we estimate the diffusion coefficient associated with these 'bundles' of lead to acceleration of electrons along field lines in the magnetopause boundary and may possibly provide an explanation for observed counterstreaming electron beams characterized by energies of 50-200 eV.

Lee, L. C.↗

Polymorphs of the n–Type Polymer P(NDI2OD–T2): A Comprehensive Description of the Impact of Processing on Crystalline Morphology and Charge Transport

A systematic study of the polymorphs emerging in P(NDI2OD-T2) (also commercially known as N2200), a prototypical organic semiconducting n-type polymer, is presented. Using a tightly integrated experimental and computational approach, detailed atomistic-level descriptions are provided investigating the three known P(NDI2OD-T2) polymorphs observed at room temperature as a function of thin-film processing. Importantly, over the course of the work, a missing link is uncovered, a fourth polymorph referred to here as Form I-β; this new form is a morphological intermediary observed upon thermal annealing, which evolves from Form I but tends to disappear upon full polymer chain melting. The computationally derived polymorph structures show excellent agreement with experimental X-ray scattering characterization. The relative stabilities of each polymorph are calculated in terms of both the bulk material and the polymorph-air interface. An energy landscape is then constructed to qualitatively compare the thermodynamic versus kinetic origins of each polymorph, and the factors driving (supra)assembly and associated transformations among polymorphs using an approach generalizable to other organic semiconducting polymers. Lastly, the relationships among preferential polymorphic crystallinity, relative chain orientations, and directional charge transport properties in P(NDI2OD-T2) are explored. Altogether, this work provides unprecedented insights into complex structure-processing-transport relationships in a representative semiconducting organic polymer.

36 MATERIALS SCIENCE↗

Rational Regulation of Layer‐by‐Layer Processed Active Layer via Trimer‐Induced Pre‐Swelling Strategy for Efficient and Robust Thick‐Film Organic Solar Cells

Thick-film (>300 nm) organic solar cells (OSCs) have garnered intensifying attention due to their compatibility with commercial roll-to-roll printing technology for the large-scale continuous fabrication process. However, due to the uncontrollable donor/acceptor (D/A) arrangement in thick-film condition, the restricted exciton splitting and severe carrier traps significantly impede the photovoltaic performance and operability. For this work, combined with layer-by-layer deposition technology, a twisted 3D star-shaped trimer (BTT-Out) is synthesized to develop a trimer-induced pre-swelling (TIP) strategy, where the BTT-Out is incorporated into the buried D18 donor layer to enable the fabrication of thick-film OSCs. The integrated approach characterizations reveal that the exceptional configuration and spontaneous self-organization behavior of BTT-Out trimer could pre-swell the D18 network to facilitate the acceptor's infiltration and accelerate the formation of D/A interfaces. This enhancement triggers the elevated polarons formation with amplified hole-transfer kinetics, which is essential for the augmented exciton splitting efficiency. Furthermore, the regulated swelling process can initiate the favorable self-assembly of L8-BO acceptors, which would ameliorate carrier transport channels and mitigate carrier traps. As a result, the TIP-modified thin-film OSC devices achieve the champion performance of 20.3% (thin-film) and 18.8% (thick-film) with upgraded stability, among one of the highest performances reported of thick-film OSCs.

36 MATERIALS SCIENCE↗