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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 91 records · Page 5

Coaxial Nanowire Electrodes Enable Exceptional Fuel Cell Durability

Polymer-electrolyte-membrane fuel cells (PEMFCs) hold great promise for applications in clean energy conversion, but cost and durability continue to limit commercialization. This work presents a new class of catalyst/electrode architecture that does not rely on Pt particles or carbon supports, eliminating the primary degradation mechanisms in conventional electrodes, and thereby enabling transformative durability improvements. The coaxial nanowire electrode (CANE) architecture consists of an array of vertically aligned nanowires, each comprising an ionomer core encapsulated by a nanoscale Pt film. This unique design eliminates the triple-phase boundary and replaces it with two double-phase boundaries, increasing Pt utilization. It also eliminates the need for carbon support and ionomer binder, enabling improved durability and faster mass transport. Fuel cell membrane electrode assemblies based on CANEs demonstrate extraordinary durability in accelerated stress tests (ASTs), with only 2% and 5% loss in performance after 5000 support AST cycles and 30000 catalysts AST cycles, respectively. The high-power density and extremely high durability provided by CANEs can enable a paradigm shift from random electrodes based on unstable platinum nanoparticles dispersed on carbon to ordered electrodes based on durable Pt nanofilms, facilitating rapid deployment of fuel cells in transportation and other clean energy applications.

25 ENERGY STORAGE↗

Role of Solvent in the Oriented Growth of Conductive Ni‐CAT‐1 Metal‐Organic Framework at Solid–Liquid Interfaces

Abstract A controlled growth of two‐dimensional (2D) π‐conjugated metal‐organic frameworks (MOFs) on solid substrates can open exciting opportunities for the application of 2D MOFs as optoelectronic devices. Some factors like solvent composition and type of substrates are known to influence the properties of solution‐processed 2D MOF crystals; however, a mechanistic understanding of how interactions between solvent, substrate, and precursors affect heterogeneous nucleation has been limited. Here, it is reported that the structure of Ni‐catecholate (Ni‐CAT‐1) MOFs at a solid–liquid interface is controlled by solvent–substrate and solvent–MOF precursor interactions. Specifically, the structure of the MOF film can be controlled by varying the affinity of the solvent to the substrate. As a fraction of N , N ‐dimethylformamide (DMF) in a binary solvent mixture of water and DMF increases, the arrangement of Ni‐CAT‐1 crystals varies from vertically aligned nanorods to the graphite substrate to less ordered nanorods with the lower initial nucleation number density of Ni‐CAT‐1 crystals on the surface.

2D materials↗

Large-Scale Plasmonic Hybrid Framework with Built-In Nanohole Array as Multifunctional Optical Sensing Platforms

Light coupling with patterned subwavelength hole arrays induces enhanced transmission supported by the strong surface plasmon mode. In this work, a nanostructured plasmonic framework with vertically built-in nanohole arrays at deep-subwavelength scale (6 nm) is demonstrated using a two-step fabrication method. The nanohole arrays are formed first by the growth of a high-quality two-phase (i.e., Au–TiN) vertically aligned nanocomposite template, followed by selective wet-etching of the metal (Au). Such a plasmonic nanohole film owns high epitaxial quality with large surface coverage and the structure can be tailored as either fully etched or half-way etched nanoholes via careful control of the etching process. The chemically inert and plasmonic TiN plays a role in maintaining sharp hole boundary and preventing lattice distortion. Optical properties such as enhanced transmittance and anisotropic dielectric function in the visible regime are demonstrated. Numerical simulation suggests an extended surface plasmon mode and strong field enhancement at the hole edges. Furthermore, two demonstrations, including the enhanced and modulated photoluminescence by surface coupling with 2D perovskite nanoplates and the refractive index sensing by infiltrating immersion liquids, suggest the great potential of such plasmonic nanohole array for reusable surface plasmon-enhanced sensing applications.

42 ENGINEERING↗

Nitride-Oxide-Metal Heterostructure with Self-Assembled Core–Shell Nanopillar Arrays: Effect of Ordering on Magneto-Optical Properties

Magneto-optical (MO) coupling incorporates photon-induced change of magnetic polarization that can be adopted in ultrafast switching, optical isolators, mode convertors, and optical data storage components for advanced optical integrated circuits. However, integrating plasmonic, magnetic, and dielectric properties in one single material system poses challenges since one natural material can hardly possess all these functionalities. Here, co-deposition of a three-phase heterostructure composed of a durable conductive nitride matrix with embedded core–shell vertically aligned nanopillars, is demonstrated. Additionally, the unique coupling between ferromagnetic NiO core and atomically sharp plasmonic Au shell enables strong MO activity out-of-plane at room temperature. Further, a template growth process is applied, which significantly enhances the ordering of the nanopillar array. The ordered nanostructure offers two schemes of spin polarization which result in stronger antisymmetry of Kerr rotation. The presented complex hybrid metamaterial platform with strong magnetic and optical anisotropies is promising for tunable and modulated all-optical-based nanodevices.

36 MATERIALS SCIENCE↗

Monolayer Films of Binary Metal Oxide Nanoparticles for Carbon Nanotube Synthesis

Binary metal oxide nanoparticles (biMO-NPs) combining transition and main-group metals with well-organized atomic architectures have unique potential as robust and economical heterogeneous catalysts. Herein, metal oxide nanoparticles (CoAlxOy) using cobalt and aluminum were synthesized, and their structure, morphology, and chemical composition were investigated using various characterization techniques. The biMO-NPs, which had a Gaussian-type size distribution (∼6 nm), were assembled on plain silicon substrates modified chemically with linker molecules bearing suitable end groups. Surface analysis revealed an ordered, uniform, close-packed arrangement of biMO-NPs forming a monolayer architecture with nanoscale thickness (∼12 nm), high surface uniformity, and negligible defects. The nanoparticle monolayer film (NP-MF) was employed as a catalyst to grow carbon nanotube (CNT) forests via the thermal chemical vapor deposition (CVD) method, similar to those grown from catalyst thin films deposited by physical vapor deposition. Structural characterization confirmed the growth of a dense, uniform, high-quality vertically aligned carbon nanotube (VA-CNT) forest with a length of ∼125 µm, which is comparable to the VA-CNTs grown from expensive thin films. Thus, CNT growth was successfully catalyzed by the biMO-NPs, highlighting a simple and inexpensive alternative for catalyst deposition. In this innovative wet-chemistry approach, the catalyst and catalyst support are combined within a single nanoparticle before NP-MF assembly. Interestingly, this approach provides a scalable and cost-effective pathway for CNT growth, eliminating the need for expensive thin deposition techniques.

Regmi, Bishow [University of Cincinnati]↗

TiN‐Au/HfO 2 ‐Au Multilayer Thin Films with Tunable Hyperbolic Optical Response

Abstract Hyperbolic metamaterials (HMM) possess significant anisotropic physical properties and tunability and thus find many applications in integrated photonic devices. HMMs consisting of metal and dielectric phases in either multilayer or vertically aligned nanocomposites (VAN) form are demonstrated with different hyperbolic properties. Herein, self‐assembled HfO 2 ‐Au/TiN‐Au multilayer thin films, combining both the multilayer and VAN designs, are demonstrated. Specifically, Au nanopillars embedded in HfO 2 and TiN layers forming the alternative layers of HfO 2 ‐Au VAN and TiN‐Au VAN. The HfO 2 and TiN layer thickness is carefully controlled by varying laser pulses during pulsed laser deposition (PLD). Interestingly, tunable anisotropic physical properties can be achieved by adjusting the bi‐layer thickness and the number of the bi‐layers. Type II optical hyperbolic dispersion can be obtained from high layer thickness structure (e.g., 20 nm), while it can be transformed into Type I optical hyperbolic dispersion by reducing the thickness to a proper value (e.g., 4 nm). This new nanoscale hybrid metamaterial structure with the three‐phase VAN design shows great potential for tailorable optical components in future integrated devices.

Chemistry↗

Exploring the Spatial Control of Topotactic Phase Transitions Using Vertically Oriented Epitaxial Interfaces

Engineering oxygen vacancy formation and distribution is a powerful route for controlling the oxygen sublattice evolution that affects diverse functional behavior. The controlling of the oxygen vacancy formation process is particularly important for inducing topotactic phase transitions that occur by transformation of the oxygen sublattice. Here we demonstrate an epitaxial nanocomposite approach for exploring the spatial control of topotactic phase transition from a pristine perovskite phase to an oxygen vacancy-ordered brownmillerite (BM) phase in a model oxide La 0.7 Sr 0.3 MnO 3 (LSMO). Incorporating a minority phase NiO in LSMO films creates ultrahigh density of vertically aligned epitaxial interfaces that strongly influence the oxygen vacancy formation and distribution in LSMO. Combined structural characterizations reveal strong interactions between NiO and LSMO across the epitaxial interfaces leading to a topotactic phase transition in LSMO accompanied by significant morphology evolution in NiO. Using the NiO nominal ratio as a single control parameter, we obtain intermediate topotactic nanostructures with distinct distribution of the transformed LSMO-BM phase, which enables systematic tuning of magnetic and electrical transport properties. The use of self-assembled heterostructure interfaces by the epitaxial nanocomposite platform enables more versatile design of topotactic phase structures and correlated functionalities that are sensitive to oxygen vacancies.

36 MATERIALS SCIENCE↗

High-yield growth kinetics and spatial mapping of single-walled carbon nanotube forests at wafer scale

Emerging commercial applications of vertically aligned, single-walled carbon nanotube (SWCNT) “forests” require synthesis that minimizes nanotube diameter while maximizing number density across substrate areas exceeding centimeter scale. To address this need, we synthesized SWCNT forests on full silicon wafers with notable reproducibility and uniformity, and co-optimized growth for small diameters and high densities across large areas to access new territory in this 3D parameter space. We mapped the spatial uniformity of key structural features using Raman microscopy, synchrotron X-ray scattering, and Rutherford backscattering spectrometry. Low C 2 H 2 flux over sub-nm Fe/Mo catalysts produced small-diameter SWCNTs (2.1 nm) at high number densities (2.26 × 10 12 cm -2 ) on wafers up to 6 in. Although removing Mo resulted in larger SWCNT diameters and lower densities (<0.7 × 10 12 cm -2 ), mass conversion rates from C 2 H 2 to SWCNT product were high and remarkably invariant for catalyst compositions and densities (i.e., 47.7% or 1.30 × 10 6 % g-catalyst -1 on 4-in. wafers). These carbon conversion efficiencies far exceed typical benchtop reactors and are on par with the best reported literature values. Our detailed elucidation of correlations among structural characteristics within this resource-efficient process is expected to guide future scale-up efforts of SWCNT forest growth beyond wafer scale.

36 MATERIALS SCIENCE↗

Transparent window film with embedded nano-shades for thermoregulation

Every year, more than 20% of the energy consumption in the United States and more than 10% of the global consumption is used towards HVAC (Heating, Ventilating, Air-Conditioning) systems in buildings. Although continued efforts in advancing renewable energy, efficient appliances, and smart building systems are desired, the most critical factors that cause extensive indoor energy consumption are thermal leakage and thermal waste generation. We demonstrate a smart window film that allows natural lighting with a clear view while blocking oblique incident sunlight to make the building interior cooler without using electricity or generating heat. Building upon the concept of, often overlooked, traditional window shades and privacy window films, we emphasize and elevate the application and impact of using magnetically arranged nanoscale material for energy conservation purpose in buildings. By embedding vertically aligned Ni flakes (VANF) in a polymer matrix film, nanoscale mirror array serve as shades to block the high-angled incident sunlight, blocking approximately 73% of total solar irradiance and bringing down the indoor temperature by 1.92 °C during the daytime in a model house while providing nearly 90% transparency. Global application was simulated by applying the respective solar angle and intensity at selected latitudes, indicating their potential. This passively energy-conserving smart film is a low cost, maintenance free, and simple product for users and easy-to-manufacture product for the industry.

36 MATERIALS SCIENCE↗

Topology-driven compressive behavior of Inconel 718 lattice structures with Z-strut reinforcement fabricated by laser powder bed fusion

This study investigates the compressive deformation behavior and mechanical performance of Inconel 718 lattice structures fabricated by laser powder bed fusion (LPBF). Four unit-cell topologies—BCC, FCC, BCCZ, and FCCZ—were designed with a unit-cell size of 3 mm and fabricated under identical process conditions to isolate the effect of topology. Measured relative densities ranged from 14.65% to 17.72%. Compressive testing showed that Z-strut-reinforced topologies (BCCZ: 54.6 MPa; FCCZ: 80.2 MPa) exhibited higher strength than their unreinforced counterparts, which may be associated with mixed-mode deformation behavior enabled by the vertically aligned Z-struts. Finite element simulations and Digital Image Correlation (DIC) analysis support the observation of a transition from node-dominated deformation in BCC/FCC to mixed-mode deformation in BCCZ/FCCZ. These findings suggest that unit-cell topology is a key design variable for tailoring deformation mechanisms in LPBF lattice structures.

36 MATERIALS SCIENCE↗

Core-shell metallic alloy nanopillars-in-dielectric hybrid metamaterials with magneto-plasmonic coupling

Combining plasmonic and magnetic properties, namely magneto-plasmonic coupling, inspires great research interest and the search for magneto-plasmonic nanostructure becomes considerably critical. In this work, we designed a nanopillar-in-matrix structure with core–shell alloyed nanopillars for both BaTiO 3 (BTO)-Au 0.5 Co 0.5 (AuCo) and BTO-Au 0.25 Cu 0.25 Co 0.25 Ni 0.25 (AuCuCoNi) hybrid systems, i.e., ferromagnetic alloy cores (e.g., Co or CoNi) with plasmonic shells (e.g., Au or Au/Cu). These core–shell alloy nanopillars are uniformly embedded into a dielectric BTO matrix to form a vertically aligned nanocomposite (VAN) structure. Both hybrid systems present excellent epitaxial quality and interesting multi-functionality, e.g., high magnetic anisotropy, magneto-optical coupling response, tailorable plasmonic resonance wavelength, tunable hyperbolic properties and strong optical anisotropy. These alloyed nanopillars-in-matrix designs provide enormous potential for complex hybrid material designs with multi-functionality and demonstrate strong interface enabled magneto-plasmonic coupling along with plasmonic and magnetic performance.

36 MATERIALS SCIENCE↗

Ionic liquid mediated one-step perpendicular assembly in block copolymer thin films for ultrafiltration membrane applications

The rapid rise of oil and gas, petrochemical, food processing, and pharmaceutical industries has added a complex mixture of contaminants like oil, particulates, metals, and other organic compounds to wastewater. Multipurpose membranes with precise pore structure can offer a solution to this problem and block copolymers (BCP) can be used to achieve such structures. Achieving vertical assembly of BCP domains provides a perfect template for developing uniform through film channels for separation and transport of material, besides being useful for the rectification of defects in photolithography patterns. Producing such morphologies may require extensive film/substrate processing and is not always feasible for scale-up. With this article, we demonstrate a facile solution casting method to induce vertical domain assembly in as-cast diblock copolymer thin films in the presence of an ionic liquid (IL) additive that preferentially segregates to one block and neutralizes interfacial interactions. We also show the tunability of domain sizes by controlling the additive concentration. These vertically aligned morphologies are important for the development of next-generation lithographic techniques and form excellent templates for ultrafiltration membranes with uniform pore sizes. In conclusion, this article demonstrates how IL additives can be used to obtain stable non-equilibrium morphologies in as-cast BCP films and the effect of BCP molecular mass, block volume fractions, and IL content on self-assembly.

59 BASIC BIOLOGICAL SCIENCES↗

Two-layer cathode architecture for high-energy density and high-power density solid state batteries

Solid state batteries with high-energy density and high-power density require the development of thick and energy dense cathodes. Structured cathode electrodes with a double-layer configuration were enabled using a freeze tape casting technique. A bottom dense layer was utilized to enhance the energy density whereas a top porous layer with vertically aligned walls was utilized to enhance the power density. The porous structure of the power layer was achieved by ice templating this layer on top of the densified energy layer of the cathode. This configuration was found to better utilize the active material of the cathodes and was optimized using numerical simulation and computer modeling. Cells with Li metal anode and LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) at approximately 5 and 20 mg/cm 2 were cycled at 70 °C at different C-rates. Poly(ethylene oxide) (PEO) with lithium bis-trifluoromethanesulfonimide (LiTFSI) was used for the catholyte and the solid-state electrolyte. The structured cathodes exhibited more than double capacity values as well as better Coulombic efficiency compared to non-structured (single-layer) thick cathodes. In conclusion, synchrotron X-ray tomography and scanning electron microscopy were used to characterize the microstructure of the cathodes.

25 ENERGY STORAGE↗

Macroscale superlubricity by a sacrificial carbon nanotube coating

Superlubricity, i.e., coefficient of friction (COF) below 0.01, was earlier limited to microscale in controlled environments in the earlier literature and more recently realized for macroscale sliding of ceramic or carbon surfaces lubricated by water or other polar fluids. However, there is lack of report of superlubricity for the most common bearing system, i.e., steel-steel contact in non-polar oil lubrication. Here, in this work, we present ultra-low COF of 0.001–0.007 by using a sacrificial coating composed of vertically-aligned carbon nanotubes (CNTs) for macroscale steel-steel sliding under minimum quantity lubrication (MQL) of a polyalphaolefin (PAO) oil in the ambient environment. Raman spectroscopy and electron microscopy analyses detected graphene-containing tribofilms on both the steel surfaces, which was produced by the fractured CNT flakes and metallic wear debris during running-in. The in situ formed graphene-graphene contact interface presumably possesses a low shear resistance leading to superlubricity. The presence of oil, despite as little as one droplet, has proven to be crucial. Such a superlubricity performance has shown good sustainability in extended testing of more than 500,000 cycles and strong ability of accommodating changes in sliding conditions. Results here demonstrate feasibility with fundamental insights for achieving ambient environment macroscale superlubricity.

36 MATERIALS SCIENCE↗

High mass loading potassium ion stabilized manganese dioxide nanowire forests for rechargeable Zn batteries

Manganese dioxide (MnO 2 ) represents an ideal cathode material for rechargeable aqueous Zn batteries due to its high theoretical capacity (308 mAh g -1 ), suitable potential (1.4 V vs. Zn 2+ /Zn), natural abundance, and negligible toxicity. However, the capacity and rate capability of MnO 2 deteriorate significantly in thick electrodes owing to its low electrical and ionic conductivities. Herein, we report the design of high mass loading potassium ion stabilized α-MnO 2 (K 0.133 MnO 2 ) nanowire forests on carbon cloth through a seed-assisted hydrothermal method for Zn batteries. Further, the vertically aligned K 0.133 MnO 2 nanowire forests with uninterrupted charge transport afford a high area capacity of 3.54 mAh cm -2 and a capacity retention of 79.2% over 1000 cycles in aqueous electrolyte. Moreover, the high area capacity and cyclability can be readily transferred to quasi-solid-state devices.

25 ENERGY STORAGE↗

Geostrophic to magnetically-damped turbulence in liquid metal rotating magnetoconvection

Understanding planetary core convection dynamics requires the study of convective flows in which the Coriolis and Lorentz forces attain a leading-order, so-called magnetostrophic balance. Experimental investigations of rotating magnetoconvection (RMC) in the magnetostrophic regime are therefore essential to broadly characterize the properties of local-scale planetary core flow. Toward this end, we present here the first thermovelocimetric measurements of magnetostrophic, liquid metal convection, which are made using liquid gallium as the working fluid, at moderate rotation rates (Ekman numbers 10 -4 ≤ Ek ≤ 10 -5 ) and in the presence of dynamically strong magnetic fields (Elsasser number Λ = 1). Complementary rotating convection (RC) experiments are performed at the same rotation rates to serve as reference cases. Our RMC velocity measurements adequately follow a geostrophic turbulent scaling for cases in which local-scale convective inertial forces exceed the Lorentz forces in the fluid bulk. In cases where Lorentz forces exceed local-scale inertia (local or convective interaction parameter N ℓ or N C ≳ 3), the root-mean-square RMC velocities are magnetically damped, yielding values below the geostrophic turbulent RC scaling prediction. An enhancement in heat transfer is observed, which we attribute to the increased coherence of vertically aligned magnetostrophic convective flow. Finally, our results and comparisons to dynamo simulations suggest that the system is in the strong-field regime, where convection-scale flows are magnetically damped with N C ≳ 3).

Convective turbulence↗

Resolving Triblock Terpolymer Morphologies by Vapor-Phase Infiltration

The spontaneous formation of well-organized three-dimensional (3D) nanostructures from self-assembled block copolymers (BCPs) holds promise for nanofabrication and lithography. The addition of a third block to BCPs provides access to a plethora of 3D geometries, but it remains difficult to resolve the geometry of such “three-color” structures when there is low contrast between the polymeric components at length scales of a few nm. Here, we apply vapor-phase infiltration synthesis to a silicon-containing triblock terpolymer, poly(1,1- dimethyl silacyclobutane-b-styrene-b-lactide) (PDMSB-b-PS-b-PLA or DSL) to distinguish the 3D microdomain morphologies of the two organic blocks, PLA and PS. Selective infiltration of ZnO within the PLA microdomains reveals morphologies consisting of three-color lamellae or lamellae combined with vertically aligned core-shell cylinders, depending on the volume fractions of each block. The infiltration produces ZnO nanoparticles throughout the 260 nm thickness of the DSL film, generating 3D nanocomposites containing ZnO and SiO x . These results provide a strategy for synthesizing multicomponent 3D nanostructures as well as visualizing the phase behavior of multi-block copolymers.

36 MATERIALS SCIENCE↗