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Results for “interfacial characterization”

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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Investigation of interfacial strength in nacre-mimicking tungsten heavy alloys for nuclear fusion applications

Abstract Tungsten heavy alloys have been proposed as plasma facing material components in nuclear fusion reactors and require experimental investigation in their confirmation. For this purpose, a 90W–7Ni–3Fe alloy has been selected and microstructurally manipulated to present a multiphase brick-and-mortar structure of W-phase ‘bricks’ surrounded by a ductile ‘mortar’. This work draws inspiration from nature to artificially imitate the extraordinary combination of strength and stiffness exhibited by mollusks and produce a nacre-mimicking metal matrix composite capable of withstanding the extremely hostile environment of the reactor interior and maintaining structural integrity. The underlying mechanisms behind this integrity have been probed through high-resolution structural and chemical characterization techniques and have revealed chemically diffuse phase boundaries exhibiting unexpected lattice coherency. These features have been attributed to an increase in the energy required for interfacial decohesion in these systems and the simultaneous expression of high strength and toughness in tungsten heavy alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Characterization of Lanthanum Monazite Surface Chemistry and Crystal Morphology through Density Functional Theory and Experimental Approaches

Monazite is a rare earth element (REE)-containing mineral that consists of (REE)PO 4 formal units and is one of the most important sources of these critical materials. The concentration of REEs from mined monazite ore often involves froth flotation, which is a beneficiation process that enhances the efficiency of downstream processing. The effectiveness of froth flotation is largely governed by the ability of collector agents to selectively bind to monazite particles. Thus, a molecular-level understanding of monazite interfacial chemistry is integral to the design of effective collector agents. To address this need, we performed density functional theory (DFT) calculations and a variety of experimental techniques to characterize La-monazite and elucidate its crystal morphology. Interestingly, we find minimal differences in the predicted morphologies of La-monazite for hydrous and anhydrous environments, which are largely dominated by low-index facets (e.g., {110}, {100}, and {010}). Indexing of synthesized La-monazite crystals via X-ray diffraction also uncovers {110} and {100} as the predominant facets. The average surface energies of 0% and 100% water coverage La-monazite crystals were predicted to be 0.87 and 0.76 J/m 2 , respectively, while calorimetry suggests values of 1.30 and 1.15 J/m 2 , respectively. The apparent discrepancies between the theoretical and experimental values are expected and attributed to defects present in physical crystals, in contrast to the perfect mineral surfaces in simulations. The difference in surface energy between the 0% and 100% water coverage morphologies predicted by theory is consistent with the value measured via calorimetry. DFT reveals a wide range of adsorption energies for water across the studied facets, but in all cases, water is predicted to strongly bind to monazite surfaces with an average adsorption energy of -92.7 kJ/mol for a La-monazite single crystal. Finally, this study provides the groundwork necessary for the rational design of froth flotation collector agents by granting molecular-level insight into the predominant facets of monazite.

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

Quantifying the dislocation content of atomically resolved grain boundary line defects using the Nye tensor

The Nye tensor, which quantifies the density of Burgers vector for a given dislocation line direction, can be effectively used to characterize dislocation content in bulk crystals from atomic-resolution transmission electron microscopy images. The Nye tensor can be calculated from these images, in part because the reference state is simply defined by the lattice of the perfect crystal. The application of the Nye tensor to interfacial line defects, for which the natural reference state is the dichromatic pattern of the two grains in their reference orientation, poses additional challenges. In this work, we present a method that employs the Nye tensor to characterize the edge dislocation content of line defects at grain boundaries from atomic-resolution images. This approach enables us to rapidly characterize all edge dislocation content along a grain boundary. Additionally, the Nye tensor provides information about line defect core structure. Finally, we demonstrate this method on two exemplar defects: a twin boundary disconnection and a facet junction in face-centered cubic Au.

Crystallographic defects↗
DOE OSTI2022

Sensitivity of the strength and toughness of concrete to the properties of the interfacial transition zone

We report Civil infrastructure is made primarily of concrete structures or components and therefore understanding durability and fracture behavior of concrete is of utmost importance. Concrete contains an interfacial transition zone (ITZ), a porous region surrounding the aggregates, that is often considered to be the weakest region in the concrete. The ITZ is poorly characterized and property estimates for the ITZ differ considerably. In this simulation study, representative concrete mesostructures are produced by packing coarse aggregates with realistic geometries into a mortar matrix. A meshless numerical method, peridynamics, is utilized to simulate the mechanical response including fracture under uniaxial compression and tension. The sensitivity of the stiffness and fracture toughness of the samples to the ITZ properties is computed, showing strong relationships between the ITZ properties and the effective modulus and effective yield strength of the concrete. These results provides insight into the influence of the poorly characterized ITZ on the stiffness and strength of concrete. This work showcases the applicability of peridynamics to concrete systems, matching experimental strength and modulus values. Additionally, relationships between the ITZ’s mechanical properties and the overall concrete strength and stiffness are presented to enable future design decisions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Imaging transient solidification behavior

Solidification processing offers the first opportunity to control microstructure, properties, and performance in metallic alloy components. Until recently, microstructural evaluations were limited to post-solidification characterization by destructive methods. We review the development of time-resolved, in situimaging techniques capable of capturing solid-liquid interfacial evolution in metallic alloys with high spatial and temporal resolution underdiverse solidification conditions relevant for applications ranging from conventional directional solidification, crystal growth, and casting,to welding and additive manufacturing. These experiments enable direct visualization of transient behaviors that would otherwise remain unknown, uniquely providinginsights into the physics that impact microstructure and defect development and strategies for microstructuralcontrol and defect mitigation. Understanding microstructural evolution and the characteristics that form under various solidification conditions is essential for the development of multiscale, experimentallyinformed predictive modeling. This is highlightedby solidification simulations that utilize in situmeasurements of solidification dynamics from state-of-the-art experimental techniques.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effect of time and spatial domains on monolayer 2D material interface thermal conductance measurement using ns ET-Raman

Raman-based approaches to characterizing thermal properties of nanoscale and microscale materials have proven to be powerful experimental methods. Here, this work explores the potential of energy-transport state-resolved Raman (ET-Raman) for the precise determination of interfacial thermal conductance (G) between monolayer 2D materials and their substrates. ET-Raman employs a continuous wave laser and nanosecond (ns) pulsed laser to induce both steady state and transient heating while simultaneously collecting 2D material temperature information from the Raman signal. A 3D numerical model built using the finite volume method simulates the two differentiated thermal transport processes. The simulated temperature rises are compared with experimental Raman temperature information to extract G. In this study, we investigate the temporal effects of the pulse frequency and pulse width of the ns laser on precise characterization of G. By running multiple simulations for a range of pulsed laser frequencies and pulse widths, we determine that ET-Raman is most sensitive to precise interfacial thermal conductance measurements with short pulse widths (~below 20 ns) and with pulsing frequencies that ensure sufficient cooling time between consecutive pulses (~below 500 kHz). We also conclude that substrate thickness and laser spot size play critical roles in heat distribution and subsequent sensitivity to meaningful G measurements. As both laser spot size and SiO 2 substrate thickness decrease, detection of interfacial thermal transport becomes more difficult. These results offer essential guidance in the design of future Raman-based approaches to thermal measurements using pulsed lasers.

2D materials↗
DOE OSTI2024

One-Step Synthesis and Operando Electrochemical Impedance Spectroscopic Characterization of Heterostructured MoP–Mo 2 N Electrocatalysts for Stable Hydrogen Evolution Reaction

Here this study presents a novel synthesis of self-standing MoP and Mo 2 N heterostructured electrocatalysts with enhanced stability and catalytic performance. Facilitated by the controlled phase and interfacial microstructure, the seamless structures of these catalysts minimize internal resistivity and prevent local corrosion, contributing to increased stability. The chemical synthesis proceeds with etching step to activate the surface, followed by phosphor-nitriding in a chemical vapor deposition chamber to produce MoP-Mo 2 N@Mo heterostructured electrocatalysts. X-ray diffraction analyses confirm the presence of MoP, Mo 2 N, and Mo phases in the electrocatalyst. Morphology studies using scanning electron microscopy characterizes the hierarchical growth of structures, indicating successful formation of the heterostructure. X-ray photoelectron spectroscopy (XPS) analyses of the as-synthesized and post-catalytic activity samples reveal the chemical shift in terms of binding energy (BE) of Mo 3d XPS peak, especially after catalytic activity. The XPS BE shifts attributed to changes in oxidation state, electron transfer, and surface reconstruction during catalysis. Electrochemical evaluation of the catalysts demonstrates the superior performance of the MoP-Mo 2 N@Mo heterostructured catalyst in hydrogen evolution reactions (HER), with lower overpotentials and enhanced Tafel slopes. Stability tests reveal changes in double layer capacitance over time, suggesting surface reconstruction and increased active surface area during catalysis. Operando electrochemical impedance spectroscopy (EIS) further elucidates the dynamic changes in resistance and charge transfer during HER. Overall, comprehensive understanding of the synthesis, characterization, and electrochemical behavior of the developed MoP-Mo 2 N@Mo heterostructured electrocatalyst as presented in this paper highlights their potential utilization in sustainable energy applications.

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

Hierarchical Materials from High Information Content Macromolecular Building Blocks: Construction, Dynamic Interventions, and Prediction

Hierarchical materials that exhibit order over multiple length scales are ubiquitous in nature. Because hierarchy gives rise to unique properties and functions, many have sought inspiration from nature when designing and fabricating hierarchical matter. More and more, however, nature’s own high-information content building blocks, proteins, peptides, and peptidomimetics, are being coopted to build hierarchy because the information that determines structure, function, and interfacial interactions can be readily encoded in these versatile macromolecules. Here, we take stock of recent progress in the rational design and characterization of hierarchical materials produced from high-information content blocks with a focus on stimuli-responsive and “smart” architectures. We also review advances in the use of computational simulations and data-driven predictions to shed light on how the side chain chemistry and conformational flexibility of macromolecular blocks drive the emergence of order and the acquisition of hierarchy and also on how ionic, solvent, and surface effects influence the outcomes of assembly. Furthermore, continued progress in the above areas will ultimately usher in an era where an understanding of designed interactions, surface effects, and solution conditions can be harnessed to achieve predictive materials synthesis across scale and drive emergent phenomena in the self-assembly and reconfiguration of high-information content building blocks.

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

Elucidating Compositional Differences in Halide Perovskites for Normal and Inverted Perovskite Solar Cells

Over the recent few years, extensive research efforts have shifted from normal (n-i-p) to inverted (p-i-n) perovskite solar cells (PSCs), owing to their promising efficiency and operational stability, enabled by low-temperature processing. Despite a fundamentally identical operation principle (only structurally inverted), the optimized perovskite compositions for normal and inverted PSCs differ significantly across the literature, suggesting an underlying design principle for perovskite composition. Here, we unveil the role of cesium cation in enhancing interfacial contact between the perovskite layer and the underlying hole-transporting layer (HTL) in inverted PSCs. Comprehensive in situ and device characterization reveal that cesium incorporation promotes the formation of initial nucleation seeds for heterogeneous nucleation at the perovskite/hydrophobic HTL interface, thereby improving their contact. The resulting compositional heterogeneity explains the focus of recent studies on resolving this issue. This study provides mechanistic insight into designing perovskite compositions to further enhance the performance and longevity of PSCs.

Park, Keonwoo↗
DOE OSTI2020

Characterization and engineering of a two-enzyme system for plastics depolymerization

Significance Deconstruction of recalcitrant polymers, such as cellulose or chitin, is accomplished in nature by synergistic enzyme cocktails that evolved over millions of years. In these systems, soluble dimeric or oligomeric intermediates are typically released via interfacial biocatalysis, and additional enzymes often process the soluble intermediates into monomers for microbial uptake. The recent discovery of a two-enzyme system for polyethylene terephthalate (PET) deconstruction, which employs one enzyme to convert the polymer into soluble intermediates and another enzyme to produce the constituent PET monomers (MHETase), suggests that nature may be evolving similar deconstruction strategies for synthetic plastics. This study on the characterization of the MHETase enzyme and synergy of the two-enzyme PET depolymerization system may inform enzyme cocktail-based strategies for plastics upcycling.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Characterization of the structure and chemistry of the solid–electrolyte interface by cryo-EM leads to high-performance solid-state Li-metal batteries

Solid-state lithium-metal (Li 0 ) batteries are gaining traction for electric vehicle applications because they replace flammable liquid electrolytes with a safer, solid-form electrolyte that also offers higher energy density and better resistance against Li dendrite formation. Solid polymer electrolytes (SPEs) are highly promising candidates because of their tunable mechanical properties and easy manufacturability; however, their electrochemical instability against lithium metal (Li 0 ), mediocre conductivity, and poorly understood Li 0 /SPE interphases have prevented extensive application in real batteries. In particular, the origin of the low Coulombic efficiency (CE) associated with SPEs remains elusive, as the debate continues as to whether it originates from unfavored interfacial reactions or lithium dendritic growth and dead lithium formation. In this work, we use state-of-the-art cryo-electromicroscopy (cryoEM) imaging and spectroscopic techniques to characterize the structure and chemistry of the interface between Li 0 and a polyacrylate-based SPE. Contradicting the conventional knowledge, we find that no protective interphase forms, owing to the sustained reactions between deposited Li dendrites and polyacrylic backbones and succinonitrile plasticizer. Due to the reaction induced volume change, large amounts of cracks form inside the Li dendrites with a stress corrosion-cracking behavior, indicating that Li0cannot be passivated in this SPE system. Based on this observation, we then introduce additive engineering leveraging on the knowledge of liquid electrolytes, and demonstrate that the Li 0 surface can be effectively protected against corrosion using fluoroethylene carbonate (FEC), leading to densely packed Li 0 domes with conformal and stable solid-electrolyte interphases (SEIs) films. Owing to the high room temperature ionic conductivity of 1.01 mS/cm -1 , the high transference number of 0.57 and the stabilized lithium electrolyte interface, this improved new SPE delivers an excellent lithium plating/stripping CE of 99% and 1800 hours of stable cycling in Li||Li symmetric cells (0.2 mA/cm -2 , 1mAh/cm -2 ). Furthermore, this improved cathodic stability along with the high anodic stability enables record high cycle life of >2000 cycles for Li||LiFePO 4 and >400 cycles for Li||LiCoO 2 full cells.

25 ENERGY STORAGE↗
DOE OSTI2020

Atomic-scale tuned interface of nickel-rich cathode for enhanced electrochemical performance in lithium-ion batteries

The Ni-rich layered LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC6 22 ) is one promising cathode for lithium-ion batteries (LIBs), but suffers from poor cycling stability under high cutoff potentials. The performance degradation was reflected as capacity fading and voltage drop, having their roots in instable interface of NMC622. Aimed at improving interfacial stability, in this study, we deposited nanoscale ZrO 2 coatings conformally over NMC622 cathodes using atomic layer deposition (ALD). We found that, under a high cutoff voltage (4.5 V), the ALD ZrO 2 coatings evidently improved the performance of NMC622 cathode, showing better cyclability and higher sustainable capacity. In addition, the ALD coatings dramatically boosted the rate capability of NMC622. All these compelling performance results are ascribed to the atomic-scale tunable ZrO 2 coatings via ALD, which create stable interface and thereby inhibit unfavorable evolutions. In the study, we utilize a suite of characterization tools and various analyses to clarify the effects of ALD ZrO 2 coatings. This study will be helpful for improving the performance of nickel-rich cathodes via interfacial engineering using ALD.

25 ENERGY STORAGE↗
DOE OSTI2025

Elucidating Electric Field-Induced Rate Promotion of Brønsted Acid-Catalyzed Alcohol Dehydration

Applied potentials have been demonstrated as a powerful tool to promote heterogeneous Brønsted acid catalysis by orders of magnitude, leveraging interfacial electric fields to stabilize protonated intermediates. However, the use of flat two-dimensional electrodes with inherently low active site densities limits the application of conventional thermochemical characterization techniques that can probe the nature of catalytic active sites. Here, we use kinetic analyses with an electrostatics-based model to elucidate the intricacies of potential-induced rate promotion, employing liquid-phase dehydration of 1-methylcyclopentanol catalyzed by carboxylic acid groups on carbon nanotubes as a probe system. By using a basket electrode to directly polarize catalyst powder, we demonstrate that thermocatalytic reaction rates can be promoted by 100,000-fold, exhibiting a log–linear dependence on applied potential with rate-potential scalings as high as 125 ± 4 mV per 10-fold rate increase. In agreement with model predictions, we show that lower ionic strengths attenuate potential sensitivity, resulting from a weakening of the interfacial electric field that interacts with the acidic proton. Furthermore, we experimentally confirm the model-predicted “isokinetic potential” (at ∼0.6 V vs Ag/AgCl)─the potential at which all rate scaling lines at various ionic strengths intersect, making the rate independent of ionic strength. Base titrations reveal that only ∼8% of the carboxylic acid sites are catalytically active, yet these same active sites are operational at the highest and lowest potentials. Collectively, our results provide a key methodology for modeling catalytic effects of electric fields, quantifying active sites under applied potential, and demonstrating fundamental principles of electric field-induced rate promotion.

Catalysts↗
DOE OSTI2025

Interface morphogenesis with a deformable secondary phase in solid-state lithium batteries

Here, the complex morphological evolution of lithium metal at the solid-state electrolyte interface limits performance of solid-state batteries, leading to inhomogeneous reactions and contact loss. Inspired by biological morphogenesis, we developed an interfacial self-regulation concept in which a deformable secondary phase dynamically aggregates at the interface in response to local electro-chemo-mechanical stimuli, enhancing contact. The stripping of a lithium electrode that contains 5 to 20 mole % electrochemically inactive sodium domains causes spontaneous sodium accumulation across the interface, with the sodium deforming to attain intimate electrical contact without blocking lithium transport. This process, characterized with operando x-ray tomography and electron microscopy, mitigates voiding and improves cycling at low stack pressures. The counterintuitive strategy of adding electrochemically inactive alkali metal to improve performance demonstrates the utility of interfacial self-regulation for solid-state batteries.

Yoon, Sun Geun [Georgia Institute of Technology, A↗
DOE OSTI2022

Mode I tensile fracture behavior of adhesively-bonded metal–metal, metal–CFRP, and CFRP–CFRP bi-material combinations analyzed by size effect method

Understanding the adhesive and interfacial fracture is important for developing and achieving better adhesive jointing in bi-materials, the location which becomes less vulnerable in engineered structure components. Still, to characterize the fracturing behavior of various adhesively-bonded materials, it was shown in this work that the Mode I fracture energies estimated from conventional methods (e.g., work-of-fracture, (modified) compliance calibration method, (modified) beam theory, etc.) can be strongly affected by adherent thickness, adhesive bond length, and material type. Consequently, this hindered the proper understanding of fracturing in adhesive jointing of bi-materials since the estimated fracture energies can exhibit unreasonable difference among various material combinations, thus leading to the confusion in the literature due to the unfair comparison on these non-objective results estimated by leveraging conventional methods on the specimens with different geometries. This work compared size effect method with conventional methods on the calculation of the Mode I fracture energies of metal-metal, metal-CFRP, and CFRP-CFRP material combinations via Double Cantilever Beam (DCB) tests. The results showed that the estimated fracture energies of various material combinations are not dependent on the specimen geometries. This aspect allowed the fair comparison particularly on the interfacial fracturing between metal/adhesive and CFRP/adhesive, and the difference was further explained and correlated with the damage morphology on the material surface after failure identified through three-dimensional profilometer.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Controlled electron transfer by molecular wires embedded in ultrathin insulating membranes for driving redox catalysis

Organic bilayers or amorphous silica films of a few nanometer thickness featuring embedded molecular wires offer opportunities for chemically separating while at the same time electronically connecting photo- or electrocatalytic components. Such ultrathin membranes enable the integration of components for which direct coupling is not sufficiently efficient or stable. Photoelectrocatalytic systems for the generation or utilization of renewable energy are among the most prominent ones for which ultrathin separation layers open up new approaches for component integration for improving efficiency. Recent advances in the assembly and spectroscopic, microscopic, and photoelectrochemical characterization have enabled the systematic optimization of the structure, energetics, and density of embedded molecular wires for maximum charge transfer efficiency. The progress enables interfacial designs for the nanoscale integration of the incompatible oxidation and reduction catalysis environments of artificial photosystems and of microbial (or biomolecular)-abiotic systems for renewable energy.

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

van der Waals Epitaxy Growth of Bi 2 Se 3 on a Freestanding Monolayer Graphene Membrane: Implications for Layered Materials and Heterostructures

Research on two-dimensional and layered materials has expanded over the past 2 decades because of their unique properties and application potential. The key hurdles in realizing this potential are the challenges in controlling their atomic structure and their incompatibility with existing semiconductor nanofabrication techniques. Here we report on high-quality van der Waals epitaxial growth and characterization of a layered topological insulator on freestanding monolayer graphene transferred to different mechanical supports. This “templated” synthesis approach enables direct interrogation of the interfacial atomic structure of the as-grown materials and opens a route toward creating device structures with more traditional semiconductor nanofabrication techniques.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A simple method for floating graphene oxide films facilitates nanoscale investigations of ion and water adsorption

Graphene oxide (GO) is a promising material for separations. Nanoscale GO thin films at the air/water interface are excellent experimental models to understand molecular-scale interactions of ions and water with GO. However, the characteristics of GO, such as functional groups and flake size, also affect the thin film properties making it difficult to make systematic studies with GO thin films. This paper reports a simple, reliable, and quick method of preparing ultra-thin GO films, irrespective of their origin, and demonstrates the new opportunities possible with the utilization of this method. The total amount of GO used to form the thin film is significantly less compared to previous examples in the literature, minimizing the dissolved GO in the subphase. X-ray reflectivity (XR) studies show that the majority of the GO film has 1.5 nm thickness over a macroscopic area (~100 cm 2 ) with very small roughness. Sum frequency generation (SFG) spectroscopy measurements show that H 2 O and D 2 O interact differently with GO films, a property that was not observed before. SFG data show that functional groups vary significantly between different commercially available GO samples. The differences are also characterized with XR at high resolution. X-ray fluorescence near total reflection (XFNTR) measurements show that these differences strongly affect ion adsorption and interfacial water behavior near GO, which are vital properties in separation applications. The results pave the way for future studies to elucidate the complex separation mechanisms with GO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗