SEARCH · Engineering Papers

Results for “Selective wetting”

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.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6

All sources NASA NTRS DOE OSTI

DOE OSTI2026

Explosive nucleation and growth of Pb islands on Ge(111) below room temperature via collective diffusion

Nucleation is a fundamental process in nature controlling phase transitions and pattern formation. Classical nucleation is based on the gradual aggregation of diffusing atoms after a critical cluster size is reached. Contrary to these expectations, we have observed in real time the formation of perfect Pb(111) islands with more than 10 5 atoms emerging out of the compressed wetting layer within a few seconds during growth of Pb on Ge(111) below room temperature. Pb deposited on Ge(111) in a temperature range between −30 °C and 10 °C exhibited explosive nucleation of height-selected islands upon reaching a critical coverage of 1.33 ± 0.07 ML with respect to Ge(111). Island nucleation was fueled by the 2% compression of the Pb wetting layer at the critical coverage. The island areas grew linearly with time, exhibiting collective diffusion, where thousands of atoms follow correlated, non-random walk diffusion. The total growth rate was higher with increasing temperature. Density functional theory simulations of the chemical potential and binding sites of the Pb/Ge(111) system give insight into the role of the compression of the wetting layer and the strain within the growing Pb layers, which explain this nonclassical behavior of the system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2022

Stable Cuprous Hydroxide Nanostructures by Organic Ligand Functionalization

Abstract Copper compounds have been extensively investigated for diverse applications. However, studies of cuprous hydroxide (CuOH) have been scarce due to structural metastability. Herein, a facile, wet‐chemistry procedure is reported for the preparation of stable CuOH nanostructures via deliberate functionalization with select organic ligands, such as acetylene and mercapto derivatives. The resulting nanostructures are found to exhibit a nanoribbon morphology consisting of small nanocrystals embedded within a largely amorphous nanosheet‐like scaffold. The acetylene derivatives are found to anchor onto the CuOH forming CuC linkages, whereas CuS interfacial bonds are formed with the mercapto ligands. Effective electronic coupling occurs at the ligand‐core interface in the former, in contrast to mostly non‐conjugated interfacial bonds in the latter, as manifested in spectroscopic measurements and confirmed in theoretical studies based on first principles calculations. Notably, the acetylene‐capped CuOH nanostructures exhibit markedly enhanced photodynamic activity in the inhibition of bacteria growth, as compared to the mercapto‐capped counterparts due to a reduced material bandgap and effective photocatalytic generation of reactive oxygen species. Results from this study demonstrate that deliberate structural engineering with select organic ligands is an effective strategy in the stabilization and functionalization of CuOH nanostructures, a critical first step in exploring their diverse applications.

Liu, Qiming↗

DOE OSTI2023

Syntheses and characterization of isotopically labeled 1,3,5-triamino-2,4,6-trinitrobenzene (TATB)

Synthesis and characterization of chemical analogues of TATB, where specific atoms in the structure have been isotopically substituted, are reported. 15 N, 2 H, and 18 O have replaced the naturally occurring isotope distributions in the amino and/or the nitro attendant sites and 13 C has replaced the carbon in the ring structure. A modified wet-amination method was used to produce the analogues, and the isotopic replacements were performed by selective choice of labeled precursors. Four 15 N-labeled compounds (N replaced in the amino and nitro positions), two deuterium-labeled compounds (hydrogens replaced on the amino groups), and one 13 C-labeled compound (C in the ring substituted) were synthesized of high isotopic and chemical purity. One partially labeled 18 O-labeled compound (O in the nitro position) was a result of incomplete labeling due to exchange reactions during synthesis. The compounds were characterized by various spectroscopic methods – mass spectrometry (MS), solid-state nuclear magnetic resonance (SS-NMR), infrared (FTIR), powder x-ray diffraction (PXRD), and differential scanning calorimetry (DSC), depending upon the substitution. In conclusion, these compounds have been critical to the efforts in understanding the decomposition pathways of TATB when exposed to abnormal thermal environments.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Effect of H + Exchange and Surface Impurities on Bulk and Interfacial Electrochemistry of Garnet Solid Electrolytes

Contact loss and current constriction pose significant challenges at the Li metal interface of solid-state batteries. For garnet-structured Li 7 La 3 Zr 2 O 12 (LLZO), these effects are amplified by Li + /H + exchange and surface contamination reactions, which lead to conductivity losses and poor Li wetting. In this study, we utilize a variety of surface treatment processes across 37 cells to selectively induce proton exchange and contamination reactions in LLZO. The resulting bulk and surface chemistry is systematically characterized and correlated to changes in electrochemical properties. Additionally, we combine impedance analysis and finite element method modeling to deconvolute sources of impedance contributions at the Li metal interface. Specifically, we show that constriction impedance at the Li metal interface arises not solely from voids, but also from ionically-resistive surface contaminants. Further, these findings emphasize the connection between ionic conductivity and constriction, demonstrating that micron-scale ionically-resistive components increase constriction even with identical contact geometries. Finally, we leverage our comprehensive dataset to highlight unstable overpotential growth as a failure mechanism, additionally showing that the phase of a cell’s impedance is a sensitive indicator for the onset of interfacial instability. Overall, this study clarifies the impacts of proton exchange and surface contamination on electrochemical properties at the Li|solid electrolyte interface and elucidates insights that are generalizable to other solid-state battery systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Synthesis of Nitro Compounds from Nitrogen Dioxide Captured in a Metal-Organic Framework

Increasing levels of air pollution are driving the need for the development of new processes that take “waste-to-chemicals”. Herein, we report the capture and conversion under ambient conditions of a major air pollutant, NO 2 , using a robust metal-organic framework (MOF) material, Zr-bptc (H 4 bptc = 3,3',5,5'-biphenyltetracarboxylic acid), comprising {Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (COO) 12 } clusters linked by 4-connected bptc 4– ligands in an ftw topology. At 298 K, Zr-bptc shows exceptional stability and adsorption of NO 2 at both low (4.9 mmol g –1 at 10 mbar) and high pressures (13.8 mmol g –1 at 1.0 bar), as measured by isotherm experiments. Dynamic breakthrough experiments have confirmed the selective retention of NO 2 by Zr-bptc at low concentrations under both dry and wet conditions. The immobilized NO 2 can be readily transformed into valuable nitro compounds relevant to construction, agrochemical, and pharmaceutical industries. In situ crystallographic and spectroscopic studies reveal strong binding interactions of NO 2 to the {Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (COO) 12 } cluster node. This study paves a circular pathway to enable the integration of nitrogen-based air pollutants into the production of fine chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Reactive boride infusion stabilizes Ni-rich cathodes for lithium-ion batteries

Engineered polycrystalline electrodes are critical to the cycling stability and safety of lithium-ion batteries, yet it is challenging to construct high-quality coatings at both the primary- and secondary-particle levels. Here, we present a room-temperature synthesis route to achieve full surface coverage of secondary particles and facile infusion into grain boundaries, thus offering a complete “coating-plus-infusion” strategy. Cobalt boride metallic glass is successfully applied to Ni-rich layered cathode LiNi 0.8 Co 0.1 Mn 0.1 O 2 . Here, it dramatically improves the rate capability and cycling stability, including under high-discharge-rate and elevated-temperature conditions and in pouch full cells. The superior performance originates from simultaneous suppression of microstructural degradation of intergranular cracking and side reactions with electrolyte. Atomistic simulations identified the critical role of strong selective interfacial bonding, which offers not only a large chemical driving force to ensure uniform reactive wetting and facile infusion but also lowered the surface/interface oxygen activity, contributing to the exceptional mechanical and electrochemical stabilities of the infused electrode.

25 ENERGY STORAGE↗

DOE OSTI2025

Dopant Sensitive Electrolytic Etching of Germanium with High Selectivity

Abstract The enhanced charge carrier mobility and photon absorption compared to silicon make germanium attractive for next-generation photo diodes. However, the complex oxidation behavior of germanium challenges dopant-dependent selective etching that is desired for the fabrication of backside imaging architectures. This report demonstrates electrolytic wet etching of p-doped germanium which proceeds up to 17,500x faster than etching of intrinsic germanium. Homoepitaxially grown layers of germanium were electrolytically etched in potassium hydroxide over a range of biases. Intermittent acquisition of cyclic voltammetry spectra during etching has suppressed the formation of electric double layers, maintained appreciable etch rates, and allowed for in operando process control. The observed etch rates scaled with dopant concentration. An effective etch rate of germanium removal of 2.100±0.044 µm/min was accomplished for a boron dopant concentration of 6E18cm-3. For nominally intrinsic germanium, however, an effective etch rate of only 0.00012±0.00011 µm/min was observed. A series of systematic electrolytic etch experiments have revealed the transfer of 4 electrons per germanium atom removed.

Wood, Joseph G.↗

NASA NTRS1979

Design, durability and low cost processing technology for composite fan exit guide vanes

A lightweight composite fan exit guide vane for high bypass ratio gas turbine engine application was investigated. Eight candidate material/design combinations were evaluated by NASTRAN finite element analyses. A total of four combinations were selected for further analytical evaluation, part fabrication by two ventors, and fatigue test in dry and wet condition. A core and shell vane design was chosen in which the unidirectional graphite core fiber was the same for all candidates. The shell material, fiber orientation, and ply configuration were varied. Material tests were performed on raw material and composite specimens to establish specification requirements. Pre-test and post-test microstructural examination and nondestructive analyses were conducted to determine the effect of material variations on fatigue durability and failure mode. Relevant data were acquired with respect to design analysis, materials properties, inspection standards, improved durability, weight benefits, and part price of the composite fan exit guide vane.

Blecherman, S. S.↗

DOE OSTI2022

Investigating Deposition Sequence During Synthesis of Pd/Al2O3 Catalysts Modified with Organic Monolayers

Modification of supported metal catalysts with self-assembled monolayers (SAMs) has been shown to improve selectivity and turnover frequencies (TOFs) for many catalytic reactions. However, these benefits are often accompanied by a decrease in overall mass activity due to partial blocking of active sites by the monolayers. Therefore, a potential method for increasing site accessibility is to deposit the active metal (e.g., Pd) after deposition of a SAM modifier on the support material. In this work, Pd/Al2O3 catalysts were synthesized using both a conventional, "metal-first" sequence in which the phosphonic acid (PA) SAM was deposited on Pd/Al2O3 and a "SAM-first" technique in which the ligands were deposited onto the support prior to deposition of the metal. Although metal-first catalysts showed a significant increase in TOF during benzyl alcohol HDO, they exhibited only a modest increase in overall mass activity due to a decrease in the number of active sites. Meanwhile, SAM-first catalysts showed similar improvements in TOF and toluene selectivity but exhibited significantly improved HDO rates compared to metal-first catalysts. The rate increase was attributed to reduced site blocking as evidenced by CO chemisorption measurements. Additionally, analysis of catalysts having high Pd loadings using transmission electron microscopy (TEM) showed that SAM-first catalysts generally resulted in lower average particle sizes than traditionally modified and unmodified catalysts, suggesting that precoating the support surface with PAs changes the way that Pd is deposited during incipient wetness, leading here to improved activity.

catalytic reactions↗

NASA NTRS2009

The Capillary Flow Experiments Aboard the International Space Station: Increments 9-15

This report provides a summary of the experimental, analytical, and numerical results of the Capillary Flow Experiment (CFE) performed aboard the International Space Station (ISS). The experiments were conducted in space beginning with Increment 9 through Increment 16, beginning August 2004 and ending December 2007. Both primary and extra science experiments were conducted during 19 operations performed by 7 astronauts including: M. Fincke, W. McArthur, J. Williams, S. Williams, M. Lopez-Alegria, C. Anderson, and P. Whitson. CFE consists of 6 approximately 1 to 2 kg handheld experiment units designed to investigate a selection of capillary phenomena of fundamental and applied importance, such as large length scale contact line dynamics (CFE-Contact Line), critical wetting in discontinuous structures (CFE-Vane Gap), and capillary flows and passive phase separations in complex containers (CFE-Interior Corner Flow). Highly quantitative video from the simply performed flight experiments provide data helpful in benchmarking numerical methods, confirming theoretical models, and guiding new model development. In an extensive executive summary, a brief history of the experiment is reviewed before introducing the science investigated. A selection of experimental results and comparisons with both analytic and numerical predictions is given. The subsequent chapters provide additional details of the experimental and analytical methods developed and employed. These include current presentations of the state of the data reduction which we anticipate will continue throughout the year and culminate in several more publications. An extensive appendix is used to provide support material such as an experiment history, dissemination items to date (CFE publication, etc.), detailed design drawings, and crew procedures. Despite the simple nature of the experiments and procedures, many of the experimental results may be practically employed to enhance the design of spacecraft engineering systems involving capillary interface dynamics.

Jenson, Ryan M.↗

NASA NTRS1990

The mechanical stability of polyimide films at high pH

Polyimide insulated electrical wire has been widely used in the aerospace industry in commercial, military, and to a lesser degree, general aviation aircraft since the early 1970s. Wiring failures linked to insulation damage have drawn much attention in the media and concerns have developed regarding the long term stability and safety of polyimide insulated electrical wire. The mechanical durability and chemical stability of polyimide insulated wire are affected by hydrolysis, notch propagation, wet and dry arc tracking, topcoat flaking, and degradation due to high pH fluids. Several polyimides were selected for evaluation for resistance to degradation by various aqueous alkaline solutions. The polyimides under evaluation include commercially available films such as KAPTON (tradename), APICAL (tradename), LARC-TPI, and UPILEX (tradename) R and S, as well as a number of experimental films prepared at NASA-Langley. Material properties investigated include viscosity, solubility, moisture absorption, glass transition temperature, dielectric constant, and mechanical properties before and after exposure to various conditions.

Croall, Catharine I.↗

DOE OSTI2026

The ever-evolving active site: transformation of single atoms to extended structures during the Rh-catalyzed reverse water–gas shift reaction

At low temperatures (< 400°C), single atoms of Rh supported on rutile TiO 2 (rTiO 2 ) are responsible for the formation of CO during the reverse water gas shift (RWGS), while methane production is associated with the Rh-TiO 2 interface due to the correlation between methane formation rates and the volume-averaged Rh nanoparticle diameter. As the temperature is increased to >540°C, there is a notable increase in CO selectivity and methane production rates tend towards zero. The time to reach zero depends on the temperature but independent of the initial Rh structure (single atoms and/or nanoparticles), which is controlled by the catalyst preparation method (wetness impregnation versus colloidal nanoparticles). At 600°C and > 4 h time on stream, the catalytic behaviour becomes completely agnostic to the initial Rh structure as well as weight loading, and the catalysts are highly selective for the reverse water gas-shift reaction. Post-reaction HR-TEM image analysis confirms Rh nanoparticles crystallize/order during the reaction; at 400°C, most of the Rh particles are disordered, while at 600°C, they are more ordered (i.e., development of defined faceting). Infrared spectroscopy of CO adsorption on Rh nanoparticles confirms the appearance of defined facets after annealing in nitrogen at high temperatures. Annealing the Rh/rTiO 2 catalysts prior to the RWGS reaction demonstrates the structural transformation of Rh depends only on time and temperature and not on reactant or product fugacity. Sites responsible for stabilizing Rh single atoms are no longer competent at higher temperatures, enabling their integration into existent nanoparticles. As the reaction temperature is increased to temperatures >540°C, the dominant active site for CO production evolves from single atoms to extended Rh structures.

36 MATERIALS SCIENCE↗

NASA NTRS1979

Investigations on transparent liquid-miscibility gap systems

Sedimentation and phase separation is a well known occurrence in monotectic or miscibility gap alloys. Previous investigations indicate that it may be possible to prepare such alloys in a low-gravity space environment but recent experiments indicate that there may be nongravity dependent phase separation processes which can hinder the formation of such alloys. Such phase separation processes are studied using transparent liquid systems and holography. By reconstructing holograms into a commercial-particle-analysis system, real time computer analysis can be performed on emulsions with diameters in the range of 5 micrometers or greater. Thus dynamic effects associated with particle migration and coalescence can be studied. Characterization studies on two selected immiscible systems including an accurate determination of phase diagrams, surface and interfacial tension measurements, surface excess and wetting behavior near critical solution temperatures completed.

Lacy, L. L.↗

DOE OSTI2021

Pretreatment of Biomass by Selected Type-III Deep Eutectic Solvents and Evaluation of the Pretreatment Effects on Hydrothermal Carbonization

Hydrothermal carbonization (HTC) is a novel thermochemical conversion that converts wet biomass into energy dense solid fuel. Residual moisture under subcritical conditions reacts with a lignin-cellulose-hemicellulose matrix with the major reactions being identified as dehydration and decarboxylation. Among other reaction parameters (e.g., temperature, time, pressure), biomass morphology often plays a key role in HTC. The hypothesis of this study was enhancing the porous structure of biomass without significantly affecting biopolymer composition would augment hydrothermal carbonization (HTC). To prove the hypothesis, two type-III deep eutectic solvents (DESs), namely choline chloride:urea (ChCl:Urea, 1:2 mol/mol) and methyltriphenylphosphonium bromide:ethylene glycol (MTPB:EG, 1:4 mol/mol), were studied to pretreat loblolly pine at room temperature and ambient pressure for 1 h. DES pretreatment shows swelling of the biomass, increasing the surface fiber-to-fiber gap length by 52% and 185% for ChCl:Urea and MPTB:EG pretreatments, respectively. The total pore volume remained intact (2.6 × 10 –3 cm 3 /g), although new small pores evolved, and existing pores were abated with DES pretreatment. Hydrochars prepared from DES pretreated loblolly pine showed a high O/C and H/C ratio resulting in a significant increase of energy content (up to 42%) and a decrease of mass yield (up to 50 wt %), indicating an enhancement of HTC severity due to the alteration of surface morphology by DES. Finally, a preliminary process economics revealed that integrated DES pretreatment-HTC would increase fixed capital investment but decrease the cost of operation and manufacturing than the standalone HTC process.

09 BIOMASS FUELS↗

DOE OSTI2025

Extraction of Pure Plastic Resins From PCR Plastic Waste by Solvent-Targeted Recovery and Precipitation (STRAP)

For this work, we have been developing a solvent‐based plastic recycling technology called STRAP. The technology is based on dissolving a targeted plastic resin in a specific solvent that does not dissolve other resins. We have demonstrated STRAP in thousands of bench scale experiments for a large variety of wastes. Recently we have demonstrated the technology for PCR, using mixed plastic wastes (MPWs), from a wet Material Recovery Facility (MRF). The process includes (1) infrared (IR) characterization to determine the plastic composition for accurate selection of the solvent to be used for the extraction of the pure resins. (2) Shredding to the right size and aspect ratio required for flowable and fast dissolvable process. (3) Mixing the MPW in the first solvent to dissolve the first resin. (4) Filtration of the solution plastic blend, to separate the nondissolved plastic from the solution. (5) Further filtration of the solution to remove micron‐sized particle of pigments and fibers. (6) Cooling for precipitation. (7) Filtration of pure resins. (8) Drying of a pure resin. (9) Extrusion of the resin to pellets. (10) Generating films or other products from the pure resin. Steps 1–10 can be considered as one‐cycle that extracted the first resin. (11) A second resin can be extracted with a respective solvent from the plastic that did not dissolve in the first cycle and following steps 1–10 described above. The process also includes characterization of interim and final products. The effort includes building a pilot system at 25 kg/h throughput. We will present specific results for various PCR.

IR characterization↗

DOE OSTI2021

BETO 2021 Peer Review - Separations in Support of Arresting Anaerobic Digestion

In support of the Bioenergy Technologies Office in converting waste feedstocks to fuels and chemicals, this project develops and demonstrates an advanced system for the production of platform carboxylic acids by Arresting Anaerobic Digestion (AAD) of wet waste feedstocks. The project addresses three technology barriers in developing the bioeconomy; (1) Feedstock availability and cost (2) Selective separation of organic acid species, and (3) First-of-a-kind technology development. This project has developed an advanced AAD system with separations that can operate in high solids environments (> 10 wt.%) and is net positive in energy consumption compared to the energy content of the carboxylic acids. Operating an in situ product recovery (ISPR) system in high solids is required for fermentation produced intermediates beyond ethanol that have volatilities less than water (e.g. carboxylic acids). Carboxylic acids form a versatile platform for the production of renewable diesel fuel, aviation fuel, monomers, and chemicals. A high solids ISPR system expands the feedstocks for AAD, which have been restricted to thin stillage, to solid food waste. Additionally, current AAD technology employs separations that consume >200x the energy content of the produced acids. This project has developed and demonstrated the first AAD technology with ISPR that is net negative in energy value and operates in solids contents >10 wt.% to produce a mixed carboxylic acid product that is carbon negative.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

DOE OSTI2022

Enhanced CO 2 Methanation Activity of Sm 0.25 Ce 0.75 O 2-δ –Ni by Modulating the Chelating Agents-to-Metal Cation Ratio and Tuning Metal–Support Interactions

Highly active and selective CO 2 methanation catalysts are critical to CO 2 upgrading, synthetic natural gas production, and CO 2 emission reduction. Wet impregnation is widely used to synthesize oxide-supported metallic nanoparticles as the catalyst for CO 2 methanation. However, as the reagents cannot be homogeneously mixed at an atomic level, it is challenging to modulate the microstructure, crystal structure, chemical composition, and electronic structure of catalysts via wet impregnation. In this work, a scalable and straightforward catalyst fabrication approach has been designed and validated to produce Sm 0.25 Ce 0.75 O 2-δ -supported Ni (SDC–Ni) as the CO 2 methanation catalyst. By varying the chelating agents-to-total metal cations ratio (C/I ratio) during the catalyst synthesis, we can readily and simultaneously modulate the microstructure, metallic surface area, crystal structure, chemical composition, and electronic structure of SDC–Ni, consequently fine-tuning the oxide–support interactions and CO 2 methanation activity. The optimal C/I ratio (0.1) leads to an SDC–Ni catalyst that facilitates C–O bond cleavage and significantly improves CO 2 conversion at 250 °C. A CO 2 -to-CH 4 yield of >73% has been achieved at 250 °C. Furthermore, a stable operation of >1500 hours has been demonstrated, and no degradation is observed. Extensive characterizations were performed to fundamentally understand how to tune and enhance CO 2 methanation activity of SDC–Ni by modulating the C/I ratio. The correlation of physical, chemical, and catalytic properties of SDC–Ni with the C/I ratio is established and thoroughly elaborated in this work. This study could be applied to tune the oxide–support interactions of various catalysts for enhancing the catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

The Consortium for Advanced Sorghum Phenomics (CASP). Final report

The goal of CASP was to accelerate breeding of biomass sorghum [Sorghum bicolor (L.) Moench] by identifying genotypes exhibiting high yield under well-watered, pre- or post-drought and/or salinity-stress conditions. We did this by combining high-throughput, non-invasive drone phenotyping with genomics and molecular profiling. Field-based phenotyping utilized a multi-modal sensor suite of LiDAR, multispectral cameras, and thermal cameras mounted on a commercial drone to detect traits required for yield prediction and selection of drought and saline tolerant lines of sorghum. Traits of interest included plant height (PH), leaf area index (LAI), wet biomass (BMW), and biomass at 65% moisture (BM65) and were measured from emergence to harvest on a weekly basis over three growing seasons. The final output were measurements of traits on a plot-by-plot basis, identified by the plot ID used by the Proprietary data processing software enabled raw field data to be turned into plant traits and delivered to the PNNL and JGI within the same workday.

09 BIOMASS FUELS↗