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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Dynamic Metal–Support Interaction Dictates Cu Nanoparticle Sintering on Al 2 O 3 Surfaces

Nanoparticle sintering remains a critical challenge in heterogeneous catalysis. In this work, we present a unified deep potential (DP) model based on the Perdew–Burke–Ernzerhof approximation of density functional theory for Cu nanoparticles on three Al 2 O 3 surfaces (γ-Al 2 O 3 (100), γ-Al 2 O 3 (110), and α-Al 2 O 3 (0001)). Using DP-accelerated simulations, we reveal that the nanoparticle size-mobility relationship strongly depends on the supporting surface. The diffusion of nanoparticles on the two γ-Al 2 O 3 surfaces is almost independent of the size of the nanoparticle, while the diffusion on α-Al 2 O 3 (0001) decreases rapidly with increasing size. Interestingly, nanoparticles with fewer than 55 atoms diffuse several times faster on α-Al 2 O 3 (0001) than on γ-Al 2 O 3 (100) at 800 K while expected to be more sluggish based on their larger binding energy at 0 K. The diffusion on α-Al 2 O 3 (0001) is facilitated by dynamic metal–support interaction (MSI), where Al atoms move out of the surface plane to optimize contact with the nanoparticle and relax back to the plane as the nanoparticle moves away. In contrast, the MSI on γ-Al 2 O 3 (100) and on γ-Al 2 O 3 (110) is dominated by more stable and directional Cu–O bonds, consistent with the limited diffusion observed on these surfaces. Our extended MD simulations provide insight into the sintering processes, showing that the dispersity of the nanoparticles strongly influences the coalescence driven by nanoparticle diffusion. We observed that the coalescence of Cu 13 nanoparticles on α-Al 2 O 3 (0001) can occur in a short time (10 ns) at 800 K even with an initial internanoparticle distance increased to 3 nm, while the coalescence on the two γ-Al 2 O 3 surfaces are inhibited significantly by increasing the initial internanoparticle distance. These findings demonstrate that the dynamics of the supporting surface is crucial to understanding the sintering mechanism and offer guidance for designing sinter-resistant catalysts by engineering the support morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Representing effects of aqueous phase reactions in shallow cumuli in global models

Aqueous phase reactions are important, sometimes dominant (e.g., for SO 2 ), pathways for the oxidation of air pollutants at the local and/or global scale. In many current chemical transport models (CTMs), the transport and aqueous reactions of chemical species are treated as split processes, and the subgrid-scale heterogeneity between cloudy and environmental air is not considered. Here using large eddy simulation (LES) with idealized aqueous reactions mimicking the oxidation of surface-originated SO 2 by H 2 O 2 in shallow cumuli, we show that the eddy diffusivity mass flux (EDMF) approach with a bulk plume can represent those processes quite well when entrainment/detrainment rates and eddy diffusivity are diagnosed using a conservative thermodynamic variable such as total water content. The reason is that a typical aqueous reaction such as SO 2 aqueous oxidation is relatively slow compared to the in-cloud residence time of air parcels in shallow cumuli. As a result, the surface-originated SO 2 is well correlated with and behaves like conservative thermodynamic variables that also have sources at the surface. Experiments with various reaction rate constants and relative abundances of SO 2 and H 2 O 2 indicate that when the reaction timescale approaches the in-cloud residence time of air parcels, the errors of the bulk plume approach start to increase. Finally, treating chemical tracer transport and aqueous reaction as split processes leads to significant errors, especially when the reaction is fast compared to the in-cloud residence time. Overall, the EDMF approach shows large improvement over the CTM-like treatments in matching the LES results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Nanoparticle shape evolution and proximity effects during tip-induced electrochemical processes

The voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When the grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag + /Ag redox reaction to Ag + -ion diffusion with the increase in the applied voltage and pulse duration. Our study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, and emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Unified Entrainment and Detrainment Closures for Extended Eddy-Diffusivity Mass-Flux Schemes

The extended Eddy Diffusivity Mass Flux (EDMF) scheme is used as a unied parameterization that simulates subgrid-scale dynamics across a range of regimes.This work presents unied entrainment and detrainment closures that allow this scheme to simulate the dry convective boundary layer, shallow convection and deep convection , while adjacent works present other necessary closures for this unied scheme and test its performance for stable, stratocumulus topped and convective boundary layers. Entrainment and detrainment are modeled as a combination of turbulent and dynamical processes. The turbulent component is taken as downgradient diffusion between subdomains. The dynamical component is based on a ratio of buoyancy and vertical velocity that ensures consistent treatment of the ratio of mass-flux at vanishing area fraction. Dynamical detrainment is controlled by the difference in relative humidity between subdomains when liquid water is present. These closures are rst evaluated with entrainment and detrainment diagnosed from Large Eddy Simulations where decaying tracers are used to identify the different subdomains and mass exchanges between them. When implemented in a single column model (SCM), these closures are tested in simulations of several observationally motivated cases of dry convective boundary layer, shallow convection and deep convection. Results show good agreement between the SCM and Large Eddy Simulations in key properties for climate models and profiles of first, second and third moments. The development of diurnal cycles and the onset of and precipitation (with simplified microphysics) are well predicted by the SCM.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

The Application of an Evolutionary Programming Process to a Simulation of the ETEX Large-Scale Airborne Dispersion Experiment

Abstract Airborne tracer simulations are typically performed using a dispersion model driven by a high-resolution meteorological model. Besides solving the dynamic equations of momentum, heat, and moisture on the resolved model grid, mesoscale models must account for subgrid-scale fluxes and other unresolved processes. These are estimated through parameterization schemes of eddy diffusion, convection, and surface interactions, and they make use of prescribed parameters set by the user. Such “free” model parameters are often poorly constrained, and a range of plausible values exists for each. Evolutionary programming (EP) is a process to improve the selection of the parameters. A population of simulations is first run with a different set of parameter values for each member, and the member judged most accurate is selected as the “parent” of a new “generation.” After a number of iterations, the simulations should approach a configuration that is best adapted to the atmospheric conditions. We apply the EP process to simulate the first release of the 1994 European Tracer Experiment (ETEX) project, which comprised two experiments in which a tracer was released in western France and sampled by an observing network. The EP process is used to improve a simulation of the RAMS mesoscale weather model, with weather data collected during ETEX being used to “score” the individual members according to how well each simulation matches the observations. The meteorological simulations from before and after application of the EP process are each used to force a dispersion model to create a simulation of the ETEX release, and substantial improvement is observed when these are validated against sampled tracer concentrations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Superdiffusion of cosmic rays: Implications for cosmic ray acceleration

Diffusion of cosmic rays (CRs) is the key process for understanding their propagation and acceleration. We employ the description of spatial separation of magnetic field lines in magnetohydrodynamic turbulence in Lazarian and Vishniac to quantify the divergence of the magnetic field on scales less than the injection scale of turbulence and show that this divergence induces superdiffusion of CR in the direction perpendicular to the mean magnetic field. The perpendicular displacement squared increases, not as the distance x along the magnetic field, which is the case for a regular diffusion, but as the x {sup 3} for freely streaming CRs. The dependence changes to x {sup 3/2} for the CRs propagating diffusively along the magnetic field. In the latter case, we show that it is important to distinguish the perpendicular displacement with respect to the mean field and to the local magnetic field. We consider how superdiffusion changes the acceleration of CRs in shocks and show how it decreases efficiency of the CRs acceleration in perpendicular shocks. We also demonstrate that in the case when the small-scale magnetic field is generated in the pre-shock region, an efficient acceleration can take place for the CRs streaming without collisions along the magnetic loops.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

An atomistically informed mesoscale model for growth and coarsening during discharge in lithium-oxygen batteries

An atomistically informed mesoscale model is developed for the deposition of a discharge product in a Li-O{sub 2} battery. This mescocale model includes particle growth and coarsening as well as a simplified nucleation model. The model involves LiO{sub 2} formation through reaction of O{sub 2}{sup −} and Li{sup +} in the electrolyte, which deposits on the cathode surface when the LiO{sub 2} concentration reaches supersaturation in the electrolyte. A reaction-diffusion (rate-equation) model is used to describe the processes occurring in the electrolyte and a phase-field model is used to capture microstructural evolution. This model predicts that coarsening, in which large particles grow and small ones disappear, has a substantial effect on the size distribution of the LiO{sub 2} particles during the discharge process. The size evolution during discharge is the result of the interplay between this coarsening process and particle growth. The growth through continued deposition of LiO{sub 2} has the effect of causing large particles to grow ever faster while delaying the dissolution of small particles. The predicted size evolution is consistent with experimental results for a previously reported cathode material based on activated carbon during discharge and when it is at rest, although kinetic factors need to be included. The approach described in this paper synergistically combines models on different length scales with experimental observations and should have applications in studying other related discharge processes, such as Li{sub 2}O{sub 2} deposition, in Li-O{sub 2} batteries and nucleation and growth in Li-S batteries.

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

Asynchronous domain dynamics and equilibration in layered oxide battery cathode

To improve lithium-ion battery technology, it is essential to probe and comprehend the microscopic dynamic processes that occur in a real-world composite electrode under operating conditions. The primary and secondary particles are the structural building blocks of battery cathode electrodes. Their dynamic inconsistency has profound but not well-understood impacts. In this research, we combine operando coherent multi-crystal diffraction and optical microscopy to examine the chemical dynamics in local domains of layered oxide cathode. Our results not only pinpoint the asynchronicity of the lithium (de)intercalation at the sub-particle level, but also reveal sophisticated diffusion kinetics and reaction patterns, involving various localized processes, e.g., chemical onset, reaction front propagation, domains equilibration, particle deformation and motion. These observations shed new lights onto the activation and degradation mechanisms of state-of-the-art battery cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2019

Characteristics of Bi-metallic Interfaces Formed During Direct Energy Deposition Additive Manufacturing Processing

Various additive manufacturing processes are being evaluated to reduce the time and cost for fabrication of low volume, complex, and multifunctional assemblies. This study evaluated two direct energy deposition processes for the fabrication of large bi-metallic structures. The materials evaluated were Inconel 625 and copper alloy C18150, which are used in various high heat flux applications. Inconel was deposited onto the C18150 substrate using blown powder and wire-fed processes. Complete bonding was obtained in both processes and the resulting interfaces were evaluated using microscopy and indentation testing. Differences were observed in the interface region suggesting the kinetic energy of the blown powder process resulted in more residual stress at the interface, promoting recrystallization and enhanced diffusion. This created a broader interface in the blown powder specimens compared to a narrower mechanically mixed interface with the wire-fed process.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Deposition pressure dependent structural and optoelectronic properties of ex-situ boron-doped poly-Si/SiO x passivating contacts based on sputtered silicon

Among common methods to form polycrystalline silicon (poly-Si) films for passivating-contact solar cells, physical vapor deposition, in particular sputtering, is the safest one as it does not require any toxic gaseous precursors. One of the critical parameters to control the properties of sputtered silicon films is their deposition pressure. In this work, structural and optoelectronic characteristics of ex-situ boron-doped poly-Si/SiO x passivating contacts, formed from sputtered intrinsic amorphous silicon (a-Si) deposited at different pressures on top of SiO x /c-Si substrates and subjected to a high-temperature boron diffusion step, are investigated. The deposition rate and density of the as-deposited a-Si films increase with reducing pressure. Low-temperature photoluminescence spectra captured from the as-deposited samples at different pressures do not show typical emissions from hydrogenated a-Si. Meanwhile, their Fourier-transform infrared absorption spectra all show Si–H stretching modes, indicating that hydrogen had been initially incorporated into the chemical SiO x layers and eventually hydrogenated the a-Si/SiO x interfaces during the sputtering process. After the high-temperature boron-diffusion step, all hydrogen-related peaks disappear. Lower pressure films (1.5 and 2.5 mTorr) show more consistent improved performance after hydrogen treatments, compared to higher pressure films (4 and 5 mTorr). Overall, the resultant passivating contacts at 2.5 mTorr achieve a low single-side recombination current density Jo of ~9 fA/cm 2 , whereas their contact resistivity is still low at 15 mO cm 2 .

14 SOLAR ENERGY↗
DOE OSTI2014

Novel insight into the hydrogen absorption mechanism at the Pd(110) surface

The microscopic mechanism of low-temperature (80 K < T < 160 K) hydrogen (H) ingress into the H{sub 2} (<2.66 × 10{sup −3} Pa) exposed Pd(110) surface is explored by H depth profiling with {sup 15}N nuclear reaction analysis (NRA) and thermal desorption spectroscopy (TDS) with isotope (H, D) labeled surface hydrogen. NRA and TDS reveal two types of absorbed hydrogen states of distinctly different depth distributions. Between 80 K and ∼145 K a near-surface hydride phase evolving as the TDS α{sub 1} feature at 160 K forms, which initially extends only several nanometers into depth. On the other hand, a bulk-absorbed hydrogen state develops between 80 K and ∼160 K which gives rise to a characteristic α{sub 3} TDS feature above 190 K. These two absorbed states are populated at spatially separated surface entrance channels. The near-surface hydride is populated through rapid penetration at minority sites (presumably defects) while the bulk-absorbed state forms at regular terraces with much lower probability per site. In both cases, absorption of gas phase hydrogen transfers pre-adsorbed hydrogen atoms below the surface and replaces them at the chemisorption sites by post-dosed hydrogen in a process that requires much less activation energy (<100 meV) than monatomic diffusion of chemisorbed H atoms into subsurface sites. This small energy barrier suggests that the rate-determining step of the absorption process is either H{sub 2} dissociation on the H-saturated Pd surface or a concerted penetration mechanism, where excess H atoms weakly bound to energetically less favorable adsorption sites stabilize themselves in the chemisorption wells while pre-chemisorbed H atoms simultaneously transit into the subsurface. The peculiarity of absorption at regular Pd(110) terraces in comparison to Pd(111) and Pd(100) is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

High temperature oxidation behavior of Ni-based superalloy GH202

The isothermal oxidation kinetic and oxidation behavior of Ni-based superalloy GH202 were investigated at temperatures from 800 °C to 1100 °C. The microstructure of GH202 was characterized by scanning electron microscope (SEM) and electron back-scattered diffraction (EBSD). The composition and morphologies of oxide scales of the surface and cross-section samples were examined by X-ray diffraction (XRD), electron probe microanalysis (EPMA), and SEM combined with energy-dispersive spectroscopy (EDS). The results show that the growth of the oxide scales on GH202 obeyed a parabolic law with an activation energy of 247.8 KJ·mol{sup −1} from 800 °C to 1100 °C. The continuous and dense oxide scales that formed at 800 °C and 900 °C were composed of Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4} and a small amount of TiO{sub 2}. Beneath the oxide scales, aluminum-rich oxides formed along the grain boundaries due to internal oxidation. After treatment at 1000 °C for 150 h, the oxide scale was separated into two layers, the outer layer with sparse holes that was mainly composed of Cr{sub 2}O{sub 3} and TiO{sub 2} and an inner layer of dense Cr{sub 2}O{sub 3}. At 1100 °C for 100 h the outer layer was spalled, due to the looser oxide scale with large blocks of TiO{sub 2} and NiCr{sub 2}O{sub 4} which provided channels for oxygen diffusion. - Highlights: •Isothermal oxidation kinetic of GH202 obeys a parabolic law from 800 °C to 1100 °C. •The activation energy of GH202 is closed to the diffusion activation of Cr{sup 3+}. •The evolution process of oxide scales from 800 °C to 1100 °C is displayed by EPMA. •The oxidation behavior of GH202 is mainly controlled by Cr{sup 3+} and Ti{sup 4+}.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Ab initio modeling of zincblende AlN layer in Al-AlN-TiN multilayers

An unusual growth mechanism of metastable zincblende AlN thin film by diffusion of nitrogen atoms into Al lattice is established. Using first-principles density functional theory, we studied the possibility of thermodynamic stability of AlN as a zincblende phase due to epitaxial strains and interface effect, which fails to explain the formation of zincblende AlN. We then compared the formation energetics of rocksalt and zincblende AlN in fcc Al through direct diffusion of nitrogen atoms to Al octahedral and tetrahedral interstitials. The formation of a zincblende AlN thin film is determined to be a kinetically driven process, not a thermodynamically driven process.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

The effect of remnant CdSe layers on the performance of CdSeTe/CdTe photovoltaic devices

Thin film CdTe-based photovoltaic devices have achieved high efficiency above 22 %. The recent improvement in efficiency is due to Se alloying in the CdTe absorbers to form a CdSeTe/CdTe structure. The subsequent band gap grading increases the short circuit current density. The Se can be introduced by depositing a precursor thin film of either CdSe or a CdSeTe alloy and then diffusing the Se into the CdTe during the high temperature cadmium chloride activation process. Using CdSe is preferred because it is easier to control the Se concentration. However, during fabrication of the CdSeTe/CdTe devices, the CdSe thickness needs to be precisely controlled to prevent the retention of a CdSe remnant layer after the activation treatment. Retention of a remnant CdSe layer causes a dramatic reduction in device efficiency. In this work, we show that the reduction in efficiency is caused by a number of factors. The remnant CdSe layer is n-type which moves the position of the p-n junction. Also, it is widely thought that the CdSe remnants are photo-inactive. In this work, we clarify that the individual CdSe grains are actually highly photo-active. However, the grain sizes in the CdSe remnant and the adjacent CdSeTe layer are very small resulting in a high grain boundary area. Although the grain boundaries are passivated with chlorine, cathodoluminescence imaging and electrical measurements show that this is only partially effective. Also, EQE measurements show that the remnant CdSe causes parasitic absorption. Overall, the remnant CdSe layer causes a reduction in short circuit current density and device efficiency. The thickness of the CdSe precursor layer and the cadmium chloride activation process conditions must be precisely optimised to ensure that all the CdSe is consumed and inter-diffused to form the CdSeTe alloy for highest efficiency devices.

CdSe remnant↗
DOE OSTI2021

RF surface resistance tuning of superconducting niobium via thermal diffusion of native oxide

Recently, Nb superconducting radio frequency cavities vacuum heat treated between 300 and 400°C for a few hours have exhibited very high quality factors (~5 × 10 10 at 2.0 K). Secondary ion mass spectrometry measurements of O, N, and C show that this enhancement in RF surface conductivity is primarily associated with interstitial O alloying via dissolution and diffusion of the native oxide. We use a theory of oxide decomposition and O diffusion to quantify previously unknown parameters crucial in modeling this process. RF measurements of a vacuum heat-treated Nb superconducting radio frequency cavity confirm the minimized surface resistance (higher Q 0 ) previously expected only from 800 °C diffusive alloying with N.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

A quantum encryption design featuring confusion, diffusion, and mode of operation

Abstract Quantum cryptography—the application of quantum information processing and quantum computing techniques to cryptography has been extensively investigated. Two major directions of quantum cryptography are quantum key distribution (QKD) and quantum encryption, with the former focusing on secure key distribution and the latter focusing on encryption using quantum algorithms. In contrast to the success of the QKD, the development of quantum encryption algorithms is limited to designs of mostly one-time pads (OTP) that are unsuitable for most communication needs. In this work we propose a non-OTP quantum encryption design utilizing a quantum state creation process to encrypt messages. As essentially a non-OTP quantum block cipher the method stands out against existing methods with the following features: 1. complex key-ciphertext relation (i.e. confusion) and complex plaintext-ciphertext relation (i.e. diffusion); 2. mode of operation design for practical encryption on multiple blocks. These features provide key reusability and protection against eavesdropping and standard cryptanalytic attacks.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

A model for droplet heating and evaporation of water-in-oil emulsified fuel

Water-in-oil (W/O) emulsified fuel is a promising alternative fuel by inducing flash boiling of water at high temperature that can improve the atomization of fuel spray. The heating and evaporation process of emulsified fuel droplet is affected by the diffusion and coalescence of small dispersed water droplets in oil during the heating. In this study, a model is developed for the droplet heating and evaporation of W/O emulsified fuel with these key physics considered. The diffusivity of dispersed water droplets in oil is calculated using the Stokes-Einstein equation. The deactivation temperature of surfactant is selected as a criterion for the water coalescence since the water coalescence is due to the deactivation of surfactant. The process of water coalescence is simplified that the dispersed water droplets coalesce into one single water sub-droplet at the center of the oil droplet instantly as the droplet temperature reaches the deactivation temperature of surfactant. The model is validated against experimental data of single droplet under different heating temperatures, surfactant concentrations, and sizes of dispersed water droplets. Based on the proposed model, the effects of fuel properties and heating conditions on the droplet heating and evaporation are analyzed.

Droplet coalescence↗
DOE OSTI2014

Three-dimensional representation of late-arriving photons for detecting inhomogeneities in diffuse optical tomography

A method for rapid detection of absorbing inhomogeneity in a strongly scattering medium having the properties of a biological tissue before the image reconstruction is described based on the principles of diffuse optical tomography. The method is based on preliminary processing of a three-dimensional surface obtained from the set of time-resolved data in the Cartesian coordinate system, followed by its conformal transformation into two surfaces in the cylindrical coordinate system. A specific feature of the method is the use of late-arriving photons, scattered and diffusely transmitted through an optically turbid object. (optical tomography)

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗