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At least 1,225 records · Page 68

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

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

25 ENERGY STORAGE↗

Selected Area Manipulation of MoS 2 via Focused Electron Beam-Induced Etching for Nanoscale Device Editing

Here we demonstrate direct-write patterning of single and multilayer MoS 2 via a focused electron beam-induced etching (FEBIE) process mediated with the XeF 2 precursor. MoS 2 etching is performed at various currents, areal doses, on different substrates, and characterized using scanning electron and atomic force microscopies as well as Raman and photoluminescence spectroscopies. Scanning transmission electron microscopy reveals a sub-40 nm etching resolution and the progression of point defects and lateral etching of the consequent unsaturated bonds. The results confirm that the electron beam-induced etching process is minimally invasive to the underlying material in comparison to ion beam techniques, which damage the subsurface material. Single-layer MoS 2 field-effect transistors are fabricated, and device characteristics are compared for channels that are edited via the selected area etching process. The source–drain current at constant gate and source–drain voltage scale linearly with the edited channel width. Moreover, the mobility of the narrowest channel width decreases, suggesting that backscattered and secondary electrons collaterally affect the periphery of the removed area. Focused electron beam doses on single-layer transistors below the etching threshold were also explored as a means to modify/thin the channel layer. The FEBIE exposures showed demonstrative effects via the transistor transfer characteristics, photoluminescence spectroscopy, and Raman spectroscopy. While strategies to minimize backscattered and secondary electron interactions outside of the scanned regions require further investigation, here, we show that FEBIE is a viable approach for selective nanoscale editing of MoS 2 devices.

36 MATERIALS SCIENCE↗

Effect of the grain arrangements on the thermal stability of polycrystalline nickel-rich lithium-based battery cathodes

One of the most challenging aspects of developing high-energy lithium-based batteries is the structural and (electro)chemical stability of Ni-rich active cathode materials at thermally-abused and prolonged cell cycling conditions. Here, we report in situ physicochemical characterizations to improve the fundamental understanding of the degradation mechanism of charged polycrystalline Ni-rich cathodes at elevated temperatures (e.g., ≥ 40 °C). Using multiple microscopy, scattering, thermal, and electrochemical probes, we decouple the major contributors for the thermal instability from intertwined factors. Our research work demonstrates that the grain microstructures play an essential role in the thermal stability of polycrystalline lithium-based positive battery electrodes. We also show that the oxygen release, a crucial process during battery thermal runaway, can be regulated by engineering grain arrangements. Furthermore, the grain arrangements can also modulate the macroscopic crystallographic transformation pattern and oxygen diffusion length in layered oxide cathode materials.

36 MATERIALS SCIENCE↗

Pressure Actuated Leaf Seals for Improved Turbine Shaft Sealing

This presentation introduces a shaft seal in which leaf seal elements are constructed from slotted shim material formed and layered into a frusto-conical assembly. Limited elastic deflection of seal leaves with increasing system pressure close large startup clearance to a small, non-contacting, steady state running clearance. At shutdown seal elements resiliently retract as differential seal pressure diminishes. Large seal clearance during startup and shutdown provides a mechanism for rub avoidance. Minimum operating clearance improves performance and non-contacting operation promises long seal life. Design features of this seal, sample calculations at differential pressures up to 2400 psid and benefit comparison with brush and labyrinth seals is documented in paper, AIAA 2005 3985, presented at the Advanced Seal Technology session of the Joint Propulsion Conference in Tucson this past July. In this presentation use of bimetallic leaf material will be discussed. Frictional heating of bimetallic leaf seals during a seal rub can relieve the rub condition to some extent with a change in seal shape. Improved leaf seal rub tolerance is expected with bimetallic material.

Grondahl, Clayton↗

Generation of out-of-plane ferroelectric behavior in a one-atom-thick monolayer

Ferroelectricity with out-of-plane polarization has so far been found in several two-dimensional (2D) materials, including monolayers comprising three to five planes of atoms, e.g. α-In 2 Se 3 and MoTe 2 . Here, we explore the generation of out-of-plane polarization within a one-atom-thick monolayer material, namely hexagonal boron nitride. We performed density-functional-theory calculations to explore inducing ferroelectric-like distortions through incorporation of isovalent substitutional impurities that are larger than the host atoms. This disparity in bond lengths causes a buckling of the h-BN, either up or down, which amounts to a dipole with two equivalent energies and opposing orientations. We tested several impurities to explore the magnitude of the induced dipole and the switching energy barrier for dipole inversion. The effects of strain, dipole–dipole interactions, and vertical heterostructures with graphene are further explored. Our results suggest a highly-tunable system with ground state antiferroelectricity and metastable ferroelectricity. Finally, we expect that this work will help foster new ways to include functionality in layered 2D-material-based applications.

36 MATERIALS SCIENCE↗

Biocompatible Electrostatic Layered Systems for Viral Elimination in the Nose/Throat

An anti-viral coating for the nose & throat is needed to quickly address the spread of COVID-19 infections and to aid future pandemics. Current nasal delivery systems are typically a 1-spray homogenous solution, which is convenient but may not be as efficient or durable as a multi-spray solution that contains a binding layer to anchor the anti-viral components. Many of the current nasal solutions being investigated to aid in pandemic response have solution-based mechanisms of action and are quickly cleared from the nose/mouth limiting their efficacy lifetime. A multi-spray approach utilizing strong intermolecular forces between polymeric materials and anti-viral agents to provide a robust biocompatible coating is expected to have increased physical and chemical properties to combat viral infection. This work evaluated which tailored biocompatible materials are needed to generate a layered system to combat viral infection. This layered system takes advantage of electrostatic interactions to bind anti-viral components, shown in Figure 1. Proof of concept success was demonstrated through cell toxicity studies and anti-viral assays on both the individual layer components and the complete layered system. Project work began with chemical modifications of Xantham Gum to hydrolyzing xanthan gum to give a negatively charged polymer with varying degrees of ionic character and investigate bonding efficiencies. However, this was abandoned in favor of comparing COTS available materials listed in Table 1 (Results section). Concentration and adhesion studies were performed on layers created using the listed polymeric materials and anti-viral agents. Finally, biocompatibility of materials, layers, and coating system were confirmed through cytotoxicity studies and the efficacy of the anti-viral properties tested with phi6 bacteriophage as a SARS-CoV2 surrogate.

36 MATERIALS SCIENCE↗

Two-dimensional parametric design of short pulse laser driven iron opacity experiments

High intensity short pulse lasers are commonly used to create high temperature and high density plasmas. These plasmas are used to study fundamental properties such as the equation of state and opacity. The targets often use small-diameter, thin buried layers of the materials of interest, surrounded by a tamper of low atomic number material such as plastic. Computational modeling is used to design and interpret experiments with short pulse lasers. Most of the modeling to date has assumed one-dimensional plane-parallel geometry. In this paper, the effects of radial gradients in the irradiation of thin planar targets are studied with one- and two-dimensional radiation/hydrodynamic simulations. It is found that the main effect of radial gradients is the averaging of plasma conditions and x-ray emission over the pattern of irradiation. Additionally, differences between one- and two-dimensional simulations arise because the plasma conditions and x-ray emission are, in general, nonlinear functions of the temperature of the plasma and thereby also nonlinear functions of the irradiation intensity. The differences increase with the ratio of the buried layer radius to the laser spot radius. The root mean square difference in the inferred iron L-shell opacity is less than 30% when the ratio is less than 1.0 and about 70% when the ratio is 1.5.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Air Force future technical requirements for silicon

Technical requirements for silicon-based bulk materials are presented, and related work on other materials and on thin layer silicon is summarized. Programs supported by the Wright-Patterson materials laboratory and the capabilities of the materials laboratory in house characterization facility are listed.

Hemenger, P. M.↗

FCET Solid Oxide Fuel Cell Testing and Development (CRADA 526) (Final Report)

Pacific Northwest National Laboratory (PNNL) tested electrolyte coatings from Fuel Cell Enabling Technologies, Inc. (FCET) for use in solid oxide fuel cells (SOFCs). The key technology held by FCET is a process to deposit thin layers of oxide materials, less than 1 μm in thickness. The range of possible materials that can be deposited with their method is broad, but this project focused on the gadolinium-doped ceria (GDC) and yttria-stabilized zirconia (YSZ) electrolytes for SOFCs. Thin, gas tight electrolyte membranes have been a long-sought target in SOFC research. The thinner the electrolyte, the lower the cell resistance, and the higher performance of the cell (or the lower the operating temperature). A YSZ thickness of 1 μm would be a step change from the state-of-the-art, tape-cast electrolytes (~10 μm). An in-house prototype SOFC stack from FCET was first tested. The sealing geometry of the prototype stack was determined to be problematic, and testing shifted to button cells. Anode-supported solid oxide electrolysis cell (SOEC) button cells without an electrolyte layer were produced at PNNL and sent to FCET for coating with electrolyte. Three cells were tested with a gadolinium-doped ceria (GDC) electrolyte applied via spin coating. GDC was chosen for its conductivity at lower temperatures than YSZ. All three cells failed during initial reduction under hydrogen at 600°C. Testing then shifted to YSZ, which is the standard SOFC electrolyte. Several button cells were coated with YSZ and examined with scanning electron microscopy (SEM). A promising coating of ~1 mm thickness was observed under SEM. A similarly coated button cell was tested and failed similarly to previous tests during reduction at 600°C. The YSZ coating appeared dense and uniform in SEM analysis. The roughness of the underlying Ni/YSZ anode is on the order of 1 μm, and that may have compromised the gas-tightness of the coating. Further development is warranted to understand and refine the coating process. Thin YSZ applied via this spin-coating technique could be used as a low-cost, drop-in replacement in large-scale SOFC manufacturing processes, improving cell performance and lowering the cost per watt of SOFCs.

30 DIRECT ENERGY CONVERSION↗

Introduction to Tools and Techniques for Surface Sampling on Europa

The NASA Jet Propulsion Laboratory (JPL) is studying excavation and collection of a sample from an icy surface for a potential landed mission to Europa. Europa presents unique challenges in planetary sampling. Very little is known about the local topography and material composition of the surface. The environmental conditions of being cryogenically cold (80-130K), low gravity (~1/7th Earth), no atmosphere, low lighting conditions, and limited ground in the loop opportunities have forced JPL to look at sampling differently than past missions. Interacting with the surface of the Jovian moon requires a sampling system that is robust to local topography on the scale of the lander and/or the tool. In addition, the sampling system must be capable both of detecting faults and automatically adjusting to them to achieve the mission objectives without ground in the loop feedback. Presented here is an overview of a sampling system concept that involves a two-stage approach for collecting a sample. The first stage uses an excavation tool to prepare the surface site for sample collection by removing the top layer of irradiated material and clearing tailings from the hole. The second stage then generates and collects a sample for delivery to instruments on-board a lander. Also presented is an introduction for how autonomy and sensing technologies might be employed to enable mission success.

Tevere, Erica L.↗

Mechanical Properties of Degraded PMR-15 Resin

Thermo-oxidative aging produces a non-uniform degradation state in PMR-15 resin. A surface layer, usually attributed to oxidative degradation, forms. This surface layer has different properties from the inner material. A set of material tests was designed to separate the properties of the oxidized surface layer from the properties of interior material. Test specimens were aged at 316 C in either air or nitrogen, for durations of up to 800 hours. The thickness of the oxidized surface layer in air aged specimens, and the shrinkage and Coefficient of Thermal Expansion (CTE) of nitrogen aged specimens were measured directly. Four-point-bend tests were performed to determine modulus of both the oxidized surface layer and the interior material. Bimaterial strip specimens consisting of oxidized surface material and unoxidized interior material were constructed and used to determine surface layer shrinkage and CTE. Results confirm that the surface layer and core materials have substantially different properties.

Tsuji, Luis C.↗

Multifunctional Nanofiber Reinforcement for Improved Thermomechanical and Chemical Stability of Perovskite Solar Cells

This project focused on the development of metal halide perovskite-polymeric nanofiber nanocomposites for robust and efficient solar cells. Metal halide perovskite solar cells are a potentially disruptive technology with high efficiencies and low-cost solution processability amenable with roll-to-roll fabrication of flexible devices. However, perovskites exhibit extreme brittleness, high internal film stresses, and chemical instabilities that significantly limit service lifetimes under normal operating conditions. To date, most work addressing these shortcomings has been focused on encapsulating devices between thick layers of rigid materials such as glass, which increases the total weight and cost of devices. Furthermore, these rigid and heavy encapsulants do not translate well to emerging solar markets vital for national security, including integrated mobile power, emergency deployments for disaster relief and military engagement, and lightweight power for space. It is therefore critical to improve the thermomechanical and chemical stability of perovskite devices in a way that is compatible with flexible and lightweight substrates. In this project, we integrated nylon-6,6 nanofibers into MAPbI3 to mechanically reinforce the perovskite, demonstrating films that exhibited fracture energies 5-fold greater than pristine MAPbI3 while also maintaining similar power conversion efficiencies due to beneficial light scattering effects from the polymeric nanofibers. These results required successful development of approaches to control the deposition thickness of nanofiber mats down to 100s of nanometers, and to ensure the polymer nanofibers did not inhibit charge transport to the at the perovskite-transport layer interface.

14 SOLAR ENERGY↗

Uncovering the phonon spectra and lattice dynamics of plastically deformable InSe van der Waals crystals

Stacking two-dimensional (2D) van der Waals (vdW) materials in a layered bulk structure provides an appealing platform for the emergence of exotic physical properties. As a vdW crystal with exceptional plasticity, InSe offers the opportunity to explore various effects arising from the coupling of its peculiar mechanical behaviors and other physical properties. Here, we employ neutron scattering techniques to investigate the correlations of plastic interlayer slip, lattice anharmonicity, and thermal transport in InSe crystals. Not only are the interlayer slip direction and magnitude well captured by shifts in the Bragg reflections, but we also observe a deviation from the expected Debye behaviour in the heat capacity and lattice thermal conductivity. Combining the experimental data with first-principles calculations, we tentatively attribute the observed evidence of strong phonon-phonon interactions to a combination of a large acoustic-optical frequency resonance and a nesting effect. These findings correlate the macroscopic plastic slip and the microscopic lattice dynamics, providing insights into the mechano-thermo coupling and modulation in 2D vdW materials.

36 MATERIALS SCIENCE↗

Resonant Transmissive Modulator Construction for Use in Beam Steering Array

An agile electronically configurable optical beam steering device for use in directional free-space transmission of optical signals is described. The device design employs an array of tunable resonant transmissive modulators constructed from multi-layered stacks of electro-optically active dielectric materials. Each modulator may be individually configured to transmit an optical signal with a specific amount of phase and group velocity modulation. The resulting diffractive interactions between modulator outputs provide a method for directional optical signal transmission. Of particular focus within this presentation is the optimized design of the individual modulator. It is widely known that periodic multi-layered stacks of dielectric materials exhibit reflective and transmissive resonances as described by the stack's transmission function. If an electric field is applied normal to the stack's layers, phenomena such as the electro-optic effect and/or the quantum-confined Stark effect may be employed to change the effective refractive index within the stack. This refractive index change alters the stack's transmission function and modulates the phase and group velocity of the transmitted optical signal. By varying the parameters that describe the stack's specific construction and operation, such as number of layers within the stack, refractive indexes of stack materials, layer thicknesses, and combinations of periodic verses non-periodic layer repetitions, custom transmittance functions may be generated. The transmitted optical signal carrier frequency and bandwidth must be carefully selected to maximize transmission and to minimize absorption. A computational optimization of the variables describing the stack's construction strives to maximize the amount of optical signal modulation verses applied voltage. Trade-offs between methods of increasing device performance verses the limitations of fabrication technologies are considered.

Keys, Andrew S.↗

High Kinetic Energy Penetrator Shielding and High Wear Resistance Materials Fabricated with Boron Nitride Nanotubes (BNNTS) and BNNT Polymer Composites

Boron nitride nanotubes (BNNTs), boron nitride nanoparticles (BNNPs), carbon nontubes (CNTs), graphites, or their combinations, are incorporated into matrices of polymer, ceramic or metals. Fibers, yarns, and woven or nonwoven mates of BNNTs are uses as toughening layers in penetration resistant materials to maximize energy absorption and/or high hardness layers to rebound or deform penetrators. They can be also uses as reinforcing inclusions combining with other polymer matrices to create composite layer like typical reinforcing fibers such as Kevlar (Registered Trademark), Spectra (Registered Trademark) ceramics and metals. Enhanced wear resistance and prolonged usage time, even under harsh conditions, are achieved by adding boron nitride nanomaterials because both hardness and toughness are increased. Such materials can be used in high temperature environments since the oxidation temperature of BNNTs exceeds 800 C in air. Boron nitride based composite materials are useful as strong structural materials for anti-micrometeorite layers for spacecraft and space suits, ultra strong tethers, protective gear for the human body as well as for vehicles, helmets, shields and safety suits/helmets for industry.

Kang, Jin Ho↗

Making Thin Sections from National Treasures: A Little Moon Rock Goes a Long Way

NASA’s Johnson Space Center curates the Apollo sample collection through their facilities in Houston, TX. It is a dual-purpose facility, intended both to store and preserve the precious samples, as well as to make them available for ongoing scientific study and public examination. The facilities consist of multiple vaults and lab spaces, including the Apollo Thin Section Lab. Although it is a part of the Curation facilities, this lab is intended to process specific lunar rock and dust samples into what are called “thin sections”. A thin section is a microscope slide with a very thin, highly polished slice of rock material mounted on it. These are used not only for microscope viewing, but also for a range of other sophisticated scientific instruments to map and measure fine details of the rock’s physical and chemical composition and structure. The process of making a thin section requires great care and patience and is an art in itself; each one is unique, and each sample can behave very differently while going through the same basic procedures. In general, it begins by taking a small chip of rock from a much larger sample. The rock fragment is placed within a small mold and liquid epoxy is poured over it and allowed to harden, producing what is called a “potted butt” (Figure 1). This is to stabilize the rock so that it won’t fragment or crumble during polishing, and to fill any cracks or voids within the rock. Once hardened, the epoxy on the bottom is carefully ground away to expose the rock surface within, which is then polished to a 1-micron finish. A thin new layer of fresh epoxy is then applied to the polished surface and used to mount it to a silica slide. Once the mounting epoxy has hardened, the potted butt is cut off less than one millimeter above the slide using a low-speed circular saw. This thin layer of sample material attached to the slide undergoes further grinding and polishing, typically bringing the sample thickness down to about 35 microns – roughly one third of the thickness of a human hair. The remaining potted butt is saved for future scientific investigations and can be re-polished and used again until all the rock material within it is used up. A single thin section can be reused countless times by numerous different researchers. In addition, thin sections are often exquisitely beautiful (Figure 2) and in some cases, lunar thin sections are used as public display samples, such as at the Smithsonian Air and Space Museum in Washington, DC. The production of thin sections allows an immense variety of research to be conducted on a tiny amount of rock or mineral material, allowing the bulk of the Apollo collection to stay pristine and unaltered, and thus, remain available for next generation of lunar scientists to further our insight into the Moon’s geological diversity, and to bring valuable new insights to our understanding of the origin of the Earth-Moon system.

J J Kent↗

Increased accuracy and signal-to-noise ratio through recent improvements in infra-red video bolometer fabrication and calibration

The infra-red video bolometer (IRVB) is a diagnostic equipped with an infra-red camera that measures the total radiated power in thousands of lines of sight within a large field of view. Recently validated in MAST-U [Fderici et al., Rev. Sci. Instrum. 94, 033502 (2023)], it offers a high spatial resolution map of the radiated power in the divertor region, where large gradients are expected. The IRVB’s sensing element comprises a thin layer of high Z absorbing material, typically platinum, usually coated with carbon to reduce reflections [Peterson et al., Rev. Sci. Instrum. 79, 10E301 (2008)].Here, the possibility of using a relatively inert material such as titanium, is explored that can be produced in layers up to 1 μm compared to 2.5 μm for Pt and then coat it with Pt of the desired thickness (0.3 μm per side here) and carbon. This leads to a higher temperature signal (about 3 times) and better spatial resolution (about 4 times), resulting in higher accuracy in the measured power [Peterson et al., Rev. Sci. Instrum. 79, 10E301 (2008)]. This assembly is also expected to improve foil uniformity, as the Pt layer is obtained via deposition rather than mechanical processes [Mukai et al., Rev. Sci. Instrum. 87, 2014 (2016)].Given its multi-material composition, measuring the thermal properties of the foil assembly is vital. Various methods using a calibrated laser as a heat source have been developed, analyzing the temperature profile shape [Sano et al., Plasma and Fusion Res. 7, 2405039 (2012)] and [Mukai et al., Rev. Sci. Instrum. 89, 10E114 (2018)] or fitting the calculated laser power for different intensities and frequencies [Fderici et al., Rev. Sci. Instrum. 94, 033502 (2023)]. Here, a simpler approach is presented, which relies on analyzing the separate components of the foil heat equation for a single laser exposure in a given area. This can then be iterated over the entire foil to capture local deviations.

Magnetic Fusion Energy↗

Mitigating leaks in membranes

Two-dimensional material based filters, their method of manufacture, and their use are disclosed. In one embodiment, a membrane may include an active layer including a plurality of defects and a deposited material associated with the plurality of defects may reduce flow therethrough. Additionally, a majority of the active layer may be free from the material. In another embodiment, a membrane may include a porous substrate and an atomic layer deposited material disposed on a surface of the porous substrate. The atomic layer deposited material may be less hydrophilic than the porous substrate and an atomically thin active layer may be disposed on the atomic layer deposited material.

36 MATERIALS SCIENCE↗