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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 1,441 records · Page 80
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Strong Evidence of the Role of H 2 O in Affecting Methanol Selectivity from CO 2 Hydrogenation over Cu-ZnO-ZrO 2

CO 2 hydrogenation to methanol with renewable H 2 is an ideal process for coupling reduction of greenhouse gas and development of sustainable methanol economy, and Cu-ZnO-ZrO 2 is regarded as a promising catalyst for this process. Identification of the key descriptors that control the catalytic activity and selectivity is one of the most important issues for this reaction. In this work, we identify the role of water in the hydrogenation of CO 2 to methanol, which strongly affects the selectivity and yield of methanol. Our results reveal that methanol is generated via the hydrolysis of methoxy formed by the hydrogenation of formate, and the desorbed water vapor facilitates the hydrolysis of methoxy. A suitable amount of water in the feed can promote the formation of methanol. The enhancement on the water vapor diffusion in catalysts by structural and/or surface modification offers a new strategy for tuning the selectivity and yield of methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Achieving high rate performance in hybrid pristine-recycled cathodes using model-informed electrode designs

Direct recycling lithium-ion battery cathodes, a process that retains the engineered oxide structures from end-of-life materials, presents a cost-effective and energy-efficient alternative to other battery recycling methods. However, while direct-recycled cathodes have demonstrated performance comparable to that of pristine materials at low cycling rates, their high-rate performance remains uncertain. Morphology changes in cathode particles, a main mode of degradation, directly impact rate performance by limiting surface kinetics and solid-phase diffusion. If direct recycling processes do not sufficiently restore pristine-like morphologies, the recycled materials may retain structural defects that hinder high-rate performance. The present work uses a physics-based pseudo-2D model to simulate hybrid electrodes with pristine and artificially “aged/recycled” NMC materials to investigate potential impacts of incorporating performance-limited aged cathode materials into cells. The study highlights how differences in transport and kinetic properties can influence rate capabilities in mixed electrodes — particularly in high-loading cells in high-demand applications. However, model results also reveal a possible mitigation strategy via dual-layer electrode architectures with lower-performing materials positioned near the current collector. Simulations of 4.0 mAh cm −2 cells cycled at 4C using a dual-layer architecture provided approximately 5%–30% more capacity in constant-current protocols compared to homogeneously blended electrode architectures with the same loadings and mixed-material compositions. These findings highlight the importance of strategic electrode design in minimizing potential performance losses and facilitating the integration of recycled materials into high-performance batteries, advancing sustainable and cost-effective battery manufacturing.

25 ENERGY STORAGE↗
DOE OSTI2020

A study of damage-free in-situ etching of GaN in metalorganic chemical vapor deposition (MOCVD) by tertiarybutylchloride (TBCl)

This paper reports a study of the effect of NH 3 flow rate and reactor temperature on the tertiarybutylchloride (TBCl) etching of patterned GaN-on-sapphire templates. It is found that a reduced NH 3 flow rate and an elevated reactor temperature can eliminate islands or dots on the surface, while at the same time, enhance the etching around dislocations. TBCl etching was also performed on planar bulk GaN templates with much lower dislocation density. We find an atomically flat and layer-by-layer etching behavior within the region free of dislocations. Surface kinetics analysis reveals a short diffusion length of etching products. Room-temperature photoluminescence (PL) and x-ray photoelectron spectroscopy (XPS) measurements confirm that TBCl etching is capable of removing the damage and impurities induced by plasma etching without introducing additional damage.

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

Hydrogen trapping energetics at BCC iron-helium interfaces

Density functional theory (DFT) calculations have been performed to assess the trapping and segregation strength of hydrogen (H) to helium (He) interfaces in BCC (Fe) as a function of He density and surface orientation. The He density ranges from 0 to 2 He/V which corresponds to equilibrium bubbles that are expected to form in the structural components in a fusion reactor environment. The DFT calculations consist of a slab of BCC metal and an initial lattice of FCC He. Here, the report on the binding energy of H to these interfaces as well as the migration barriers into and away from the surface, which together provide information on the de-trapping energy for H at He bubbles. It was found that the binding energy of H to He-Fe interfaces decreases with increasing He density. Migration barriers are also modified due to the He density, which are sensitive to the surface orientation as well as the diffusion pathway. These results provide valuable first-principles energetics that are necessary for higher-order, mesoscale models, and provide insight into the extent to which He bubbles may trap tritium in fusion structural materials.

42 ENGINEERING↗
DOE OSTI2018

Volatile organic compound sensing based on coral rock-like ZnO

Highlights: • A coral rock-like ZnO with porous structure was successfully synthesized. • Coral rock-like ZnO realized the large gas response towards VOCs. • The porous structure may play an essential role in the surface sensing reaction. - Abstract: This work presented highly sensitive coral rock-like ZnO to investigate the sensing performances for volatile organic compounds (VOCs), including formaldehyde, methylbenzene, methanol and acetone. The coral rock-like ZnO with porous structure was synthesized using a solvothermal process and subsequent calcination. The gas response of the sensor based on the coral rock-like ZnO was reported for the four types of VOC vapors at different operating temperatures and gas concentrations. It was found that the fabricated sensor was sensitive to the four gases, revealing large gas response as well as fast response and recovery speed, which was ascribed to its distinctive porous nanostructure, resulting in adequate surface sensing reaction and effective gas diffusion.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Fiber-Shaped Fluidic Nanogenerator with High Power Density for Self-Powered Integrated Electronics

Flow-based hydrovoltaic nanogenerators have attracted particular attention as efficient and facile miniature energy-harvesting devices. However, they deliver relatively low output power density and limited power conversion efficiency owing to inefficient charge separation and poor charge accumulation. Here, we report the fabrication of high-performance, fiber-shaped fluidic nanogenerators (FFNGs) that use MoS 2 -encapsulated C fibers. The FFNGs deliver stable output voltages of 540 mV and an ultrahigh power density of 10.8 W m -2 . With experiments and density functional theory calculations, improvements in output performance can be attributed to smaller energy requirements for Na + cation adsorption, increased charge separation, and diffusion layer formations on the near surface. Moreover, self-powered, integrated devices achieve a maximum total power conversion-storage efficiency of ~11% and stable output voltage up to 3.1 V, which is applicable for use in consumer electronics devices.

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

NMR and Theoretical Study of In-Pore Diffusivity of Ionic Liquid–Solvent Mixtures

We report despite having a lower energy density than common batteries, electric double-layer capacitors (EDLCs) offer several advantages for high-power applications, including high power density, quick charge and discharge time, and long cycle life. Room-temperature ionic liquids (RTILs) have been intensely studied as promising electrolytes for applications in ELDCs because of their wide potential window, low volatility, as well as thermal and chemical stability. The main deficiency of neat RTILs in such applications is the sluggish diffusivity, which restricts the EDLCs’ power density. To alleviate the slow diffusivity, RTILs can be used in a mixture with organic solvents. In this study, we applied two-dimensional exchange nuclear magnetic resonance spectroscopy (2D EXSY NMR) and molecular dynamics (MD) simulations to investigate the diffusivity of anions of an RTIL, namely, 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (BMIM + –TFSI – ), dissolved in five different organic solvents, in the micropores of activated carbon. We determined that the relative concentrations of ions in solutions in the micropores were higher than those in the bulk solutions and were also solvent-dependent. The ion diffusivities in the pores were found to be almost 2 orders of magnitude slower than in the bulk solutions, with methanol showing the largest relative disparity. These results suggested that the interactions of solvents with the activated carbon are critical not only to the power density of EDLCs but also to the energy density. The comparisons of ion diffusivities between the experiments and the MD simulations suggest the need to consider also the surface functionalities of activated carbon for the simulation of ion diffusion in the micropores of activated carbon.

electric double layer capacitors↗
DOE OSTI2019

H Atom Production and Reaction in the Gamma Radiolysis of Thermally Modified Boehmite

The correlation between the formation of H atoms and H2 was observed in the radiolysis of thermally modified boehmite (?-AlOOH). Boehmite was pretreated by heating to 300, 400, and 550°C, loaded with adsorbed water, and irradiated with gamma rays. Long-lived H atoms trapped in the interstitial matrix was observed by electron paramagnetic resonance techniques and the amount of gaseous H2 by gas chromatography. Heating the boehmite to 400°C before radiolysis results in the collapse of the matrix with loss of trapped H atoms and a substantial increase in the production of H2. Samples without added water post-heating showed no production of H2 suggesting that it is formed by the diffusion of H atoms to the surface followed by an abstraction reaction with water. Boehmite heated to 550°C has completely converted to alumina and the radiolytic responses of each are similar. Post-irradiation heating of boehmite to 300°C results in a doubling of the H2 yield at pretreated temperatures below 300°C due to the release of trapped H atoms.

La Verne, Jay A.↗
DOE OSTI2020

Ion Transport and Mechanical Properties of Non-Crystallizable Molecular Ionic Composite Electrolytes

Polymer electrolytes show promise as alternatives to conventional electrolytes in energy storage and conversion devices but have been limited due to their inverse correlation between ionic conductivity and modulus. In this study, we examine surface morphology, linear viscoelastic, dielectric and diffusive properties of molecular ionic composites (MICs), materials produced through the combination of a rigid and charged double helical polymer, known as poly(2,2’)-disulfonyl-4,4’benzidine terepthalamide (PBDT), with ionic liquids (ILs). To probe temperature extremes, we incorporate a non-crystallizable IL to allow measurements from to -90 to 200°C. As we increase PBDT weight percentage (wt%), shear moduli increase and do not decay up to 200°C while maintaining room temperature ionic conductivity within a factor of two of the neat IL. We connect diffusion coefficients of IL ions with ionic conductivity through the Haven ratio across a wide temperature range and analyze trends in ion transport based on a relatively high and composition-dependent static dielectric constant. This behavior may result from collective rearrangement of IL ions in these networks. We propose that these properties are driven by a two-phase system in MICs corresponding to IL-rich “puddles” and PBDT-IL associated “bundles” where IL ions form alternating sheaths of cations and anions around each PBDT rod. Furthermore, these polymer-based MIC electrolytes show great promise for use in electrochemical devices that require fast ion transport, high modulus, and a broad thermal window.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Long-Term 13 C Uptake by 12 C-Enriched Calcite

Knowledge of the exchange of carbon isotopes between dissolved inorganic carbon and calcite minerals is of long-standing importance for the interpretation of sedimentary paleoclimate records and 14 C transport in the geosphere. To assess the mechanism and rates of carbon isotope exchange, we equilibrated 12 C-pure synthetic calcite particles in water, first in a glovebox and then in contact with atmospheric P CO 2 and 13 C/ 12 C ratio, at two different temperatures. Cavity ring-down infrared spectroscopy δ 13 C measurements of the solid revealed sustained 13C incorporation for over a period of 500 days (21 °C) and 125 days (50 °C). We developed a quantitative model for recrystallization and isotope exchange, assuming that the interfacial free energy provides a thermodynamic driving force for the growth of larger particles at the expense of smaller ones. Furthermore, this Ostwald ripening model did not reproduce the kinetics of 13C uptake and required greater coarsening than observed. Rather, the data were best explained by a mechanism involving surface exchange and solid-phase diffusion of 13C into the particles with an inferred effective diffusion constant at 21 °C of about 10 –25 m 2 /s. Although this work cannot rule out the possibility that structural or chemical aspects of the synthetic particles enabled faster 13 C uptake than could be observed in natural systems, this study adds to the body of the recent work, suggesting that fast exchange processes are possible, likely through grain boundaries and other defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Uncovering the predictive pathways of lithium and sodium interchange in layered oxides

Ion exchange is a powerful method to access metastable materials with advanced functionalities for energy storage applications. However, high concentrations and unfavourably large excesses of lithium are always used for synthesizing lithium cathodes from parent sodium material, and the reaction pathways remain elusive. Here, using layered oxides as model materials, we demonstrate that vacancy level and its corresponding lithium preference are critical in determining the accessible and inaccessible ion exchange pathways. Taking advantage of the strong lithium preference at the right vacancy level, we establish predictive compositional and structural evolution at extremely dilute and low excess lithium based on the phase equilibrium between Li 0.94 CoO 2 and Na 0.48 CoO 2 . Such phase separation behaviour is general in both surface reaction-limited and diffusion-limited exchange conditions and is accomplished with the charge redistribution on transition metals. Guided by this understanding, we demonstrate the synthesis of Na y CoO 2 from the parent Li x CoO 2 and the synthesis of Li 0.94 CoO 2 from Na y CoO 2 at 1-1,000 Li/Na (molar ratio) with an electrochemical assisted ion exchange method by mitigating the kinetic barriers. Our study opens new opportunities for ion exchange in predictive synthesis and separation applications. Ion exchange is a powerful method to access metastable materials for energy storage, but identifying lithium and sodium interchange in layered oxides remains challenging. Using such model materials, vacancy level and corresponding lithium preference are shown to be crucial for ion exchange pathway accessibility.

25 ENERGY STORAGE↗
DOE OSTI2018

A comparative study on the oxidation of two-dimensional Ti 3 C 2 MXene structures in different environments

The oxidation of two-dimensional Ti 3 C 2 MXene structures has been recognized as a promising method for the formation of hybrid structures of carbon supported nanotitania. Here, we studied the oxidation of Ti 3 C 2 MXene structures using reactive force field (ReaxFF) based molecular dynamics simulations. To investigate the effect of oxidizing agent, we used three different environments including dry air (oxygen molecules), wet air (oxygen and water molecules) and hydrogen peroxide (H 2 O 2 molecules). Oxidation simulations were performed at different temperatures of 1000, 1500, 2000, 2500 and 3000 K. We found that by controlling the temperature, carbon supported titania can be formed by diffusion of Ti atoms to the surface of MXene structures during the oxidation. These results were confirmed by the increase in the average bond orders of C–C and Ti–O and decrease in the average bond orders of Ti–C. Moreover, it was revealed that by increasing the temperature, the oxidation rate increases, and the rate depends on the oxidant according to the following order: H 2 O 2 > wet air > dry air. This was validated by heating the MXene in wet air and dry air followed by examining the products using X-ray diffraction and Raman spectroscopy. To investigate the effect of the presence of the oxidant, the MXene structure was also heated under vacuum, and it was found that in this case the MXene structure was converted to cubic TiC. Furthermore, it was indicated that during the heating process of the MXene structure in a vacuum, the average bond orders for C–C, Ti–C and Ti–O do not change significantly due to the lack of oxidants in the environment, leaving room for only topotactic transformation of atoms during the heating. In conclusion, the formation of the TiC structure by heating the MXene in an inert environment was confirmed experimentally as well.

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

Lattice modification in KTiOPO{sub 4} by hydrogen and helium sequentially implantation in submicrometer depth

We investigated lattice modification and its physical mechanism in H and He co-implanted, z-cut potassium titanyl phosphate (KTiOPO{sub 4}). The samples were implanted with 110 keV H and 190 keV He, both to a fluence of 4 × 10{sup 16 }cm{sup −2}, at room temperature. Rutherford backscattering/channeling, high-resolution x-ray diffraction, and transmission electron microscopy were used to examine the implantation-induced structural changes and strain. Experimental and simulated x-ray diffraction results show that the strain in the implanted KTiOPO{sub 4} crystal is caused by interstitial atoms. The strain and stress are anisotropic and depend on the crystal's orientation. Transmission electron microscopy studies indicate that ion implantation produces many dislocations in the as-implanted samples. Annealing can induce ion aggregation to form nanobubbles, but plastic deformation and ion out-diffusion prevent the KTiOPO{sub 4} surface from blistering.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Classification of computed thermal tomography images with deep learning convolutional neural network

Thermal tomography (TT) is a computational method for the reconstruction of depth profile of the internal material defects from Pulsed Infrared Thermography (PIT) nondestructive evaluation. Here, the PIT method consists of recording material surface temperature transients with a fast frame infrared camera, following thermal pulse deposition on the material surface with a flashlamp and heat diffusion into material bulk. TT algorithm obtains depth reconstructions of thermal effusivity, which has been shown to provide visualization of the subsurface internal defects in metals. In many applications, one needs to determine the defect shape and orientation from reconstructed effusivity images. Interpretation of TT images is non-trivial because of blurring, which increases with depth due to the heat diffusion-based nature of image formation. We have developed a deep learning convolutional neural network (CNN) to classify the size and orientation of subsurface material defects in TT images. CNN was trained with TT images produced with computer simulations of 2D metallic structures (thin plates) containing elliptical subsurface voids. The performance of CNN was investigated using test TT images developed with computer simulations of plates containing elliptical defects, and defects with shapes imported from scanning electron microscopy images. CNN demonstrated the ability to classify radii and angular orientation of elliptical defects in previously unseen test TT images. We have also demonstrated that CNN trained on the TT images of elliptical defects is capable of classifying the shape and orientation of irregular defects.

42 ENGINEERING↗
DOE OSTI2026

Effects of confinement and pressure on the structure and dynamics of carbon dioxide in silica slit pores

An understanding of carbon dioxide fluid properties within geological mesopores is important in applications ranging from carbon sequestration to shale oil recovery. Here, a molecular dynamics study is presented that aims to shed light on these systems by simulation of CO 2 fluid confined in β-cristobalite silica slit pores with different pore widths and pressure conditions. The weakly associating nature of carbon dioxide leads to little difference in structural and interfacial dynamical properties for different pore sizes and pressures. Rather, the behavior is found to be dominated by the entropic effects, namely, how the CO 2 organizes next to the silica surface. The CO 2 self-diffusion coefficient shows the strongest pore size dependence. It is strongly diminished in small pores and does not reach the bulk fluid value even in 6 nm pores. It also decreases with pressure, yielding an activation volume that increases with pore size. These results provide new insight into the behavior of a compressible fluid in nanoscale confinement.

Godahewa, Sahan M. [Univ. of Kansas, Lawrence, KS ↗
DOE OSTI2017

Formation and crystallisation of a liquid jet in a film exposed to a tightly focused laser beam{sup *}

This paper considers the effect of an ultrashort laser pulse on a thin gold film on a glass substrate at a focal spot size near 1 μm. We analyse the motion and thermal history of a film that has peeled off from the substrate in the heating spot as a consequence of melting. The detached zone is shown to form a dome-shaped bump whose motion is hindered by surface tension. After the dome stops and turns back, towards the substrate, a jet begins to grow on its top. Concurrently, because of the heat dissipation in the film, melt recrystallisation begins, involving first the dome and then the jet. The liquid part of the jet elongates and breaks up into droplets because of the Plateau – Rayleigh instability development. The formation of a neck and the detachment of the last droplet occur in the solidification zone between the crystalline and liquid parts of the jet. The propagation of the crystallisation zone in the jet leads the necking process, so neck disruption occurs in the solid phase under nonequilibrium crystallisation conditions (the melt temperature is hundreds of kelvins lower than the melting point), at limiting mechanical stress and at high deformation rates. As a result, the jet transforms into a high needle with an extremely small tip radius (a few nanometres). (paper)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Dark Energy Survey Year 1 results: the effect of intracluster light on photometric redshifts for weak gravitational lensing

Herein, we study the effect of diffuse intracluster light on the critical surface mass density estimated from photometric redshifts of lensing source galaxies, and the resulting bias in a weak lensing measurement of galaxy cluster mass. Under conservative assumptions, we find the bias to be negligible for imaging surveys like the Dark Energy Survey with a recommended scale cut of ≥200 kpc distance from cluster centres. For significantly deeper lensing source galaxy catalogues from present and future surveys like the Large Synoptic Survey Telescope program, more conservative scale and source magnitude cuts or a correction of the effect may be necessary to achieve percent level lensing measurement accuracy, especially at the massive end of the cluster population.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

Structural and dynamic properties of liquid tin from a new modified embedded-atom method force field

We developed a new modified embedded-atom method (MEAM) force field for liquid tin. Starting from the Ravelo and Baskes force field [Phys. Rev. Lett. 79, 2482 (1997)], the parameters are adjusted using a simulated annealing optimization procedure in order to obtain better agreement with liquid-phase data. The predictive capabilities of the new model and the Ravelo and Baskes force field are evaluated using molecular dynamics by comparing to a wide range of first-principles and experimental data. The quantities studied include crystal properties (cohesive energy, bulk modulus, equilibrium density, and lattice constant of various crystal structures), melting temperature, liquid structure, liquid density, self-diffusivity, viscosity, and vapor-liquid surface tension. We show that although the Ravelo and Baskes force field generally gives better agreement with the properties related to the solid phases of tin, the new MEAM force field gives better agreement with liquid tin properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗