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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 325 records · Page 18

Physical and Electrochemical Characterization of Aluminum Electrodes during Electrocoagulation

Electrocoagulation (EC) of synthetic groundwater was conducted using a sacrificial aluminum electrode in a flow-through EC reactor with short retention times (<1 min) under varying hydrodynamic and electrochemical conditions. The treated water was allowed to settle for 24 h and achieved silicate removal of up to 50 ± 4%, and hardness removal of 11 ± 1%. Physical, chemical, and electrochemical characterization was performed to explore changes in electrode surface morphology and composition. Electrochemical impedance spectroscopy (EIS) showed that chemical reactions at the electrode/water interface are sensitive to changes in the immediate chemical environment. We demonstrate that the most energy-intensive step in EC is aluminum dissolution at the anode, which remained fairly constant due to the continuous renewal of the anode’s surface, a result of aluminum dissolution. At the cathode, a structural change in the oxide layer, from γ-Al 2 O 3 to gibbsite, was detected by grazing-incidence X-ray diffraction, which decreased the resistance to charge transfer at the cathode surface, resulting in decreased electrode resistance. The high flow rate in the system minimized the accumulation of aluminum hydroxide solids and aluminum ions at the electrode/water interface, which minimized the formation of thick scalants and amorphous Al(OH) 3 on the cathode and anode, respectively. In conclusion, it was further demonstrated by EIS that under these conditions the resistance to charge transfer was constant throughout the duration of the experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hybrid gels via bulk interfacial complexation of supramolecular polymers and polyelectrolytes

Hierarchical self-assembly leading to organized supramolecular structures across multiple length scales has been of great recent interest. Earlier work from our laboratory reported the complexation of peptide amphiphile (PA) supramolecular polymers with oppositely charged polyelectrolytes into a single solid membrane at a macroscopic interface. We report here the formation of bulk gels with many internal interfaces between the covalent and supramolecular polymer components formed by the rapid chaotic mixing of solutions, one containing negatively charged PA nanofibers and the other the positively charged biopolymer chitosan. We found that formation of a contact layer at the interface of the solutions locks the formation of hydrogels with lamellar microstructure. The nanofiber morphology of the supramolecular polymer is essential to this process since gels do not form when solutions of supramolecular assemblies form spherical micelles. Here, we found that rheological properties of the gels can be tuned by changing the relative amounts of each component. Furthermore, both positively and negatively charged proteins are easily encapsulated within the contact layer of the gel, which provides an interesting biomedical function for these systems.

36 MATERIALS SCIENCE↗

LIvermore SEM image Tools

Scanning Electron Microscopy (SEM) images provide a variety of structural and morphological information for the characterization of the nanomaterials. This code offers automatic recognition and quantitative analysis of SEM images in a high-throughput manner using computer vision and machine learning techniques. The main function of this application is to extract particle size and morphology information of overlapping nanoparticles and core-shell nanostructures in a user friendly interface. The code is written in C++ with QT environment, and has been tested on MacOSX.

KIM, HYOJIN↗

The earth's magnetosphere

A qualitative description of the general magnetospheric configuration is given, with emphasis on some of the physical processes governing the magnetosphere that are the main targets of current research. The magnetosphere behaves like a huge 'bag' of plasma and radiation that swells and contracts under the influence of the solar wind. The electric field, the magnetospheric plasma, the magnetospheric substorm, and the radiation belt and wave particle interactions are discussed. During the past 15 years, the study of the earth's magnetosphere man's immediate plasma and radiation environment - has undergone a successful stage of discovery and exploration. Investigators have obtained a morphological description of the magnetospheric field, the particle population embedded in it, and its interface with the solar wind, and have identified and are beginning to understand many of the physical processes involved. Quite generally, the magnetosphere reveals itself as a region where it is possible to observe some of the fundamental plasma processes at work that are known to occur elsewhere in the universe.

Roederer, J. G.↗

Effect of surface tension anisotropy on cellular morphologies

A three-dimensional weakly nonlinear analysis for conditions near the onset of instability at the crystal-melt interface was carried out to second order, taking into account the effects of latent heat generation and surface-tension anisotropy of the crystal-melt interface; particular consideration was given to the growth of a cubic crystal in the 001-, 011-, and 111-line directions. Numerical calculations by McFadden et al. (1987), performed for an aluminum-chromium alloy with the assumption of a linear temperature field and an isotropic surface tension, showed that only hexagonal nodes (and not hexagonal cells) occurred near the onset of instability. The results of the present analysis indicate that the nonlinear temperature field (which occurs when thermal conductivities of the crystal and the melt are different and/or the latent heat effects are not negligible) can modify this result and, for certain alloys and processing conditions, can cause the occurrence of hexagonal cells near the onset of instability.

Mcfadden, G. B.↗

Progressive Damage Failure Analysis of Post-Buckled Composite Single-Stringer Panel with Teflon Inserts

The high strength-to-weight and stiffness-to-weight ratio materials, such as laminated composites, are advantageous for modern aircraft. Laminated composites with initial flaws are susceptible to delamination under buckling loads. PDA tools help enhance the industry’s understanding of the mechanisms for damage initiation and growth in composite structures while assisting in the design, analysis, and sustainment methods of these composite structures. The global-local modeling approach for the single-stringer post-buckled panel was evaluated through this effort, using Teflon inserts to simulate the defect of damage during manufacturing. This understanding is essential for designing the post-buckled structure, reducing weight while predicting damage initiation location, and addressing a potential design review for future aircraft repairs. In this work, the initial damage was captured with Teflon inserts as the starting configuration; and any reference to the damage initiation refers to any damage beyond the “initial unbonded region.” The effort aims to develop, evaluate, and enhance methods to predict damage initiation and progression and the failure of post-buckled hat-stiffened panels using multiple Abaqus FEA Virtual Crack Closure Technique (VCCT) definitions. Validation of the PDA using the VCCT material model was performed on a large single-stringer panel subjected to compressive loading. The compressive loading of the panel caused the skin to buckle before any damage began to occur locally. In addition, comparisons are made for critical aspects of the damage morphology, such as a growth pattern that included delamination from the skin-stiffener interface to the skin and ply interfaces. When compared against the experimental data produced through the NASA Advanced Composites Project (ACP), the present model captured damage migration from one surface to another, and model validations were within 4% of the experimental data.

PDA↗

Fundamental Understanding of “Fresh” Lithium Nucleation and Growth in Sulfide-Based Anode-Free Solid-State Batteries: Effects of Substrate, Current Density, and Li + Supply

Understanding the electrochemical extraction and deposition of lithium (Li) from cathode is crucial for advancing anode-free solid-state batteries (AFSSBs). Herein, cryo-transmission electron microscopy (cryo-TEM) and electrochemical studies are employed to investigate how current collector surface properties, current densities, and cathode loadings influence the morphology of fresh electrochemically deposited Li and the electrochemical performance in sulfide-based AFSSBs. Cryo-TEM reveals that Cu current collectors induce irregular, dendritic Li deposits due to their lithiophobic nature and reactivity with Li 5.4 PS 4.4 Cl 1.6 (LPSC), while Ni and Au facilitate more uniform, planar-like Li growth. The morphology of the deposited Li also depends on current density: higher rates produce smaller, porous particles versus larger, denser deposits at lower rates. Importantly, for the first time, we discovered that low cathode loadings lead to poor cycling stability due to insufficient Li + supply for complete anode coverage, contrary to conventional solid-state batteries with preloaded Li metal anodes. This finding establishes a design principle where adequate cathode Li + reservoirs are essential for anode interface stability in AFSSBs. Overall, this work elucidates the interplayed effect of current collectors, current densities, and cathode loadings on Li morphology and cycle stability, offering fundamental insights into cathode-derived Li behavior and practical guidelines for optimizing AFSSBs performance through nucleation control and interface engineering.

25 ENERGY STORAGE↗

Influence of gravity driven convection on the directional solidification of Bi/MnBi eutectic composites

The role of gravity on Bridgman-Stockharger directional solidification of eutectic Bi/MnBi has been studied in reduced gravity aboard NASA sounding rocket SPAR flight experiments and contrasted with normal gravity investigations. The directional solidification of eutectic Bi/MnBi results in a low volume fraction, faceted/nonfaceted aligned rod eutectic whose MnBi rod size, interrod spacing, thermal and magnetic properties are sensitive functions of solidification processing conditions. The morphology of the low-gravity samples showed striking differences compared with identically processed, normal gravity samples grown in the same apparatus. The MnBi rod diameter and interrod spacing distributions were significantly smaller, approximately 50 percent, for the low gravity samples compared with identically processed one gravity samples. Accompanying the smaller MnBi rod diameters observed in the flight samples, was an increase in permanent magnet properties which reached greater than 97 percent of the theoretical maximum. Gravitationally induced thermal instabilities in one-gravity which result in irregular interface movement and associated difficulty of the faceted MnBi phase to branch are suggested to explain the morphological differences between one and low gravity solidification.

Pirich, R. G.↗

Self-similar mesocrystals form via interface-driven nucleation and assembly

Crystallization by particle attachment (CPA) is a frequently occurring mechanism of colloidal crystallization that results in hierarchical morphologies. CPA has been exploited to create nanomaterials with unusual properties and is implicated in the development of complex mineral textures. Oriented attachment–a form of CPA in which particles align along specific crystallographic directions–produces mesocrystals that diffract as single crystals do, although the constituent particles are still discernible. The conventional view of CPA is that nucleation provides a supply of particles that aggregate via Brownian motion biased by attractive interparticle potentials. However, mesocrystals often exhibit regular morphologies and uniform sizes. Although many crystal systems form mesocrystals and individual attachment events have been directly visualized10, how random attachment events lead to well defined, self-similar morphologies remains unknown, as does the role of surface-bound ligands, which are ubiquitous in nanoparticle systems. Attempts to understand mesocrystal formation are further complicated in many systems by the presence of precursor nanoparticles with a phase distinct from that of the bulk. Some studies propose that such particles convert before attachment, whereas others attribute conversion to the attachment process itself and yet others conclude that transformation occurs after the mesocrystals exceed a characteristic size. Here we investigate mesocrystal formation by iron oxides, which are important colloidal phases in natural environments and classic examples of systems forming ubiquitous precursor phases and undergoing CPA accompanied by phase transformations. Combining in situ transmission electron microscopy (TEM) at 80 degrees Celsius with ‘freeze-and-look’ TEM, we tracked the formation of haematite (Hm) mesocrystals in the presence of oxalate (Ox), which is abundant in soils, where iron oxides are common. In this work, we find that isolated Hm particles rarely appear, but once formed, interfacial gradients at the Ox-covered surfaces drive Hm particles to nucleate repeatedly about two nanometres from the surfaces, to which they then attach, thereby generating mesocrystals. Comparison to natural and synthetic systems suggests that interface-driven pathways are widespread.

36 MATERIALS SCIENCE↗

Novel inverse oxide/metal catalysts for methanol synthesis: impact of oxide–metal interactions and reversible morphological changes

Inverse oxide/metal catalysts have proved to be excellent systems for the generation of methanol by CO 2 hydrogenation or the partial oxidation of methane. These systems can exhibit unique structural and chemical properties due to the nano size of the oxide component and strong oxide–metal interactions. Recent studies for ZnO/Cu, CeO 2 /Cu, TiO 2/ Cu, MgO/Cu, In 2 O 3 /Cu, and In 2 O 3 /Au catalysts have shown large variations in the composition and morphology of the oxide overlayer as a function of temperature and chemical environment. These oxide–metal interfaces are able to react with CO 2 and CH 4 at room temperature, and both reactants have a strong influence on the physical and chemical properties of the catalysts. Under reaction conditions, switches between oxide–metal and metal–metal interfaces can take in the catalyst surface. A dynamic behavior that can be linked to a high selectivity for methanol production over systems such as ZnO/Cu, CeO 2 /Cu and In 2 O 3 /Au. Finally, this type of correlation deserves additional systematic studies since it could be a powerful tool for designing highly efficient catalysts for methanol synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Precision Subsampling System for Mars Surface Missions

The ability to analyze heterogeneous rock samples at fine spatial scales would represent a powerful addition to our planetary in situ analytical toolbox. This is particularly true for Mars, where the signatures of past environments and, potentially, habitability are preserved in chemical and morphological variations across sedimentary layers and among mineral pr.ases in a given rock specimen. On Earth, microbial life often associates with surfaces at the interface of chemical nutrients, and ultimately retains sub-millimeter to millimeter-scale layer confinement in fossilization. On Mars, and possibly other bodies, trace chemical markers (elemental, organic/molecular, isotopic, chiral, etc.) and fine-scale morphological markers (e.g., micro-fossils) may he too subtle, degraded, or ambiguous to be detected, using miniaturized instrumentation, without some concentration or isolation. This is because (i) instrument sensitivity may not be high enough to detect trace markers in bulk averages; and (ii) instrument s~lectiviry may not be sufficient to distinguish such markers from interfering/counteracting signals from the bulk. Moreover from a fundamental chemostratigraphic perspective there would be a great benefit to assessing specific chemical and stable isotopic gradients, over millimeter-to-centimeter scales and beyond, with higher precision than currently possible in situ. We have developed a precision subsampling system (PSS) that addresses this need while remaining relatively flexible to a variety of instruments that may take advantage of the capability on future missions. The PSS is relevant to a number of possible lander/rover missions, especially Mars Sample Return. Our specific PSS prototype is undergoing testing under Mars ambient conditions, on a variety of natural analog rocks and rock drill cores, using a set of complementary flight-compatible measurement techniques. The system is available for testing with other contact instruments that may benefit from precision sampling.

Mahaffy, P. R.↗

Transient Mixing Driven by Buoyancy Flows

Mixing driven by buoyancy-induced flows is of particular interest to microgravity processes, as the body force that governs the intensity of flow fields can be directly controlled. We consider a model experimental system to explore the dynamics of mixing which employs two miscible liquids inside a cavity separated initially by a divider. The two liquids are oriented vertically inside a rectangular cavity with constant width and height, and varying depths to span the range of a Hele-Shaw cell to a 3-[) configuration. The two miscible liquids can be sufficiently diluted and died, for example water and deuterium oxide, such that a distinct interface exists across the divider. The transient mixing characteristic of the two fluids is addressed by following the Lagrangian history of the interface for various aspect ratios in the z-plane (depth variation) as well as a range of pulling velocities of the divider. The mixing characteristics of the two fluids are quantified from measurement of the length stretch of the interface and its flow field using respectively image processing techniques and Particle Imaging Velocimetry. Scaling analysis shows that the length stretch depends on four governing parameters, namely the Grashof number (Gr), Schmidt number (Sc), aspect ratio (Ar), and Reynolds number (Re). Variation of the Schmidt number is taken into account through thermophysical property variation. Thus our problem reduces to a codimension three bifurcation in parametric space for Gr, Ar, and Re. Our experimental results show that for Gr on the order of 106 and a nominal cavity aspect ratio Ar = 0.2, the net effect of removal of the divider and the overwhelming buoyancy force causes an overturning motion which stretches and folds the interface to produce ml internal breakwave. The structure of the breakwave is similar to the ubiquitous Rayleigh-Taylor instability morphology. The breakwave is dissipated either through internal or wall collision depending on the impulsive velocity of the divider as prescribed by the Reynolds number. The decay of the collision event occurs through sloshing oscillations over a short time scale. The two fluids then become stably stratified with a diffusive band at the interface indicating local mass transport. The local bifurcation of the internal breakwave is investigated as a function of aspect ratio. Results show that for narrow cavities on the order of 2mm (Ar = 0.04) folding does not occur, the interface only stretches. As the cavity size increases folding occurs through a supercritical bifurcation. Insight into the mechanism of folding is obtained from measurement of the flow field which shows that in the neighborhood of the folding event, there exists hyperbolic points caused by multiple vortex interactions. The global length stretch of the interface as a function of time is nearly Gaussian; calculations of finite-time Liapunov exponents as well as construction of horseshoe maps indicate the likelihood of a chaotic transient.

W.M.B. Duval↗

The Impact of Lithium Anode Interface on Capacity Fade in Polymer Electrolyte-Based Solid-State Batteries

This study investigates the Li stripping-plating morphology and failure mechanisms in full cells consisting of a solid polymer electrolyte (SPE) with two commercial Li anodes: Li chip and Li foil. The primary identified failure mechanism of the SPE cell is capacity fade, regardless of the Li manufacturer. While the cathode’s role in capacity fade is evident, the Li anode significantly influences cycling performance, with Li foil cells cycling 50% longer than Li chip cells, a statistical difference. Further, post-mortem scanning electron microscopy and X-ray photoelectron spectroscopy results attribute the Li chip’s faster capacity fade to a loss of contact and continuous growth of the solid electrolyte interphase (SEI). Conversely, Li foil maintains consistent contact with the solid polymer, displaying a thin and stable SEI. Additionally, failure mechanisms between a gel electrolyte in previous work and the dry SPE are compared.

25 ENERGY STORAGE↗

Orientation matters: Measuring the correct surface of polyamide membranes with quartz crystal microbalance

The surface of polyamide reverse osmosis (RO) membranes which regulates interface-dominated phenomena, such as partitioning and fouling, is the one facing the feed during operation. However, the opposite surface of the polyamide selective layer, the one facing the permeate and in contact with the polysulfone porous support, is commonly analyzed in quartz crystal microbalance (QCM) measurements due to limitations of state-of-the-art transfer methodologies. Such measurements on the back surface cannot be generalized because the polyamide layer is chemically and morphologically asymmetric. Herein, we introduce a simple method to coat QCM sensors with polyamide active layers in the correct orientation (i.e., exposing their front surface) and show that interface-dominated phenomena differ significantly between orientations. We start by describing a transfer protocol to coat any surface with a polyamide layer on its front surface orientation. We then systematically analyze the chemical and morphological differences between the two surfaces of the polyamide layer of a commercial RO membrane. Finally, we demonstrate that interface-dominated phenomena depend on the orientation by showing that NaCl partitioning at pH 6 was 1.3 to 2.3-fold higher on the front surface and that organic fouling with humic acid occurred at a lower rate on this surface. The new method presented herein enables measurements on the front surface of polyamide RO membranes, which should be the standard in any future QCM studies.

Fouling behavior↗

Ferro-ionic states and domains morphology in Hf x Zr 1–x O 2 nanoparticles

Unique polar properties of nanoscale hafnia-zirconia oxides (Hf x Zr 1–x O 2 ) are of great interest for condensed matter physics, nanophysics, and advanced applications. These properties are connected (at least partially) to the ionic–electronic and electrochemical phenomena at the surface, interfaces, and/or internal grain boundaries. Here, we calculated the phase diagrams, dielectric permittivity, spontaneous polar, and antipolar ordering, as well as the domain structure morphology in Hf x Zr 1–x O 2 nanoparticles covered by ionic–electronic charge originating from surface electrochemical adsorption. We revealed that the ferro-ionic coupling supports the polar long-range order in nanoscale Hf x Zr 1–x O 2 , induces, and/or enlarges the stability region of the labyrinthine domains toward smaller sizes and smaller environmental dielectric constant at low concentrations of the surface ions. The ferro-ionic coupling causes the transition to the single-domain ferro-ionic state at high concentrations of the surface ions. We predict that the labyrinthine domain states, being multiple-degenerated, may significantly affect the emergence of the negative differential capacitance state in the nanograined/nanocrystalline Hf x Zr 1–x O 2 films.

36 MATERIALS SCIENCE↗

Surface Reconstruction in Hydrated Amphiphilic Block Copolymer Thin Films Probed by Fluid Cell Atomic Force Microscopy

In many thin film materials, nuanced interplays of interfacial energies control the surface morphology and rearrangement. This work evaluates polymer−solvent interactions and solvent-driven surface reconstructions via ex situ and in situ fluid cell Atomic Force Microscopy (fc-AFM) analysis of amphiphilic block copolymer (BCP) thin films upon exposure to deionized (DI) water. We examine the differences in surface morphology, whole-film swelling, and force response in thin films of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) and polystyrene- block-poly[(allyl glycidyl ether)-co-(ethylene oxide)] (PS-b- P[AGE-co-EO]) processed into standing-up cylinder morphologies perpendicular to a silicon substrate (⊥C). Using Amplitude Modulation AFM (AM-AFM) and Amplitude-Phase Distance (APD) force spectroscopy, this work probes the mechanoresponsive nature of the dynamic surface layers of these films, unveiling surface layer stratification and surface chain rearrangement via minimal tip−sample stimulation. To help rationalize the observed reconfigurations, the energetic driving forces were estimated using the harmonic mean approximations of interfacial energies. Given the nonionizable nature of the minority P(AGE-co-EO) block and the energetic driving forces for chain mobility, this work shows how the elimination of unfavorable PS−water interfaces drives chain rearrangement and coverage of the PS surface by chains of the hydrophilic block. This work highlights considerations for increasing the heterogeneity and complexity of BCP thin films via random blocks and how those changes to local interfacial energies may drive larger scale film morphology reconstructions, with broader implications for tuning interface hydrophilicity.

Copolymers↗

Insights into Heterogeneous Catalysts under Reaction Conditions by In Situ/Operando Electron Microscopy

The advancement of clean energy and environment depends strongly on the development of efficient catalysts in a wide range of heterogeneous catalytic reactions, which has benefited from transmission electron microscopic techniques in determining the atomic-scale morphologies and structures. However, it is the morphology and structure under the catalytic reaction conditions that determine the performance of the catalyst, which has captured a surge of interest in developing and applying in situ/operando transmission electron microscopic techniques in heterogeneous catalysis. The major theme of this review is to highlight some of the most recent insights into heterogeneous catalysts under the relevant reaction conditions using in situ/operando transmission electron microscopic techniques. Rather than a comprehensive overview of the basic principles of in situ/operando techniques, this review focuses on the insights into the atomic-scale/nanoscale details of various catalysts ranging from single-component to multicomponent catalysts under heterogeneous catalytic, electrocatalytic, and photocatalytic reaction conditions involving both gas–solid and liquid–solid interfaces. Here, this focus is coupled with discussions of the correlation of the atomic, molecular, and nanoscale morphology, composition, and structure with the catalytic properties under the reaction conditions, shining light on the challenges and opportunities in design of nanostructured catalysts for clean and sustainable energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Effect of Solidification Rate on Morphological Stability

At low solidification rates, the criterion for the onset of morphological instability parallels closely the criterion of constitutional supercooling. At somewhat larger rates of solidification, however, the results of the perturbation theory of morphological instability differ significantly from the predictions of constitutional supercooling. This arises because the critical wave length for instability decreases as solidification rate increases and thus the effects of capillarity (solid-liquid surface tension) play a strong stabilizing role. This gives rise to the concept of absolute stability, according to which the system will always be stable for a sufficiently large rate of solidification. This enhanced stabilization by capillarity is present only so long as local equilibrium is maintained at the solid-liquid interface. If the interfacial temperature drops below its equilibrium value by an amount dependent on growth rate, oscillatory morphological instabilities can occur. The differences among these various stability criteria are illustrated by means of some simple two-dimensional diagrams that should supplant the conventional plots of (temperature gradient)/(growth rate) vs. alloy concentration.

Sekerka, R. F.↗