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Results for “diffusion barriers”

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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

Transport Between the Tropical and Midlatitude Lower Stratosphere: Implications for Ozone Response to High Speed Civil Transport Emissions

Several recent studies have quantified the air exchange rate between the tropics and midlatitudes in the lower stratosphere using airborne and satellite measurements of chemical species. It is found that the midlatitude air is mixed into the tropical lower stratosphere with a replacement timescale of 13.5 months (with 20% uncertainty) for the region from the tropopause to 21 km and at least 18 months for the region of 20-28 km. These estimates are used to adjust the horizontal eddy diffusion coefficients, K(sub yy), in a two-dimensional chemistry transport model. The value of K(sub yy) previously used to simulate the subtropical barrier, 0.03 x 10(exp 6)sq m/s, generates an exchange time of about 4 years, and the model without subtropical barrier (K(sub yy) = 0.3 x 10(exp 6)sq m/s) has an exchange time of 5 months. Adjusting the K(sub yy) to 0.13 x 10(exp 6) sq m/s from the tropopause to 21 km and 0.07 x 10(exp 6)sq m/s above 21 km produces the exchange timescales which match the estimates deduced from the measurements. The subtropical barrier prevents the engine emissions of the high-speed civil transport (HSCT) aircraft from being transported into the tropics and subsequently lifted into the upper atmosphere or mixed into the southern hemisphere. The model results show that the calculated ozone response to HSCT aircraft emissions using the K(sub yy), adjusted to observed mixing rates is substantially smaller than that simulated without the subtropical barrier.

Shia, R.-L.↗
NASA NTRS1998

Transport Between the Tropical and Midlatitude Lower Statosphere: Implications for Ozone Response to High-Speed Civil Transport Emissions

Several recent studies have quantified the air exchange rate between the tropics and midlatitudes in the lower stratosphere using airborne and satellite measurements of chemical species. It is found that the midlatitude air is mixed into the tropical lower stratosphere with a replacement timescale of 13.5 months (with 20% uncertainty) for the region from the tropopause to 21 km and at least 18 months for the region of 20-28 km. These estimates are used to adjust the horizontal eddy diffusion coefficients, K(sub yy), in a two-dimensional chemistry transport model. The value of K(sub yy) previously used to simulate the subtropical barrier, 0.03 x 10(exp 6) sq m/s, generates an exchange time of about 4 years, and the model without subtropical barrier (K(sub yy) = 0.3 x 10(exp 6) sq m/s) has an exchange time of 5 months. Adjusting the K(sub yy) to 0.13 x 10(exp 6) sq m/s from the tropopause to 21 km and 0.07 x 10(exp 6) sq m/s above 21 km produces the exchange timescales which match the estimates deduced from the measurements. The subtropical barrier prevents the engine emissions of the high-speed civil transport (HSCT) aircraft from being transported into the tropics and subsequently lifted into the upper atmosphere or mixed into the southern hemisphere. The model results show that the calculated ozone response to HSCT aircraft emissions using the K(sob yy) adjusted to observed mixing rates is substantially smaller than that simulated without the subtropical barrier.

Shia, R.-L.↗
NASA NTRS1995

Theoretical Study of Response of InGaAs Metal-Semiconductor-Metal Photodetectors

We present a theoretical investigation of the response of metal-semiconductor-metal (MSM) photodetectors made of InGaAs lattice-matched to InP using a two-dimensional drift-diffusion model with a thermionic-field emission boundary condition for the heterojunctions. The effect of including a top InAlAs layer to increase the effective barrier height of the metal fingers on the InGaAs active layer is thoroughly examined and found to limit the collection of the photocurrent signal due to the electron and hole barriers that it forms with InGaAs. Due to the thickness and height of the InAlAs barrier layer in existing designs, the tunneling current obtained from the model is found to be negligibly small to significantly affect the output signal current. In an attempt to obtain a better response, different design structures including one where a quasi-Schottky contact is utilized are studied and their speed of response, breakdown voltage, and dark current are compared to that of the usual InGaAs device.

Salem, Ali F.↗
DOE OSTI2025

Heterobinuclear Molecular Precursors Direct the Formation of Supported Subnanometer Cu–M Clusters with Tunable Catalytic Behavior

Subnanometer bimetallic clusters hold great promise for catalytic applications due to their unique electronic properties and high surface-to-volume ratios. However, precise control over their composition and size remains a major challenge, particularly for immiscible metal pairs. Here, we report a surface-anchored molecular approach for synthesizing ∼0.7–0.8 nm Cu–M (M = Ru, Mo, W, Fe) bimetallic clusters on mesoporous silica supports, using heterobinuclear N-heterocyclic carbene (NHC)-based complexes as precursors. The NHC ligand functionalized with an alkoxysilane anchor enables robust grafting to the silica interface. Controlled calcination and reduction lead to subnanometer clusters with tunable composition, dictated by the metal–metal bond stability in the precursor. In situ transmission electron microscopy reveals cluster growth proceeds via sintering of adjacent surface-bound units, while elevated temperatures above 300 °C triggering diffusion and phase separation. Catalytic testing in ethylene hydrogenation demonstrates composition-dependent activity and kinetics, with CuRu and CuW clusters exhibiting lower apparent activation energy barriers compared with monometallic Cu nanoparticles. This study establishes a generalizable strategy for the interfacial synthesis of alloyed clusters from molecular precursors and provides mechanistic insight into how precursor design governs nanostructure formation and catalytic behavior.

N-heterocyclic carbene↗
DOE OSTI2026

Lithium–Divertor Interactions and Helium/Hydrogen Trapping in Lithiated Metals (Final Technical Report)

The goal of this project was to develop a fundamental understanding of helium and hydrogen behavior in lithium, both in bulk and at interfaces with tungsten, in order to inform the design of lithium based plasma facing components for fusion devices. Over the course of the award, the project produced the first comprehensive, peer reviewed dataset describing helium energetics, migration behaviors, and defect interactions in lithium. The research demonstrated that helium behaves in ways not previously observed in any other body centered cubic (BCC) metal: its interstitial configurations are more stable than substitutional ones, and its migration barriers are extraordinarily low, in some cases more than an order of magnitude below those in tungsten or iron. These discoveries reveal that helium in lithium diffuses so rapidly that its transport may be dominated by translational motion rather than the vibrationally activated mechanisms that underpin conventional solid state diffusion. This work lays a scientific foundation for understanding gas retention, bubble formation, and wall evolution in lithium based fusion environments and provides new computational tools, most notably a newly developed Li–He interatomic potential, for advancing future modeling efforts.

36 MATERIALS SCIENCE↗
NASA NTRS1992

Venus internal magnetic field and its interaction with the interplanetary magnetic field

In a previous study, Knudsen et al. suggested that Venus has a weak internal magnetic dipole field of the order of 7 x 10 + 20 G cm(exp -3) that is manifested in the form of magnetic flux tubes threading the ionospheric holes in the Venus nightside ionosphere. They pointed out that any internal field of Venus, dipole or multipole, would be weakened in the subsolar region and concentrated in the antisolar region of the planet by the supersonic transterminator convection of the dayside ionosphere into the nightside hemisphere. The inferred magnitude of the dipole field does not violate the upper limit for an internal magnetic field established by the Pioneer Venus magnetometer experiment. The most compelling objection to the model suggested by Knudsen et al. has been the fact that it does not explain the observed interplanetary magnetic field (IMF) control of the polarity of the ionospheric hole flux tubes. In this presentation I suggest that a magnetic reconnection process analogous to that occurring at earth is occurring at Venus between the IMF and a weak internal dipole field. At Venus in the subsolar region, the reconnection occurs within the ionosphere. At Earth it occurs at the magnetopause. Reconnection will occur only when the IMF has an appropriate orientation relative to that of the weak internal field. Thus, reconnection provides a process for the IMF to control the flux tube polarity. The reconnection in the subsolar region takes place in the ionosphere as the barrier magnetic field is transported downward into the lower ionosphere by downward convection of ionospheric plasma and approaches the oppositely directed internal magnetic field that is diffusing upward. The reconnected flux tubes are then transported anti-Sunward by the anti-Sunward convecting ionospheric plasma as well as by the anti-Sunward-flowing solar wind. Reconnection will also occur in the Venus magnetic tail region, somewhat analogously to the reconnection that occurs in the magnetotail of the Earth. The possibility that reconnection is occurring between the IMF and an internal dipole field may be tested by measuring the orientation of the IMF projected into a plane perpendicular to the solar wind velocity during time intervals for which ionospheric holes are observed. The orientations of the IMV components should fall within a 180 deg angle.

Knudsen, W. C.↗
NASA NTRS2013

Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

Ahlborg, Nadia L.↗
DOE OSTI2026

Restoring Escaped Zincate in Rechargeable Alkaline Zinc Batteries with a Seed-in-Nanoshell Design

Rechargeable alkaline zinc batteries are promising candidates for safe and low-cost energy storage, but suffer from ZnO dissolution that causes irreversible active material loss and rapid capacity decay. Here, we report a seed-in-nanoshell ZnO anode architecture that mitigates dissolution by combining physical confinement with electrochemical restoration of dissolved zincate species. ZnO particles are encapsulated within an ion-sieving carbon nanoshell that restricts zincate diffusion, maintains electrical conductivity, and stabilizes repeated solid–solution–solid transformations. Silver (Ag) nanoparticles incorporated into the nanoshell act as zincophilic nucleation seeds, lowering the Zn deposition barrier and directing the redeposition of dissolved zincate back to metallic Zn during charging. This confinement-enabled restoration mechanism converts zincate dissolution from an irreversible loss pathway into a recoverable process, enabling improved performance under harsh test conditions. The anode also delivers 227.9 mAh g −1 at −40 °C. Finally, a scalable tens-of-gram synthesis of ZnO@Ag is demonstrated, underscoring the practical potential of this strategy for advanced aqueous zinc batteries.

25 ENERGY STORAGE↗
NASA NTRS1991

Surface effects on hydrogen permeation through Ti-14Al-21Nb alloy

Hydrogen transport through Ti-14Al-21Nb (wt percent) alloy is measured using ultrahigh vacuum permeation techniques over the temperature range of 500 to 900 C and hydrogen pressure range of 0.25 to 10 torr. Hydrogen permeability through the alloy can be described through two different mechanisms depending on th temperature of exposure. In the 675 to 900 C range, the process is diffusion-limited: the permeability has a weak temperature dependence, but the diffusivity has a strong temperature dependence. Below 675 C, the permeation rate of hydrogen is very sensitive to surface controlled processes such as the formation of a barrier layer from contaminants. A physical model explaining the role of surface films on the transport of hydrogen through Ti-14Al-21Nb alloy was described.

Sankaran, Sandara N.↗
DOE OSTI2024

Critical Role of Framework Flexibility and Disorder in Driving High Ionic Conductivity in LiNbOCl 4

Understanding Li-ion transport is key for the rational design of superionic solid electrolytes with exceptional ionic conductivities. LiNbOCl 4 is reported to be one of the most highly conducting materials in the recently realized new class of soft oxyhalide solid electrolytes, exhibiting an ionic conductivity of ~11 mS·cm -1 . Here, we apply X-ray/neutron diffraction and pair distribution function analysis - coupled with density functional theory/ab-initio molecular dynamics - to determine a structural model that provides a rationale for the high conductivity that we observe experimentally in this nanocrystalline solid. We show that it arises from unusually high framework flexibility at room temperature. This owes to isolated 1-D [NbOCl 4 ] - anionic chains which exhibit energetically favorable orientational disorder that is - in turn - correlated to multiple, disordered and equi-energetic Li + sites in the lattice. As the Li-ions sample the 3-D energy landscape with a fast predicted diffusion coefficient of 5.1 x 10 -7 cm 2 /s at room temperature (σ i calc = 17.4 mS·cm -1 ), the inorganic polymer chains can reorient or vice versa. The activation energy barrier for Li migration through the frustrated energy landscape is especially reduced by the elastic nature of the NbO 2 Cl 4 octahedra evident from very widely dispersed Cl-Nb-Cl bond angles in AIMD snapshots at 300 K. The phonon spectra are predominantly influenced by Cl vibrations in the low energy range, and there is strong overlap between the framework (Cl, Nb) and Li partial pDOS in the region between 1.2 - 4.0 THz. The framework flexibility is also reflected in a relatively low bulk modulus of 22 GPa. In conclusion, our findings pave the way for investigation of future “flex-ion” inorganic solids and open up a new direction for the design of high conductivity, soft solid electrolytes for all-solid-state batteries.

AIMD↗
DOE OSTI2025

Cobalt–Nickel Exchange in Exfoliated Battery Layered Cathode Sheets with Application to Recycling

With the emerging dominance of electric vehicles (EV) in the transportation sector, recycling or upcycling spent battery materials will be required to reduce EV costs, lessen waste, and ease critical material supply chain issues for EV batteries. Here, motivated by work in the literature describing the exfoliation of layered oxides, first‐principles calculations are performed to show that Li x CoO 2 , if exfoliated into nanosheets, can readily undergo transition metal cation exchange in aqueous media. The substitution of Co 3+ or Co 4+ cations inside the sheet by Ni 2+ is associated with modest reaction barriers (Δ G* ≈ 0.3–0.7 eV) and is at most mildly endothermic (Δ G ≈ 0.2–0.3 eV). In contrast, previous battery degradation studies have shown that Co 3+ diffusion is strongly inhibited inside bulk layered oxides. This suggests that processing spent layered oxides as nanosheets can provide a potentially low‐energy‐cost pathway to altering the transition metal and/or dopant stoichiometry, which can be used toward developing new room‐temperature upcycling routes for cathodes from end‐of‐life batteries.

battery recycling↗
NASA NTRS2004

Kinetic Roughening Transition and Energetics of Tetragonal Lysozyme Crystal Growth

Interpretation of lysozyme crystal growth rates using well-established physical theories enabled the discovery of a phenomenon possibly indicative of kinetic roughening. For example, lysozyme crystals grown above a critical supersaturation sigma, (where supersaturation sigma = ln c/c(sub eq), c = the protein concentration and c(sub eq) = the solubility concentration) exhibit microscopically rough surfaces due to the continuous addition of growth units anywhere on the surface of a crystal. The rate of crystal growth, V(sub c), for the continuous growth process is determined by the continuous flux of macromolecules onto a unit area of the crystal surface, a, from a distance, xi, per unit time due to diffusion, and a probability of attachment onto the crystal surface, expressed. Based upon models applied, the energetics of lysozyme crystal growth was determined. The magnitudes of the energy barriers of crystal growth for both the (110) and (101) faces of tetragonal lysozyme crystals are compared. Finally, evidence supportive of the kinetic roughening hypothesis is presented.

Gorti, Sridhar↗
NASA NTRS2013

Wear and Reactivity Studies of Melt infiltrated Ceramic Matrix Composite

As interest grows in the use of ceramic matrix composites (CMCs) for critical gas turbine engine components, the effects of the CMCs interaction with the adjoining structure needs to be understood. A series of CMC/material couples were wear tested in a custom elevated temperature test rig and tested as diffusion couples, to identify interactions. Specifically, melt infiltrated silicon carbide/silicon carbide (MI SiC/SiC) CMC was tested in combination with a nickel-based super alloy, Waspaloy, a thermal barrier coating, Yttria Stabilized Zirconia (YSZ), and a monolithic ceramic, silicon nitride (Si3N4). To make the tests more representative of actual hardware, the surface of the CMC was kept in the as-received state (not machined) with the full surface features/roughness present. Test results include: scanning electron microscope characterization of the surfaces, micro-structural characterization, and microprobe analysis.

Jarmon, David C.↗
DOE OSTI2026

Buried Interfaces in Organic Photocathodes for H 2 Evolution: Fermi-Level Pinning and Recombination

Herein, we demonstrate how Fermi-level pinning at buried contacts impacts solar fuel generation in all-polymer photocathodes by systematically comparing the effects of work function, hydroxyl coverage, and hydrogen evolution using chemically modified indium tin oxide (ITO) supports. Photovoltages and net photocathode performance are improved when the ITO is passivated using phosphonic acids, independent of work function, suggesting that the passivation reduces Fermi-level pinning at the buried interface arising from blended heterojunction interactions with surface metal hydroxyls. Transient photovoltage decay reveals differences in recombination mechanisms, supported by light intensity-dependent measurements. Briefly, nonpassivated, hydrophilic contacts exhibit trap-assisted recombination, while passivated, hydrophobic contacts follow bimolecular recombination. We then investigate changes in electroactivity of hole-transfer processes as a function of scan rate and repetitive cycling using a diffusion-controlled molecular redox probe, analogous to a hole-only device achieved via the electrolyte. The nonpassivated buried contacts exhibit higher overpotentials for oxidation, indicative of hole injection/extraction barriers. We observe irreversible electron transfer via the hole-transport level of the blended heterojunction and a strong cycle dependence, consistent with changes in the hole trap state density. Passivation results in more reversible redox behaviors, consistent with more Ohmic-like contacts. Collectively, these results provide context toward the realization of durable organic photoelectrodes with optimized photovoltages and net solar-to-hydrogen conversion efficiencies via fundamental understanding of the rates of carrier generation, recombination, and transport in high-dielectric aqueous environments and opportunities to characterize buried interfaces under device-relevant electric fields.

buried interfaces↗
DOE OSTI2026

Structured electrolytes facilitate Grotthuss-type transport for enhanced proton-coupled electron transfer reactions

Concentrated hydrogen-bonded electrolytes (CoHBEs) are structured, electrochemically stable, less-volatile alternatives to aqueous and dilute nonaqueous electrolytes, however, with high viscosities that limit molecular diffusion. This work provides an understanding of the proton conduction mechanism in CoHBEs based on mixtures of acids and azoles and establishes a link between the structurally dictated transport properties and the proton-coupled electron transfer (PCET) reaction rates that can be leveraged for enhancing electrochemical reactions. Diffusion and relaxation NMR studies suggest a breaking of the viscosity–conductivity tradeoff, where at high azole concentrations (>45 mol%), Grotthuss transport is more likely with lowered proton transfer energy barriers between the azole and the acid according to the machine learning (ML) accelerated ab initio path integral MD (AI-PIMD) simulations. Proton conduction pathways are found to be switchable between the hydrogen bonding networks of the acid and the azole, with imidazole chain forming structures better facilitating Grotthuss hopping. Supported by small-angle neutron scattering studies, the chains are found to have six member molecules on average with maximum of 3 to 4 imidazole/imidazoliums at 50 to 60 mol%. Despite their high viscosities, the measured PCET rates for quinones and phenazines measured in the protic CoHBEs present relatively high electron transfer rate constants (k 0 ~ 10 −4 cm/s), validated by rotating disc electrode and scanning electrochemical microscopy measurements. The results demonstrate that strategic tuning of hydrogen-bond donor–acceptor interactions enables the decoupling of proton transport and viscosity, thereby impacting PCET reactions.

electrokinetics↗
NASA NTRS1975

Studies on the Al2O3-Ti-Mo-Au metallization system

The behavior of Ti-Mo-Au metallization on Al2O3 and C has been investigated by backscattering spectrometry. Results show that Mo-Au bimetal films typically mix during deposition. Diffusion of Ti in Mo film occurs at 600 C, but is inhibited by the presence of oxygen in the Ti film. Even 1000 A of Mo is not a barrier against interdiffusion of Ti and Au during 20-min anneals at 600 C. The amount of mixing observed also depends on the nature of the substrate which supports the Ti-Mo-Au metallization.

Harris, J. M.↗
NASA NTRS1981

Creep of oxide dispersion strengthened materials /with special reference to T-D nichrome/

Analyses of oxide dispersion strengthened (ODS) alloys shows that their characteristics are mainly due to the creep behavior of the matrix material. Diffusion-controlled slip creep is established as the rate-controlling process in the alloys investigated, with the glide and climb of edge dislocations associated with the subgrain structure as barriers being the specific rate-controlling step. It is found that the stable subgrain size in ODS alloys is usually associated with the spacing between particles 500-1000 A in size, and that their creep behavior is distinguished from that of the matrix material by the existence of a threshold stress that is not well defined microscopically but appears to be related to particles of less than 500 A size.

Lin, J.↗