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Results for “Effective diffusivity”

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 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Superior CO 2 /N 2 separation performance of highly branched Poly(1,3 dioxolane) plasticized by polyethylene glycol

With its high content of CO 2 -philic ether oxygen groups, poly(1,3-dioxolane) (PDXLA) has emerged as an attractive platform to achieve excellent CO 2 /N 2 separation properties for post-combustion carbon capture. Herein we demonstrate that the separation properties of PDXLA can be further enhanced by plasticizing with miscible polyethylene glycol (PEG)-based additives using an integrated experimentation and modeling approach. The effects of the chain end groups and loading level of the additives on the physical properties of the blends are thoroughly investigated, including glass transition temperature (T g ), fractional free volume, and gas transport properties, and the effects can be satisfactorily described using models available for homogeneous blends. Notably, a T g -integrated free volume model is adapted to successfully interpret the unified effect of the blend composition and temperature on gas diffusivity and permeability. A sample containing 45 mass% PEG dimethyl ether (PEGDME with a molecular mass of 240 g/mol) displays stable mixed-gas CO 2 permeability of 1540 Barrer and CO 2 /N 2 selectivity of 40 when challenged with a model flue gas at 60 °C, outperforming Robeson's 2008 upper bound. Elucidating how small plasticizers impact gas transport in homogeneous blends may unravel a facile way to design high-performance membranes for gas separations.

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

Challenges in computationally designing high temperature Fe-based austenitic alloys: Addressing the role of Ni additions

Alumina-forming austenitic (AFA) alloys are relatively inexpensive high performance materials which combine the creep resistance of low-cost austenitic alloys and the oxidation resistance of expensive alumina forming alloys. However, a fundamental understanding of the role of key alloying elements such as Ni, Cr, Al, Nb, Ti, V, B and C in the experimentally observed oxidation behavior of these alloys is still lacking. The present work is a first in a series of studies aiming to quantitatively describe the role of Ni in promoting or disrupting protective Al 2 O 3 scale formation on AFA alloys. Here, ternary Fe-Al-xNi model alloys with three different Ni contents were isothermally exposed in an atmosphere with a low partial pressure of oxygen between 800–1000 °C for 24 h to evaluate the role of Ni in the observed internal oxidation behavior. Increasing Ni contents had no impact on the internal oxidation behavior of the alloys. The experimental and theoretical analyses in the present work suggested a negligible effect of the internal oxide precipitates on the inward diffusion of oxygen, typically expected in these systems, while simultaneously highlighting the barriers in the development of reliable models for computation-assisted design of these alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Volatilization Behavior of Supported Au Nanoparticle Arrays under H 2 at High Temperature

In this work, the fabrication and experimental study of model Au nanoparticle arrays (nanodots) was used to allow a direct comparison of reactive evaporation at elevated temperatures and nonambient H 2 -containing gas atmospheres with theoretical models. Strong temperature and H 2 -concentration dependencies were confirmed as expected, and the observed dependence in particle diameter with time was effectively described using a reactive evaporation and gas phase diffusion based quantitative model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Defect-driven anomalous transport in fast-ion conducting solid electrolytes

We report solid-state ionic conduction is a key enabler of electrochemical energy storage and conversion. The mechanistic connections between material processing, defect chemistry, transport dynamics, and practical performance are of considerable importance, but remain incomplete. Here, inspired by studies of fluids and biophysical systems, we re-examine anomalous diffusion in the iconic two-dimensional fast-ion conductors, the β- and β"-aluminas. Using large-scale simulations, we reproduce the frequency dependence of alternating-current ionic conductivity data. We show how the distribution of charge-compensating defects, modulated by processing, drives static and dynamic disorder, which lead to persistent sub-diffusive ion transport at macroscopic timescales. We deconvolute the effects of repulsions between mobile ions, the attraction between the mobile ions and charge-compensating defects, and geometric crowding on ionic conductivity. Our quantitative framework based on these model solid electrolytes connects their atomistic defect chemistry to macroscopic performance with minimal assumptions and enables mechanism-driven 'atoms-to-device' optimization of fast-ion conductors.

25 ENERGY STORAGE↗
DOE OSTI2020

Defect-mediated metastability and carrier lifetimes in polycrystalline (Ag,Cu)(In,Ga)Se 2 absorber materials

Using a combination of optical and electrical measurements, we develop a model for metastable defects in Ag-alloyed Cu(In,Ga)Se 2 , one of the leading thin film photovoltaic materials. By controlling the pre-selenization conditions of the back contact prior to the growth of polycrystalline (Ag,Cu)(In,Ga)Se 2 absorbers and subsequently exposing them to various stresses (light soaking and dark-heat), we explore in this paper the nature and role of metastable defects on the electro-optical and photovoltaic performance of high-efficiency solar cell materials and devices. Positron annihilation spectroscopy indicates that dark-heat exposure results in an increase in the concentration of the selenium–copper divacancy complex (V Se –V Cu ), attributed to depassivation of donor defects. Deep-level optical spectroscopy finds a corresponding increase of a defect at Ev+0.98 eV, and deep-level transient spectroscopy suggests that this increase is accompanied by a decrease in the concentration of mid-bandgap recombination centers. Time-resolved photoluminescence excitation spectroscopy data are consistent with the presence of the V Se –V Cu divacancy complex, which may act as a shallow trap for the minority carriers. Light-soaking experiments are consistent with the V Se –V Cu optical cycle proposed by Lany and Zunger, resulting in the conversion of shallow traps into recombination states that limit the effective minority carrier recombination time (and the associated carrier diffusion length) and an increase in the doping density that limits carrier extraction in photovoltaic devices.

14 SOLAR ENERGY↗
DOE OSTI2024

First-principles study of the Stark shift effect on the zero-phonon line of the NV center in diamond

Point defects in semiconductors are attractive candidates for quantum information science applications owing to their ability to act as spin-photon interface or single-photon emitters. However, the coupling between the change of dipole moment upon electronic excitation and stray electric fields in the vicinity of the defect, an effect known as Stark shift, can cause significant spectral diffusion in the emitted photons. In this work, using first principles computations, we revisit the methodology to compute the Stark shift of point defects up to the second order. The approach consists of applying an electric field on a defect in a slab and monitoring the changes in the computed zero-phonon line (i.e., difference in energy between the ground and excited state) obtained from constraining the orbital occupations (constrained-DFT). Here, we study the Stark shift of the negatively charged nitrogen-vacancy (NV) center in diamond using this slab approach. We discuss and compare two approaches to ensure a negatively charged defect in a slab and we show that converged values of the Stark shift measured by the change in dipole moment between the ground and excited states (Δ⁢μ) can be obtained. We obtain a Stark shift of Δ⁢μ = 2.68⁢D using the semilocal GGA-PBE functional and of Δ⁢μ = 2.23⁢D using the HSE hybrid functional. These values are in good agreement with experimental results. We also show that modern theory of polarization can be used on constrained-DFT to obtain Stark shifts in very good agreement with the slab computations.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Using Membranes with Internal Microchannels to Prevent Drying-out during CO 2 Electrolysis

Scaling up CO 2 electrolysis is a vital aspect in the transition to manufacturing sustainable fuels and chemical compounds, satisfying the demand for chemicals and demand for storing renewable electricity. Depending on the employed catalyst, different products can be produced, such as carbon monoxide and ethylene, by applying a voltage on a CO 2 and H 2 O fed electrolyzer. CO is a desirable product according to techno-economic analysis, because it can be produced selectively using a silver catalyst and is a precursor for hydrocarbons in the Fischer–Tropsch process. In a state-of-the-art CO 2 electrolyzer, two electrodes are directly pressed against an ion-exchange membrane – this is called a zero-gap configuration. Therefore, the membrane is a crucial component for the system, since it has the role of providing a conductive medium between the electrodes. One of the challenges in CO 2 electrolysis is that water is consumed in the reaction. At high current density, this may cause the membrane's surface near the cathode to dry out, lowering efficiency or perhaps stopping the process entirely, since there is no longer a conductive medium. As a result, water management is critical for this process. In this work, we approach the drying-out challenge by studying the novel concept of a membrane with internal microchannels. These channels allow the circulation of water or an electrolyte inside the membrane, which reduces the water diffusion path and affects the membrane’s conductivity. The effects of channel geometry, location, and concentrations of electrolyte inside on water content, conductivity and overall performance are studied in a 2D COMSOL model. In addition, the effect of internal concentration of electrolyte on the membrane’s resistance, on the process performance and the K + cross-over to cathode side were investigated experimentally. Our modeling results prove that the presence of the channels can keep the membrane hydrated. The highest current densities are observed when the channel is closest to the cathode, and with smaller pores. Smaller pores are advantageous due to the trade-off between enhanced membrane conductivity and the lower conductivity of the liquid itself. If water is circulated in a large channel, it increases the membrane’s ionomer conductivity due to hydration but the overall conductivity is decreased since water is not highly conductive. Nonetheless, the results also show that a higher concentration of electrolyte inside the microchannels can significantly increase the total conductivity of the membrane, and therefore the energy efficiency of the process. These effects are most significant at higher current densities. In the experimental results, we’ve observed similar effects in terms of membrane conductivity and current density of the process – the higher the electrolyte concentration the higher the current density. Furthermore, a low concentration decreases the amount of potassium which crosses over to the cathode side, inhibiting salt deposition. We’ve concluded that a small channel, up to 90 µm wide, close to the pore with an electrolyte with a concentration of up to 10 mM could be very beneficial for the water management and energy efficiency of the process. This helps to keep the membrane hydrated at higher current densities, improves the conductivity of the membrane, and it doesn’t have significant impacts on the salt deposition.

Petrov, Kostadin Veselinov↗
DOE OSTI2024

The ab initio amorphous materials database: Empowering machine learning to decode diffusivity

Amorphous materials exhibit unique properties that make them suitable for various applications in science and technology, ranging from optical and electronic devices and solid-state batteries to protective coatings. However, data-driven ex- ploration and design of amorphous materials is hampered by the absence of a com- prehensive database covering a broad chemical space. In this work, we present the largest computed amorphous materials database to date, generated from sys- tematic and accurate ab initio molecular dynamics (AIMD) calculations. We also show how the database can be used in simple machine-learning models to connect properties to composition and structure, here specifically targeting ionic conductiv- ity. These models predict the Li-ion diffusivity with speed and accuracy, offering a cost-effective alternative to expensive density functional theory (DFT) calculations. Furthermore, the process of computational quenching amorphous materials provides a unique sampling of out-of-equilibrium structures, energies, and force landscape, and we anticipate that the corresponding trajectories will inform future work in uni- versal machine learning potentials, impacting design beyond that of non-crystalline materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Super-Kamiokande Operations (Final Scientific/Technical Report)

The Super-Kamiokande experiment (SK, or Super-K) is based on a 50-kton water Cherenkov detector with 11,129 photomultiplier tubes. The detector is located in the Kamioka mine near Toyama, Japan. The detector has been operating since 1996. The collaboration is now around 165 people, mostly from the U.S. and Japan, but including Canada, the UK, S. Korea, Italy, China, Poland, France and Spain. Notable accomplishments so far include: the discovery of neutrino oscillations using atmospheric and solar neutrinos (and thus demonstrating that neutrinos have mass), the confirmation of these oscillations as the far detector of the K2K long baseline experiment, the first observation of v e appearance and non-zero θ 13 in a long baseline (T2K) beam, the world’s strictest limits on proton decay, the world’s best limits on indirect dark matter annihilation at moderate energies, sensitivity to a galactic supernova over most of the running time since 1996, the world’s best limit on diffuse supernova neutrinos, the first direct indication of matter effects on neutrino oscillations, and a number of other published results and theses in particle astrophysics.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Graphite Oxidation Modeling

Oxidation modeling importance ASME consideration Effect on graphite properties Model Overview Numerical Model Oxidation Diffusion Reaction Kinetics Model Parameterization Example problems Editing the model Simple problem example Conclusions Coupling to stress analysis Oxidation result analysis

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

, Experimental Investigation of Electrically Charged Water Droplets Two-Phase Cross-Flow Interactions with Humid

Electrically charged water droplets can capture water vapor molecules in surrounding moist air and promote vapor condensation. This concept unfolds an alternative to mechanical cooling-based air dehumidification systems that separate sensible and latent cooling loads in HVAC applications. The effect of dielectrophoresis, electro-hydrodynamic, and micro-diffusive flows due to highly electrically charged water droplets traveling through moist air were investigated as new methods to reduce the air’s water vapor content. This paper presents new experimental data on humidification and power consumption for a system consisting of highly energized electrosprays in combination with mist eliminators. Electrosprays produced highly charged water spray cones crossing the air perpendicularly and upwardly. The moist air stream was circulated in a horizontal duct at 22C, 80% relative humidity, and 0.24 ms-1 airspeed. Mist eliminators made of stainless wire clothes of 36 and 25 μm pore diameter were used to screen the droplets growing during their flight trajectory. The mist eliminators blocked some of the largest diameter droplets. Still, they could not prevent re-evaporation of the droplets into the bulk air from the droplets deposited on their wire clothes. The equilibrium between the dielectrophoresis condensation from the electrosprays and the droplets’ re-evaporation phenomena resulted in reduced humidification when compared to conventional-type spray evaporative cooling systems. However, to dehumidify the air, the droplets injected by the electrosprays must be separated entirely and promptly removed from the bulk airflow at the end of their flight trajectory.

Electrostatic droplets, Electrospray, humidificati↗
DOE OSTI2020

Transient magnetic field diffusion considerations relevant to magnetically assisted indirect drive inertial confinement fusion

We report application of a magnetic field to an indirect drive inertial confinement fusion target requires diffusion of the field through the high-Z and electrically conducting Hohlraum. The onset of the external field generates eddy currents in the Hohlraum wall that result in (1) a reduction of the peak field at the capsule, (2) heating of the Hohlraum wall through Ohmic dissipation, and (3) wall movement due to the inward force from the eddy current interacting with the field. Heating of the wall causes an increase in blackbody radiation which can preheat the capsule and frozen deuterium–tritium fuel, while wall motion leads to potential misalignment of the lasers at the Hohlraum wall. Limiting these detrimental effects sets requirements on the tolerable magnitude of each effect. We present a nonlinear model for B-field diffusion through an infinitely long thin-walled cylinder with a temperature dependent resistivity, to show that a 15 μm thick wall of pure gold fails to meet these requirements. A new Hohlraum material made from an alloy of Au and Ta has a measured resistivity of ≥60 times that of Au and is shown with the nonlinear model to meet the requirements for magnetization. We compare the nonlinear model to simulations of the actual Hohlraum target using a finite element code which includes temperature-dependent Hohlraum resistivity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Pore connectivity influences mass transport in natural rocks: Pore structure, gas diffusion and batch sorption studies

For this work, six rocks (one granodiorite, one limestone, two chalks, one mudstone, and one dolostone) with different extents of heterogeneity at six different particle sizes (from 75 to 8000 μm) were studied to describe the effects of pore connectivity on mass transport. The methods applied were (i) porosity measurement of granular rocks, (ii) analyses of gas-phase diffusive transport in a bed of packed particles, along with a solid quartz method at these six particle sizes being developed to identify the contribution of intraparticle diffusion, and (iii) batch sorption tests of multiple ions (anions and cations) with subsequent analyses of inductively coupled plasma-mass spectrometry. Granular porosity measurement results reveal that with decreasing particle sizes, the effective porosities for the “heterogenous” group of rocks (Grimsel granodiorite and Edwards limestone) increase, whereas the porosities of another “homogeneous” group (two Israel chalk samples, Japan mudstone, and Wyoming dolostone) remain constant. Gas diffusion results show that the intraparticle gas diffusion coefficient among these two sample groups, varying in the magnitude of 10 -8 to 10 -6 m 2 /s, are not directly correlated to the porosity differences. Moreover, the batch sorption work displays a different affinity of rocks for various tracers. For Grimsel granodiorite, Japan mudstone, and Wyoming dolostone, the adsorption capacity of Sm 3+ and Eu 3+ increases as the particle size decreases. In general, this integrated research of grain size distribution, granular rock porosity, intraparticle diffusivity, and ionic sorption capacity gives insights into the pore connectivity effect on both physical and chemical transport behaviors for different lithologies and/or different particle sizes.

58 GEOSCIENCES↗
DOE OSTI2021

Self-induced spin-orbit torques in metallic ferromagnets

Herein we present a phenomenological theory of spin-orbit torques in a metallic ferromagnet with spin-relaxing boundaries. The model is rooted in the coupled diffusion of charge and spin in the bulk of the ferromagnet, where we account for the anomalous Hall effects as well as the anisotropic magnetoresistance in the corresponding constitutive relations for both charge and spin sectors. The diffusion equations are supplemented with suitable boundary conditions reflecting the spin-sink capacity of the environment. In inversion-asymmetric heterostructures, the uncompensated spin accumulation exerts a dissipative torque on the order parameter, giving rise to a current-dependent linewidth in the ferromagnetic resonance with a characteristic angular dependence. We compare our model to recent spin-torque ferromagnetic resonance measurements, illustrating how rich self-induced spin-torque phenomenology can arise even in simple magnetic structures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Dynamic restructuring of supported metal nanoparticles and its implications for structure insensitive catalysis

Some fundamental concepts of catalysis are not fully explained but are of paramount importance for the development of improved catalysts. An example is the concept of structure insensitive reactions, where surface-normalized activity does not change with catalyst metal particle size. Here we explore this concept and its relation to surface reconstruction on a set of silica-supported Ni metal nanoparticles (mean particle sizes 1–6 nm) by spectroscopically discerning a structure sensitive (CO 2 hydrogenation) from a structure insensitive (ethene hydrogenation) reaction. Using state-of-the-art techniques, inter alia in-situ STEM, and quick-X-ray absorption spectroscopy with sub-second time resolution, we have observed particle-size-dependent effects like restructuring which increases with increasing particle size, and faster restructuring for larger particle sizes during ethene hydrogenation while for CO 2 no such restructuring effects were observed. Furthermore, a degree of restructuring is irreversible, and we also show that the rate of carbon diffusion on, and into nanoparticles increases with particle size. We finally show that these particle size-dependent effects induced by ethene hydrogenation, can make a structure sensitive reaction (CO 2 hydrogenation), structure insensitive. We thus postulate that structure insensitive reactions are actually apparently structure insensitive, which changes our fundamental understanding of the empirical observation of structure insensitivity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Kinetic pathways of fast lithium transport in solid electrolyte interphases with discrete inorganic components

The transport of lithium ions in the solid electrolyte interphase (SEI) has been previously accepted to proceed in two steps: a fast pore diffusion through the outer, porous organic layer followed by a slow knock-off or vacancy diffusion in the inner, dense inorganic layer. The second step is believed to be the rate-limiting step during fast-charging. In this study, we have intentionally constructed a thicker SEI (SEI-rich) structure on the surface of monoclinic Nb 2 O 5 (H-Nb 2 O 5 ) by adding LiNO 3 into a conventional ethylene carbonate based electrolyte. The electrochemical performance of two electrodes, one SEI-rich and one with few SEI (SEI-lean), was found to be almost the same, including their fast-charging capability and cycling stability, despite the significant difference in their SEI structure. Importantly, analysis using cryogenic scanning/transmission electron microscopy showed the discrete decoration of individual inorganic particles (e.g., Li 2 O) and amorphous species (LiN x O y /organic components) over the surface of H-Nb 2 O 5 . These discrete inorganic particles are in contradiction to the formation of dense inner inorganic layer, which has been commonly postulated. Based on these findings, we propose a new mechanism for Li ion transport through the SEI: one-step pore diffusion, without the second step slow diffusion. This one-step pore diffusion process provides an extremely fast Li ion transport, and effectively removes the kinetic limitation of Li ion transport in the SEI for fast charging. Finally, these results strongly suggest that the influence of SEI structure on the transport kinetics of lithium ions is much less significant than previously accepted. These results offer a new understanding of possible lithium ion transport pathway within SEI and may have implications for the future designs of fast-charging battery materials.

25 ENERGY STORAGE↗
DOE OSTI2024

Constrained Local Approximate Ideal Restriction for Advection-Diffusion Problems

Herein this paper focuses on developing a reduction-based algebraic multigrid (AMG) method that is suitable for solving general (non)symmetric linear systems and is naturally robust from pure advection to pure diffusion. Initial motivation comes from a new reduction-based AMG approach, $\ell \text{AIR}$ (local approximate ideal restriction), that was developed for solving advection-dominated problems. Though this new solver is very effective in the advection-dominated regime, its performance degrades in cases where diffusion becomes dominant. This is consistent with the fact that in general, reduction-based AMG methods tend to suffer from growth in complexity and/or convergence rates as the problem size is increased, especially for diffusion-dominated problems in two or three dimensions. Motivated by the success of $\ell \text{AIR}$ in the advective regime, our aim in this paper is to generalize the AIR framework with the goal of improving the performance of the solver in diffusion-dominated regimes. To do so, we propose a novel way to combine mode constraints as used commonly in energy-minimization AMG methods with the local approximation of ideal operators used in $\ell \text{AIR}$. The resulting constrained $\ell \text{AIR}$ algorithm is able to achieve fast scalable convergence on advective and diffusive problems. In addition, it is able to achieve standard low complexity hierarchies in the diffusive regime through aggressive coarsening, something that was previously difficult for reduction-based methods.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Unraveling Interdiffusion Phenomena and the Role of Nanoscale Diffusion Barriers in the Copper–Gold System

Diffusion is one of the most fundamental concepts in materials science, playing a pivotal role in materials synthesis, forming, and degradation. Of particular importance is solid state interdiffusion of metals which defines the usable parameter space for material combinations in the form of alloys. This parameter space can be explored on the macroscopic scale by using diffusion couples. However, this method reaches its limit when going to low temperatures, small scales, and when testing ultrathin diffusion barriers. Therefore, this work transfers the principle of the diffusion couples to small scales by using core–shell nanowires and in situ heating. This allows us to delve into the interdiffusion dynamics of copper and gold, revealing the interplay between diffusion and the disorder–order phase transition. Our in situ TEM experiments in combination with chemical mapping reveal the interdiffusion coefficients of Cu and Au at low temperatures and highlight the impact of ordering processes on the diffusion behavior. The formation of ordered domains within the solid-solution is examined using high-resolution imaging and nanodiffraction including strain mapping. In addition, we examine the effectiveness of ultrathin Al 2 O 3 barrier layers to control interdiffusion of the diffusion couple. Our findings indicate that a 5 nm thick layer serves as an efficient diffusion barrier. Furthermore, this research provides valuable insights into the interdiffusion behavior of Cu and Au on the nanoscale, offering potential applications in the development of miniaturized integrated circuits and nanodevices.

alloys↗