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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 37 records · Page 2

Mechanically robust hydrophobized double network hydrogels and their fundamental salt transport properties

Abstract Water swollen polymer networks are attractive for applications ranging from tissue regeneration to water purification. For water purification, charged polymers provide excellent ion separation properties. However, many ion exchange membranes (IEMs) are brittle, necessitating the use of thick support materials that ultimately decrease throughput. To this end, novel double network hydrogels (DNHs) with variable water content are prepared and characterized in terms of mechanical and ion transport properties to evaluate their potential utility as tough membrane materials. The first network contains fixed anionic charges, while the other is comprised of a copolymer with varied ratios of hydrophobic ethyl acrylate (EA) and hydrophilic dimethyl acrylamide (DMA) repeat units. Characterization of freestanding DNH films reveals a reduction in water content from 88 to 53 wt% and a simultaneous increase in ultimate stress and strain by ~3.5× and ~4.5×, respectively, for 95%/5% EA/DMA, relative to 100% DMA. Fundamental salt transport properties relevant to water purification, including permeability, solubility, and diffusivity, are measured and systematically compared with conventional membrane materials to inform the development of DNHs for membrane applications. The ability to simultaneously reduce water content and increase mechanical integrity highlights the potential of DNHs as a synthetic platform for future membrane applications.

Allen, Marshall J.↗

Elucidating Polymer Binder Entanglement in Freestanding Sulfide Solid-State Electrolyte Membranes

This study advances the development of flexible, sheet-type sulfide solid-state electrolytes (SSEs) for use in all-solid-state batteries, emphasizing the important and previously insufficiently investigated role of polymer binder entanglement. Here, the molecular weight of polymer binders is pivotal in crafting robust, freestanding SSE films. Our research uncovers a dual impact: higher molecular weight binders bolster the structural integrity of SSE films but elevate grain boundary resistance and diminish critical current density, whereas lower molecular weight poly(isobutylene) films, despite their more uniform distribution, lack the essential strain hardening or strength for sustained active material contact. Crucially, full cells employing higher molecular weight binders demonstrate improved discharge capacity retention, contrasting sharply with the notable capacity degradation in lower molecular weight cells. Our findings not only deepen the comprehension of binder influences in solid-state batteries but also chart a course for refining all-solid-state battery technologies, a key stride for the future of energy storage solutions.

25 ENERGY STORAGE↗

Optical constants of magnetron sputtered aluminum in the range 17–1300 eV with improved accuracy and ultrahigh resolution in the L absorption edge region

This work determines a new set of EUV/x-ray optical constants for aluminum (Al), one of the most important materials in science and technology. Absolute photoabsorption (transmittance) measurements in the 17–1300 eV spectral range were performed on freestanding Al films protected by carbon (C) layers, to prevent oxidation. The dispersive portion of the refractive index was obtained via the Kramers–Kronig transformation. Our data provide significant improvements in accuracy compared to previously tabulated values and reveal fine structure in the Al L 1 and L 2,3 regions, with photon energy step sizes as small as 0.02 eV. The implications of this work in the successful realization of EUV/x-ray instruments and in the validation of atomic and molecular physics models are also discussed.

74 ATOMIC AND MOLECULAR PHYSICS↗

New Aptes Cross-linked Polymers from Poly(ethylene oxide)s and Cyanuric Chloride for Lithium Batteries

A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.

Tigelaar, Dean M.↗

Freestanding and Flexible Micrometer-Thick PEDOT:PSS Film with High Power Factor

High-efficiency thermoelectric materials are vital for sustainable energy. This work presents a reliable method to fabricate freestanding, flexible micrometer-thick films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), achieving a power factor of 204 μW m –1 K –2 , 4 orders of magnitude higher than pristine films. Furthermore, this improvement stems from polymer chain realignment and enhanced charge transport via solvent doping, coupled with PSS reduction during post-treatment, which also strengthens film mechanics. Crucially, the freestanding nature ensures transferability, making them ideal for versatile applications. Besides thermoelectrics, these highly conductive, robust, and flexible PEDOT:PSS films provide attractive solutions for organic solar cells, battery electrodes, and flexible electronics.

Conjugated Polymers↗

Large spin Hall effect in Si at room temperature

Silicon's weak intrinsic spin-orbit coupling and centrosymmetric crystal structure are a critical bottleneck to the development of Si spintronics, because they lead to an insignificant spin Hall effect (spin current generation) and inverse spin Hall effect (spin current detection). In this work, we undertake current, magnetic field, crystallography dependent magnetoresistance, and magnetothermal transport measurements to study the spin transport behavior in freestanding Si thin films. We observe a large spin Hall magnetoresistance in both $\mathcal{p}$ – Si and $\mathcal{n}$ – Si at room temperature and it is an order of magnitude larger than that of Pt. One explanation of the unexpectedly large and efficient spin Hall effect is spin-phonon coupling instead of spin-orbit coupling. The macroscopic origin of the spin-phonon coupling can be large strain gradients that can exist in the freestanding Si films. This discovery in a light, earth abundant and centrosymmetric material opens a new path of strain engineering to achieve spin dependent properties in technologically highly developed materials.

36 MATERIALS SCIENCE↗

The role of lattice dynamics in ferroelectric switching

Reducing the switching energy of ferroelectric thin films remains an important goal in the pursuit of ultralow-power ferroelectric memory and logic devices. Here, we elucidate the fundamental role of lattice dynamics in ferroelectric switching by studying both freestanding bismuth ferrite (BiFeO 3 ) membranes and films clamped to a substrate. We observe a distinct evolution of the ferroelectric domain pattern, from striped, 71° ferroelastic domains (spacing of ~100 nm) in clamped BiFeO 3 films, to large (10’s of micrometers) 180° domains in freestanding films. By removing the constraints imposed by mechanical clamping from the substrate, we can realize a ~40% reduction of the switching voltage and a consequent ~60% improvement in the switching speed. Our findings highlight the importance of a dynamic clamping process occurring during switching, which impacts strain, ferroelectric, and ferrodistortive order parameters and plays a critical role in setting the energetics and dynamics of ferroelectric switching.

36 MATERIALS SCIENCE↗

Nanotube Film Electrode and an Electroactive Device Fabricated with the Nanotube Film Electrode and Methods for Making Same

Disclosed is a single wall carbon nanotube (SWCNT) film electrode (FE), all-organic electroactive device systems fabricated with the SWNT-FE, and methods for making same. The SWCNT can be replaced by other types of nanotubes. The SWCNT film can be obtained by filtering SWCNT solution onto the surface of an anodized alumina membrane. A freestanding flexible SWCNT film can be collected by breaking up this brittle membrane. The conductivity of this SWCNT film can advantageously be higher than 280 S/cm. An electroactive polymer (EAP) actuator layered with the SWNT-FE shows a higher electric field-induced strain than an EAP layered with metal electrodes because the flexible SWNT-FE relieves the restraint of the displacement of the polymeric active layer as compared to the metal electrode. In addition, if thin enough, the SWNT-FE is transparent in the visible light range, thus making it suitable for use in actuators used in optical devices.

Kang, Jin Ho↗

Methods for Making an Electroactive Device Fabricated with a Nanotube Film Electrode

Disclosed is a single wall carbon nanotube (SWCNT) film electrode (FE), all-organic electroactive device systems fabricated with the SWNT-FE, and methods for making same. The SWCNT can be replaced by other types of nanotubes. The SWCNT film can be obtained by filtering SWCNT solution onto the surface of an anodized alumina membrane. A freestanding flexible SWCNT film can be collected by breaking up this brittle membrane. The conductivity of this SWCNT film can advantageously be higher than 280 S/cm. An electroactive polymer (EAP) actuator layered with the SWNT-FE shows a higher electric field-induced strain than an EAP layered with metal electrodes because the flexible SWNT-FE relieves the restraint of the displacement of the polymeric active layer as compared to the metal electrode. In addition, if thin enough, the SWNT-FE is transparent in the visible light range, thus making it suitable for use in actuators used in optical devices.

Kang, Jin Ho↗

Spectroscopic characterization of electronic structures of ultra-thin single crystal La0.7Sr0.3MnO3

Abstract We have successfully fabricated high quality single crystalline La 0.7 Sr 0.3 MnO 3 (LSMO) film in the freestanding form that can be transferred onto silicon wafer and copper mesh support. Using soft x-ray absorption (XAS) and resonant inelastic x-ray scattering (RIXS) spectroscopy in transmission and reflection geometries, we demonstrate that the x-ray emission from Mn 3 s -2 p core-to-core transition (3 s PFY) seen in the RIXS maps can represent the bulk-like absorption signal with minimal self-absorption effect around the Mn L 3 -edge. Similar measurements were also performed on a reference LSMO film grown on the SrTiO 3 substrate and the agreement between measurements substantiates the claim that the bulk electronic structures can be preserved even after the freestanding treatment process. The 3 s PFY spectrum obtained from analyzing the RIXS maps offers a powerful way to probe the bulk electronic structures in thin films and heterostructures when recording the XAS spectra in the transmission mode is not available.

36 MATERIALS SCIENCE↗

Fabrication of ultrathin suspended membranes from atomic layer deposition films

In this report, ultrathin films suspended as freestanding membranes are critical to many microelectronic and materials science applications. However, fabrication methods are currently limited in either their flexibility, due to material selectivity issues during the final membrane release, or their scalability. Here, we demonstrate a novel fabrication process for suspending ultrathin films with thicknesses as low as 4 nm and lateral dimensions up to 20 x 1000 μm from a variety of materials grown by atomic layer deposition. A silicon nitride membrane serves as the support for a sacrificial polymer layer and an ultrathin atomic layer deposition film which, after plasma etching, will form the membrane. The high chemical selectivity between atomic layer deposition-grown transition metal nitrides and oxides and the sacrificial polymer means that ultrathin films of a variety of materials can be released without damage using a single process. Electrically conductive titanium nitride membranes can be produced by this method and are of significant interest for electron microscopy applications. Electron transparency of titanium nitride membranes was found to be ~14% higher than silicon nitride of the same thickness, and of similar conductivity to graphite, meaning that ultrathin, conductive, and electron transparent membranes can be fabricated at scale. These membranes are ideal supports for electron and photon characterization techniques, as well as microelectromechanical system applications that require a conductive membrane.

36 MATERIALS SCIENCE↗

Toward non-Si electronics: From remote epitaxy to layer splitting of 2D materials for mixed dimensional heterostructures

The current electronics has been mainly dominated by Si-based devices due to their mature processing system and exceptional cost-effectiveness. However, next generation electronics needs novel functionalities that cannot be realized by Si because of intrinsic limitation of Si. Accordingly, demand for non-Si electronics has been getting substantially high. Unfortunately, current methodology requires extremely high cost for non-Si materials, which impedes the progress in developing the non-Si based electronics. Here, I will discuss about our group’s efforts to address this issue. Our team recently conceived a new crystalline growth, termed as “remote epitaxy”, which can copy/paste crystalline information from substrates remotely through graphene, thus generating single-crystalline films on graphene. As interfacial binding energy is attenuated by inserting graphene at interface, the single-crystalline films can be easily exfoliated from the slippery graphene surface. Also, the graphene-coated substrates can be, in principle, reused infinitely to produce single-crystalline films. Thus, the remote epitaxy can produce non-Si semiconductor films with unprecedented cost efficiency while allowing additional flexible device functionality required for current ubiquitous electronics. Next, I will discuss about a layer splitting technique which can be a potential solution to overcome the problem in obtaining large-scale and monolayer 2D materials. A 2D material-based heterostructure has been intensively studied because of its unique device functionalities and novel physics. However, it is extremely challenging to secure large-scale and monolayer 2D materials because of following issues: 1) poor scalability for laboratory fabrication processes of 2D heterostructures and 2) lack of well-defined control parameters for kinetics of 2D materials and predictable number of layers of 2D materials. To resolve this issue, we conceived a new approach called “layer-resolved splitting” which obtains multiple monolayer from multilayer 2D materials by controlling interfacial toughness contrast. As this method is versatile and universal, we can, in principle, apply to all 2D materials. We succeeded in having large-scale, monolayer 2D materials through our approach and, thereby 2D heterostructures were demonstrated for functional devices. Lastly, I would like to discuss opportunities of mixed-dimensional heterostructure demonstrated by remote epitaxy and layer-resolved splitting. As they produce freestanding 3D bulk films and 2D atomic layers, a new type of 3D/2D heterostructures can be realized where a new physics and new device architecture are revealed. Therefore, I believe that a new opportunity will be discovered through the mixed-dimensional heterostructures.

Bae, Sang-Hoon↗

Grazing Incidence Wide-Angle X-ray Scattering of Water Adsorption in Polyamide Barrier Layers of Reverse Osmosis Membranes

To understand the relationship between the intermolecular structure of aromatic polyamide (PA) scaffold and the water molecules in the barrier layers of reverse osmosis (RO) membranes, a grazing incidence wide-angle X-ray scattering (GIWAXS) study was carried out on freestanding PA thin films at varying relative humidity (RH) conditions. The scattering results were analyzed by an interference scattering model, containing a phase factor between a PA chain and an adsorbed water molecule. This model yielded good fits to the GIWAXS profiles where the water adsorption was found to vary linearly with RH. Atomistic molecular dynamics (MD) simulations were also performed to complement the experimental study. Furthermore, the simulations revealed that a rapid condensation layer initially formed on the PA film surface, followed by the slow water molecule diffusion inside the PA membrane. Sparse adsorbed water, isolated in subnanopores of the PA film adjacent to the polar atoms, even in very low quantities, modifies the X-ray scattering. Atomistic simulations at the microscopic scale provide partial support for several X-ray scattering findings.

36 MATERIALS SCIENCE↗

Surface dependence of electronic growth of Cu(111) on MoS 2

Scanning tunneling microscopy shows that copper deposited at room temperature onto a freshly exfoliated MoS 2 surface forms Cu(111) clusters with periodic preferred heights of 5, 8, and 11 atomic layers. These height intervals correlate with Fermi nesting regions along the necks of the bulk Cu Fermi surface, indicating a connection between physical and electronic structures. Density functional theory calculations of freestanding Cu(111) films support this as well, predicting a lower density of states at the Fermi level for these preferred heights. This is consistent with other noble metals deposited on MoS 2 that exhibit electronic growth, in which the metal films self-assemble as nanostructures minimizing quantum electronic energies. Here, we have discovered that it is critical for the metal deposition to begin on a clean MoS 2 surface. If copper is deposited onto an already Cu coated surface, even if the original film displays electronic growth, the resulting Cu film lacks quantization. Instead, the preferred heights of the Cu clusters simply increase linearly with the amount of Cu deposited upon the surface. We believe this is due to different bonding conditions during the initial stages of growth. Newly deposited copper would bond strongly to the already present copper clusters, rather than the weak bonding, which exists to the van der Waals terminated surface of MoS 2 . The stronger bonding with previously deposited clusters hinders additional Cu atoms from reaching their lowest quantum energy state. The interface characteristics of the van der Waals surface enable surface engineering of self-assembled structures to achieve different applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Self-assembled Ag(111) nanostructures induced by Fermi surface nesting

Scanning tunneling microscopy measurements on Ag(111)/MoS 2 reveal atomically flat preferred, or “magic,” heights occurring at 6, 10, and 14 atomic layers. We note these results are consistent with Ag growth on a variety of semiconducting substrates and correlate with electronic energy savings in electronic structure calculations of freestanding Ag(111) films. Thus, under certain conditions, Ag will spontaneously form quantized structures independent of the substrate. To explain this, we have found Fermi surface nesting vectors in the bulk Ag band structure which account for these results and the fact Ag that is gapped along the surface normal. This model extends to a range of metallic systems which exhibit electronic confinement, epitaxial growth, and minimal strain. As with Au/MoS 2 , the Ag/MoS 2 system exhibits this behavior at unusually high temperatures so that these principles might be used for control over device features at the nanometer scale under standard fabrication conditions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Sorption Enhanced Mixed Matrix Membranes for Hydrogen (H 2 ) Purification and Carbon Dioxide (CO 2 ) Capture

The technical objective of this project was to develop sorption enhanced mixed matrix membranes with H 2 permeance of 500 gas permeance units (GPU) and H 2 /CO 2 selectivity of 30 at 150-200 °C. These membranes will be the central component in the design of membrane based systems for 90% capture of CO 2 from coal-derived syngas, with 95% CO 2 purity at a cost of electricity 30% less than baseline capture approaches. The unique approach in this proposal is to design crosslinked polymers containing Pd-based nanoparticles achieving strong H 2 sorption and size sieving ability and thus H 2 /CO 2 selectivity. The specific objectives for each budget period (BP) are described below. BP 1: Identify polymer matrix with strong size sieving ability and palladium (Pd)-containing nanomaterials to prepare freestanding mixed matrix films with H 2 permeability of 50 Barrer and H 2 /CO 2 selectivity of 30 at 150-200°C with simulated syngas. BP 2: Prepare and optimize thin film mixed matrix composite membranes materials with H 2 permeance of 500 GPU and H 2 /CO 2 selectivity of 30 at 150-200 °C, and complete the modification of the membrane test unit for the field test in the BP 3. BP 3: Conduct a 20-day field test of the membranes with real syngas at Center for Advanced Energy Research (CAER) of the University of Kentucky (UKy). During the BP2, we have successfully prepared thin-film composite (TFC) membranes based on mixed matrix materials (MMMs) containing Pd nanoparticles in polymers, and demonstrated their superior and robust performance for H 2 /CO 2 separation at 150 – 225 °C. (1) Production of the Pd based nanoparticles with a diameter of 4 nm has been scaled up to 200 mg/day. (2) We have prepared TFC membranes with H 2 permeance above 500 GPU and H 2 /CO 2 selectivity above 30 at temperatures up to 225 °C, which meet the targets for the BP2. (3) We have conducted parametric studies of TFC membranes with a mixed gas containing H 2 S and H 2 O and demonstrated the stability of the membranes. (4) We have established a new testing plan at the Center for Advanced Energy Studies (CAER) at the University of Kentucky because NCCC decided to shut down their gasifier. During this project, four Ph.D. students received the inter-disciplinary training and graduated, including Shailesh Konda, Maryam Omidvar, Deqiang Yin, and Lingxiang Zhu. One postdoctoral researcher (Dr. Liang Huang) and two Ph.D. students (Abhishek Kumar and Hien Nguyen) are involved in this project. The project leads to one provisional patent application, eight peer-reviewed articles, and one manuscript in preparation. The details are shown below.

01 COAL, LIGNITE, AND PEAT↗

Micromachined Tunable Fabry-Perot Filters for Infrared Astronomy

Micromachined Fabry-Perot tunable filters with a large clear aperture (12.5 to 40 mm) are being developed as an optical component for wide-field imaging 1:1 spectroscopy. This program applies silicon micromachining fabrication techniques to miniaturize Fabry-Perot filters for astronomical science instruments. The filter assembly consists of a stationary etalon plate mated to a plate in which the etalon is free to move along the optical axis on silicon springs attached to a stiff silicon support ring. The moving etalon is actuated electrostatically by electrode pairs on the fixed and moving etalons. To reduce mass, both etalons are fabricated by applying optical coatings to a thin freestanding silicon nitride film held flat in drumhead tension rather than to a thick optical substrate. The design, electro-mechanical modeling, fabrication, and initial results will be discussed. The potential application of the miniature Fabry-Perot filters will be briefly discussed with emphasis on the detection of extra-solar planets.

Barclay, Richard↗