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Results for “reactive 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.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

A reactive wetting strategy improves lithium metal reversibility

The cycling of lithium metal (Li 0 ) anode is often accompanied by irregular lithium plating/stripping, leading to poor Li 0 reversibility, and posing a grand challenge to constructing reliable Li 0 batteries. Hereby, we report a reactive wetting strategy to enable conformal and highly reversible Li 0 plating/stripping through a lithium-reactive substrate. In this study, the reactive wetting, smooth nucleation, and conformal growth behaviors of Li 0 are visualized through in-situ transmission electron microscopy, ex-situ scanning electron microscope, and in-situ optical microscope characterizations. Based on the reactive wetting substrate, high average Coulombic efficiencies (99.0% at 0.5 mA cm -2 for 400 cycles) are realized for Li 0 anodes. By pre-plating Li 0 into the reactive wetting substrate as anodes and leveraging LiFePO 4 as cathodes, high capacity retention (76.0% after 200 cycles in low N/P ratio conditions) is also achieved in the as-constructed Li 0 full cells. This work establishes a fundamental understanding of reactive wetting dynamics of Li 0 and provides a drop-in solution to improving Li 0 reversibility.

25 ENERGY STORAGE↗
DOE OSTI2024

A data-driven multiscale model for reactive wetting simulations

Here, we describe a data-driven, multiscale technique to model reactive wetting of a silver–aluminum alloy on a Kovar™ (Fe-Ni-Co alloy) surface. We employ molecular dynamics simulations to elucidate the dependence of surface tension and wetting angle on the drop’s composition and temperature. A design of computational experiments is used to efficiently generate training data of surface tension and wetting angle from a limited number of molecular dynamics simulations. The simulation results are used to parameterize models of the material’s wetting properties and compute the uncertainty in the models due to limited data. The data-driven models are incorporated into an engineering-scale (continuum) model of a silver–aluminum sessile drop on a Kovar™ substrate. Model predictions of the wetting angle are compared with experiments of pure silver spreading on Kovar™ to quantify the model-form errors introduced by the limited training data versus the simplifications inherent in the molecular dynamics simulations. The paper presents innovations in the determination of “convergence” of noisy MD simulations before they are used to extract the wetting angle and surface tension, and the construction of their models which approximate physio-chemical processes that are left unresolved by the engineering-scale model. Together, these constitute a multiscale approach that integrates molecular-scale information into continuum scale models.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2013

Predictive modeling of reactive wetting and metal joining.

The performance, reproducibility and reliability of metal joints are complex functions of the detailed history of physical processes involved in their creation. Prediction and control of these processes constitutes an intrinsically challenging multi-physics problem involving heating and melting a metal alloy and reactive wetting. Understanding this process requires coupling strong molecularscale chemistry at the interface with microscopic (diffusion) and macroscopic mass transport (flow) inside the liquid followed by subsequent cooling and solidification of the new metal mixture. The final joint displays compositional heterogeneity and its resulting microstructure largely determines the success or failure of the entire component. At present there exists no computational tool at Sandia that can predict the formation and success of a braze joint, as current capabilities lack the ability to capture surface/interface reactions and their effect on interface properties. This situation precludes us from implementing a proactive strategy to deal with joining problems. Here, we describe what is needed to arrive at a predictive modeling and simulation capability for multicomponent metals with complicated phase diagrams for melting and solidification, incorporating dissolutive and composition-dependent wetting.

van Swol, Frank B.↗
DOE OSTI2025

Tuning Catalytic Reactivity via Wetting Control through Oxygen Vacancies: Ru Clusters on Anatase TiO 2 and CeO 2 Supports

The shape of supported metal particles regulates their catalytic reactivity and is determined by the degree of wetting between the metal particle and the support surface. Flattened particles that wet support surfaces were reported in various catalytic systems, particularly in the subnanometer size regime. Such consequential metal–support wetting phenomena are poorly understood, and methods to study them on powder catalysts under realistic conditions are lacking. Here, we investigate the size-dependent wetting behaviors of Ru particles on two reducible-oxide supports, anatase TiO 2 (TiO 2 -A) and CeO 2 , under reducing catalytic conditions. X-ray absorption spectroscopy (XAS), low-energy ion scattering (LEIS), and density functional theory (DFT) are combined to determine the shape of Ru particles. Ru particles remain three-dimensional without wetting the TiO 2 -A support within the coverage range studied (0.06–0.98 Ru nm –2 ). In contrast, at low coverages (<0.25 Ru nm –2 ), Ru wets the CeO 2 support to form flat, disordered structures. The higher wettability of CeO 2 than TiO 2 -A is attributed to oxygen vacancies in the near-surface region. The shape difference between small Ru particles or clusters on the two supports leads to drastically contrasting catalytic reactivities in polyolefin hydrogenolysis, despite similar diameters. As a result, this work highlights the implications of metal–support wetting, or cluster shape, on catalytic behaviors of small metal clusters, while establishing the foundation for future systematic studies of such a phenomenon in realistic systems, by delivering a multitechnique methodology and revealing governing fundamental principles.

42 ENGINEERING↗
DOE OSTI2025

Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalysts

The performance of bimetallic dilute alloy catalysts is largely determined by the size of minority metal ensembles on the nanoparticle surface. By analyzing the synthesis of catalysts comprising Pd 8 Au 92 nanoparticles supported on silica using surface-sensitive techniques, we report that whether Pd overgrowth occurs before or after Au nanoparticle deposition onto the support controls the surface Pd ensemble size and abundance. These differences in Pd ensembles influence catalytic reactivity in H 2 –D 2 isotope exchange and benzaldehyde hydrogenation, which, in correlation with theoretical calculations, is used to elucidate the active site(s) in each reaction. To clarify how the synthetic sequence controls the formation of Pd ensembles, we combine numerical wetting calculations and molecular dynamics simulations (with a machine-learned force field) to visualize Pd deposition and migration on the nanoparticle surface, respectively. Our results suggest that the nanoparticle–support interface restricts nanoparticle accessibility to Pd deposition, which consequently controls the Pd ensemble size, illustrating the critical role of nanoscale wetting phenomena during bimetallic catalyst preparation.

36 MATERIALS SCIENCE↗
DOE OSTI2014

WETTING AND REACTIVE AIR BRAZING OF BSCF FOR OXYGEN SEPARATION DEVICES

Reactive air brazes Ag-CuO and Ag-V2O5 were evaluated for brazing Ba0.5Sr0.5Co0.8Fe0.2O(3-δ) (BSCF). BSCF has been determined in previous work to have the highest potential mixed ionic/electronic conducting (MIEC) ceramic material based on the design and oxygen flux requirements of an oxy-fuel plant such as an integrated gasification combined cycle (IGCC) used to facilitate high-efficiency carbon capture. Apparent contact angles were observed for Ag-CuO and Ag-V2O5 mixtures at 1000 °C for isothermal hold times of 0, 10, 30, and 60 minutes. Wetting apparent contact angles (θ<90°) were obtained for 1%, 2%, and 5% Ag-CuO and Ag-V2O5 mixtures, with the apparent contact angles between 74° and 78° for all compositions and furnace dwell times. Preliminary microstructural analysis indicates that two different interfacial reactions are occurring: Ag-CuO interfacial microstructures revealed the same dissolution of copper oxide into the BSCF matrix to form copper-cobalt-oxygen rich dissolution products along the BSCF grain boundaries and Ag-V2O5 interfacial microstructures revealed the infiltration and replacement of cobalt and iron with vanadium and silver filling pores in the BSCF microstructure. The Ag-V2O5 interfacial reaction product layer was measured to be significantly thinner than the Ag-CuO reaction product layer. Using a fully articulated four point flexural bend test fixture, the flexural fracture strength for BSCF was determined to be 95 ± 33 MPa. The fracture strength will be used to ascertain the success of the reactive air braze alloys. Based on these results, brazes were fabricated and mechanically tested to begin to optimize the brazing parameters for this system. Ag-2.5% CuO braze alloy with a 2.5 minute thermal cycle achieved a hermetic seal with a joint flexural strength of 34 ± 15 MPa and Ag-1% V2O5 with a 30 minute thermal cycle had a joint flexural strength of 20 ± 15 MPa.

Ag-CuO↗
DOE OSTI2018

Wetting Behavior of TiO{sub 2} by Calcium Ferrite Slag at 1523 K

The wetting behaviors of a TiO{sub 2} substrate by calcium ferrite (CF) series slags were investigated using an improved sessile drop method at 1523 K (1250 °C). The initial contact angles were in the range 35 to 50 deg, the final equilibrium apparent contact angles were < 20 deg, and the spreading durations were in the range 75 to 180 seconds. The CF-TiO{sub 2} system showed reactive wetting, which was categorized into four dynamic stages. Stage I: physical spreading, stage II: slow linear spreading, stage III: fast linear spreading, and stage IV: equilibrium. Interfacial reactions yielded CaTiO{sub 3} during reactive spreading, thereby transitioning TiO{sub 2} wetting into CaTiO{sub 3} wetting and then forming Fe{sub 2}TiO{sub 5} and FeTiO{sub 3} owing to the excess Fe{sub 2}O{sub 3} and FeO that had accumulated in the interfacial zone. Although stage III spreading was faster than stage II spreading, adding MgO to the slag slowed stage III spreading. The interfacial microstructure of the residual slag was roughly divided into three layers owing to the different densities of the slag and solid products. The top layer was composed of CaTiO{sub 3} and Fe{sub 2}O{sub 3}, the middle one was composed of CaTiO{sub 3} and Fe{sub 2}TiO{sub 5}, and the bottom one was composed of Fe{sub 2}TiO{sub 5} and FeTiO{sub 3}. Adding TiO{sub 2} to the slag produced a dense CaTiO{sub 3}-containing interfacial layer, resulting in CF being detected in the residual slag.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Bioinspired nacre-like alumina with a bulk-metallic glass-forming alloy as a compliant phase

Bioinspired ceramics with micron-scale ceramic "bricks" bonded by a metallic "mortar" are projected to result in higher strength and toughness ceramics, but their processing is challenging as metals do not typically wet ceramics. To resolve this issue, we made alumina structures using rapid pressureless infiltration of a zirconium-based bulk-metallic glass mortar that reactively wets the surface of freeze-cast alumina preforms. The mechanical properties of the resulting Al 2 O 3 with a glass-forming compliant-phase change with infiltration temperature and ceramic content, leading to a trade-off between flexural strength (varying from 89 to 800 MPa) and fracture toughness (varying from 4 to more than 9 MPa·m ½ ). The high toughness levels are attributed to brick pull-out and crack deflection along the ceramic/metal interfaces. Since these mechanisms are enabled by interfacial failure rather than failure within the metallic mortar, the potential for optimizing these bioinspired materials for damage tolerance has still not been fully realized.

36 MATERIALS SCIENCE↗
NASA NTRS1987

Acid dew and the role of chemistry in the dry deposition of reactive gases to wetted surfaces

A formalism is developed to describe the dry deposition of soluble reactive gases to wetted surfaces in terms of the relevant meteorological conditions, the surface roughness, the total amount of liquid water present on the surface, the rate of accumulation of this water, and the species' solubility and reactivity in the surface water. This formulation is then incorporated into a model designed to simulate the generation of acidic dew from the deposition of HNO3, SO2, S(IV) oxidants, H2O2, and O3. Similar to the observations of dew in the continental U.S., the model generates a dewdrop pH of about 4 by the end of the night; the pH can rapidly fall to toxic levels due to rapid evaporation after sunrise. Relatively low deposition velocities are predicted for the SO2 and O3 because of their lower solubilities and hence larger surface resistances than those of the other oxidants. Because the chemical lifetime of the SO2 in the dew is influenced by the atmospheric levels of H2O2, O3, and SO2, the SO2 deposition velocity is a strong function of these species' atmospheric abundances.

Chameides, William L.↗
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 OSTI2018

Wetting Behavior and Reactivity of Molten Silicon with h-BN Substrate at Ultrahigh Temperatures up to 1750 °C

For a successful implementation of newly proposed silicon-based latent heat thermal energy storage systems, proper ceramic materials that could withstand a contact heating with molten silicon at temperatures much higher than its melting point need to be developed. In this regard, a non-wetting behavior and low reactivity are the main criteria determining the applicability of ceramic as a potential crucible material for long-term ultrahigh temperature contact with molten silicon. In this work, the wetting of hexagonal boron nitride (h-BN) by molten silicon was examined for the first time at temperatures up to 1750 °C. For this purpose, the sessile drop technique combined with contact heating procedure under static argon was used. The reactivity in Si/h-BN system under proposed conditions was evaluated by SEM/EDS examinations of the solidified couple. It was demonstrated that increase in temperature improves wetting, and consequently, non-wetting-to-wetting transition takes place at around 1650 °C. The contact angle of 90° ± 5° is maintained at temperatures up to 1750 °C. The results of structural characterization supported by a thermodynamic modeling indicate that the wetting behavior of the Si/h-BN couple during heating to and cooling from ultrahigh temperature of 1750 °C is mainly controlled by the substrate dissolution/reprecipitation mechanism.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Wetting and Interfacial Reactivity of Zn-Coated Steel Products with Cu-Si, Cu-Sn and Al-Si Filler Metals for Laser Brazing Application

The laser brazing process is successfully applied in automotive industry for joining of roofs and hatchbacks of vehicles. The bad wetting of the brazing alloy during the process can lead to the formation of random external porosities which are not allowed on visible parts. This paper describes the wettability and reactivity mechanisms at short contact time of Cu and Al matrix brazing alloys with different reactive elements (Si, Sn) on different steel products such as hot-dip galvanized steels, galvannealed steel and bare steel. Wetting experiments were carried out by the dispensed drop technique. The effects of alloying elements and brazing alloy matrix on interfacial reactivity are discussed. It was found that Cu matrix containing 3 wt.% Si is the most favorable for short time liquid/solid adhesion relatively to the other studied brazing alloy compositions. The brazing ability of different steel products is well correlated with the wettability and interfacial reactivity results.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Hierarchical calibration and validation for modeling bench-scale solvent-based carbon capture. Part 1: Non-reactive physical mass transfer across the wetted wall column

A hierarchical model calibration and validation are proposed here for quantifying the confidence level of mass transfer prediction using a computational fluid dynamics (CFD) model, where the solvent-based carbon dioxide (CO 2 ) capture is simulated and the predicted results are compared to the corresponding bench-scale experimental data. Two unit problems with an increasing level of complexity are proposed to break down the complex physical/chemical processes of solvent-based CO 2 capture into relatively simpler problems to separate the effects of physical transport and chemical reaction. This paper focuses on the calibration and validation of the first unit problem, i.e., the CO 2 mass transfer across a falling ethanolamine (MEA) film in the absence of chemical reaction. This problem is investigated both experimentally and numerically using non-reactive nitrous oxide (N 2 O) as a surrogate for CO 2 . To capture motion of the gas-liquid interface, a volume of fluid method is employed with a one-fluid formulation to compute the mass transfer between the two phases. Parallel bench-scale experiments are designed and conducted to validate and calibrate the CFD models using a general Bayesian calibration approach. Two important transport parameters, Henry's constant and gas diffusivity, are calibrated to produce the posterior distributions, which will be used as input for the second unit problem to address the chemical absorption of CO 2 across the MEA falling film, where both mass transfer and chemical reaction are involved. Finally, mass transfer coefficients predicted by CFD are also compared with those predicted by the traditional/empirical correlations under both steady and wavy falling film conditions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Amphilic Water-Lean Carbon Capture Solvent Wetting Behavior through Decomposition by Stainless-Steel Interfaces

In this work, we report on a combined experimental and theoretical study of the wetting and reactivity of water-lean carbon capture solvents on the surface of common column packing materials. Paradoxically, we find that these solvents are equally able to wet hydrophobic and hydrophilic surfaces. The solvents are amphiphilic and are able to adapt to any interfacial environment due to their inherent heterogeneous molecular structure. Ab initio molecular dynamics indicates that these structures enable the formation of a strong adlayer on the surface of hydrophilic surfaces like oxidized steel which promotes solvent decomposition akin to hydrolysis from surface oxides and hydroxides. This decomposition passivates the surface, making it effectively hydrophobic, and the decomposed solvent promotes leaching of the iron into the bulk fluid. This study links the wetting behavior to the observed corrosion of the steels via decomposition of solvent at steel interfaces. The overall affect is strongly dependent on the chemical composition of the solvent, in that amines are stable, whereas imines and alcohols are not. We also observed that plastic packing shows little to no solvent degradation, but an equal degree of wetting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1995

Reactively Deposited Aluminum Oxide and Fluoropolymer Filled Aluminum Oxide Protective Coatings for Polymers

Reactive ion beam sputter deposition of aluminum simultaneous with low energy arrival of oxygen ions at the deposition surface enables the formation of highly transparent aluminum oxide films. Thick (12 200 A), adherent, low stress, reactively deposited aluminum oxide films were found to provide some abrasion resistance to polycarbonate substrates. The reactively deposited aluminum oxide films are also slightly more hydrophobic and more transmitting in the UV than aluminum oxide deposited from an aluminum oxide target. Simultaneous reactive sputter deposition of aluminum along with polytetrafluoroethylene (PTFE Teflon) produces fluoropolymer-filled aluminum oxide films which are lower in stress, about the same in transmittance, but more wetting than reactively deposited aluminum oxide films. Deposition properties, processes and potential applications for these coatings will be discussed.

Rutledge, Sharon K.↗
DOE OSTI2013

Density functional simulations as a tool to probe molecular interactions in wet supercritical CO2

Recent advances in mixed Gaussian and plane wave algorithms have made possible the effective use of density functional theory (DFT) in ab initio molecular dynamics (AIMD) simulations for large and chemically complex models of condensed phase materials. In this chapter, we are reviewing recent progress on the modeling and characterization of co-sequestration processes and reactivity in wet supercritical CO2 (sc-CO2). We examine the molecular transformations of mineral and metal components of a sequestration system in contact with water-bearing scCO2 media and aim to establish a reliable correspondence between experimental observations and theory models with predictive ability and transferability of results in large scale geomechanical simulators. This work is funded by the Department of Energy, Office of Fossil Energy. A portion of the research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory. The Pacific Norhtwest National Laboratory (PNNL) is operated by Battelle for DOE under contract DE-AC06-76RL01830.

Glezakou, Vassiliki Alexandra↗
DOE OSTI2019

Quantitative Review of Olivine Carbonation Kinetics: Reactivity Trends, Mechanistic Insights, and Research Frontiers

Magnesium-dominant olivine (Mg2SiO4) has received considerable attention for geologic and ex situ carbon mineralization due to its reaction potential with CO2 and its abundance in mafic and ultramafic rocks. To enable better predictions and optimization of its carbonation rate, here we compile the results of 15 separate studies into an internally consistent kinetic framework. Time-dependent transformation curves were determined, analyzed, and used to calculate temperature-dependent carbonation rate constants from 50-300 °C. The unified results clearly show that olivine carbonation is optimized at 185-200 °C, and indicate a change in the carbonation reaction mechanism above 90 °C. By comparison with related efforts focused solely on olivine dissolution rates, we demonstrate that the kinetics are controlled by growth of magnesium carbonates. Additional outcomes include the identification of important knowledge gaps and research frontiers for carbon mineralization, including those related to unraveling competitive serpentinization reactions, H2O-saturated supercritical CO2 (wet scCO2) reactivity, and the formation and impacts of secondary surface coatings. In addition to supporting the deployment of carbon storage technologies in a climate-responding world, the findings may help improve understanding of how carbonation and serpentinization processes influence critical geochemical cycles.

Miller, Quin RS↗