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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 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Nanoimprinted Chiral Plasmonic Substrates with Three-Dimensional Nanostructures

Here, we report a large-area fabrication method to prepare chiral substrates patterned with arrays of multilayer, three-dimensional nanostructures using a combination of nanoimprint lithography and glancing angle deposition. Several structures are successfully fabricated using this method, including L-shaped, twisted arc and trilayer twisted Au nanorod structures, demonstrating its generality. As one typical example, arrays of L-shaped nanostructures, consisting of two layers of orthogonally oriented Au nanorods separated by a Ge dielectric layer in the thickness direction, exhibit giant optical chirality in the infrared region with an experimentally achieved g-factor as high as 0.38. Electromagnetic simulations show that the optical chirality results from plasmon hybridization between the two orthogonal Au segments. To demonstrate scalability, a 1 cm 2 chiral substrate is fabricated with uniform chiral optical property. This method combines both high throughput and precise geometrical control and is therefore promising for applications of chiral metamaterials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Hierarchical TiO 2 :Cu 2 O Nanostructures for Gas/Vapor Sensing and CO 2 Sequestration

We investigate the effect of high-surface-area self-assembled TiO 2 :Cu 2 O nanostructures for CO 2 and relative humidity gravimetric detection using polyethylenimine (PEI), 1-ethyl-3-methylimidazolium (EMIM), and polyacrylamide (PAAm). Introduction of hierarchical TiO 2 :Cu 2 O nanostructures on the surface of quartz crystal microbalance sensors is found to significantly improve sensitivity to CO 2 and to H 2 O vapor. The response of EMIM to CO 2 increases fivefold for 100 nm-thick TiO 2 :Cu 2 O as compared to gold. At ambient CO 2 concentrations, the hierarchical assembly operates as a sensor with excellent reversibility, while at higher pressures, the CO 2 desorption rate decreases, suggesting possible application for CO 2 sequestration under these conditions. The gravimetric response of PEI to CO 2 increases by a factor of 3 upon introduction of a 50 nm TiO 2 :Cu 2 O layer. The PAAm gravimetric response to water vapor also increases by a factor of 3 and displays improved reversibility with the addition of 50 nm TiO 2 :Cu 2 O structures. We found that TiO 2 :Cu 2 O can be used to lower the detection limits for CO 2 sensing with EMIM and PEI and lower the detection limits for H 2 O sensing with PAAm by over a factor of 2. Coarse-grained and all-atom molecular dynamics simulations indicate the dissociative character of ionic liquid assembly on TiO 2 :Cu 2 O interfaces and different distributions of CO 2 and H 2 O molecules on bare and ionic liquid-coated surfaces, confirming experimental observations. Overall, our results show high potential of hierarchical assemblies of TiO 2 :Cu 2 O/room temperature ionic liquid and polymer films for sensors and CO 2 sequestration.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Modularly Constructed Polyhedral Oligomeric Silsesquioxane-Based Giant Molecules for Unconventional Nanostructure Fabrication

Controlled assembly of nanoscale building blocks is a promising approach to obtain functional materials with unique properties. In this paper, we report a way to manipulate the supramolecular structures of giant molecules based on discotic triangle cores and isobutyl polyhedral oligomeric silsesquioxanes (BPOSS) nanoparticles (NPs). It is found that depending upon the number of BPOSS at the periphery of the discotic cores, the packing of these nanoscale components (discotic core and POSS) could be manipulated into either cylindrical or Frank–Kasper (F–K) A15 ($Pm\overline 3n$) phases. The formation of these supramolecular nanostructures is mandated by the balance between the stacking of the discotic cores and the steric hindrance effect of the BPOSS NPs. This strategy to manipulate the packing of nanoscale building blocks for different supramolecular nanostructures including the fabrication of cylindrical structures and A15 ($Pm\overline 3n$) phases may be extended to other nanoscale building blocks for future development of materials with complex structures as well as tailored functionalities and properties.

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

High Energy Density Shape Memory Polymers Using Strain-Induced Supramolecular Nanostructures

Shape memory polymers are promising materials in many emerging applications due to their large extensibility and excellent shape recovery. However, practical application of these polymers is limited by their poor energy densities (up to ~1 MJ/m 3 ). Here, we report an approach to achieve a high energy density, one-way shape memory polymer based on the formation of strain-induced supramolecular nanostructures. As polymer chains align during strain, strong directional dynamic bonds form, creating stable supramolecular nanostructures and trapping stretched chains in a highly elongated state. Upon heating, the dynamic bonds break, and stretched chains contract to their initial disordered state. This mechanism stores large amounts of entropic energy (as high as 19.6 MJ/m 3 or 17.9 J/g), almost six times higher than the best previously reported shape memory polymers while maintaining near 100% shape recovery and fixity. The reported phenomenon of strain-induced supramolecular structures offers a new approach toward achieving high energy density shape memory polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Stabilizing Dendritic Electrodeposition by Limiting Spatial Dimensions in Nanostructured Electrolytes.

The tendency of metals to form uncontrolled dendritic morphologies during electrodeposition hinders the development of safe and reliable metal batteries. Multiphase nanostructured electrolytes can suppress dendritic growth if the mechanical modulus of the electrolyte is high relative to that of the metal or if the conducting channels are confined to nanoscale dimensions. Direct visualization and analysis of electrodeposition within polymeric nanostructures elucidates the structure-property relationships and mechanisms underlying the suppression of dendrite growth. Here, we fabricate precisely structured multiphase films composed of nanochannels of a polymeric electrolyte in a background of nonconductive polymer on top of coplanar electrodes. The devices enable imaging and analysis of electrodeposition behavior as a function of channel width by scanning electron microscopy. We find that electrodeposition is confined to individual conductive channels and that radial propagation of the dendritic morphology is suppressed in channels for which the width is smaller than the characteristic dendritic nucleation size.

Sharon, Daniel↗
DOE OSTI2017

Nanostructured Bulk-Heterojunction Solar Cells Based on Amorphous Carbon

Amorphous carbon (a-C) has the potential to provide properties important to solar photovoltaics that are comparable to those of silicon-based materials with further advantages such as low cost, solution processing, air stability, and higher thermal resistance. We employ accurate computational approaches to explore and understand active layers based on bulk heterojunctions containing a-C. Our results show that interfaces with a-C and other carbon nanostructures could enable successful electron and hole extraction as well as reduced sources for carrier recombination. Ab initio molecular dynamics and density functional theory calculations are carried out for a large statistical set of interfaces between a-C structures of different densities and either carbon nanotubes or fullerenes. Here, we show that the energy alignment at such interfaces can be widely tuned as a function of a-C density, doping chemistry, or nanostructure size to obtain type-II heterostructures and that the optical properties of such interfaces would be highly favorable for sunlight harvesting.

14 SOLAR ENERGY↗
DOE OSTI2023

Residual Strain and Nanostructural Effects during Drying of Nanocellulose/Clay Nanosheet Hybrids: Synchrotron X-ray Scattering Results

Cellulose nanofibrils (CNF) with 2D silicate nanoplatelet reinforcement readily form multifunctional composites by vacuum-assisted self-assembly from hydrocolloidal mixtures. The final nanostructure is formed during drying. The crystalline nature of CNF and montmorillonite (MTM) made it possible to use synchrotron X-ray scattering (WAXS, SAXS) to monitor structural development during drying from water and from ethanol. Nanostructural changes in the CNF and MTM crystals were investigated. Changes in the out-of-plane orientation of CNF and MTM were determined. Residual drying strains previously predicted from theory were confirmed in both cellulose and MTM platelets due to capillary forces. The formation of tactoid platelet stacks could be followed. We propose that after filtration, the constituent nanoparticles in the swollen, solid gel already have a “fixed” location, although self-assembly and ordering processes take place during drying.

36 MATERIALS SCIENCE↗
DOE OSTI2015

High Performance Ultrathin GaAs Solar Cells Enabled with Heterogeneously Integrated Dielectric Periodic Nanostructures

Due to their favorable materials properties including direct bandgap and high electron mobilities, epitaxially grown III–V compound semiconductors such as gallium arsenide (GaAs) provide unmatched performance over silicon in solar energy harvesting. Yet, their large-scale deployment in terrestrial photovoltaics remains challenging mainly due to the high cost of growing device quality epitaxial materials. In this regard, reducing the thickness of constituent active materials under appropriate light management schemes is a conceptually viable option to lower the cost of GaAs solar cells. In this work, we present a type of high efficiency, ultrathin GaAs solar cell that incorporates bifacial photon management enabled by techniques of transfer printing to maximize the absorption and photovoltaic performance without compromising the optimized electronic configuration of planar devices. Nanoimprint lithography and dry etching of titanium dioxide (TiO 2 ) deposited directly on the window layer of GaAs solar cells formed hexagonal arrays of nanoscale posts that serve as lossless photonic nanostructures for antireflection, diffraction, and light trapping in conjunction with a co-integrated rear-surface reflector. Systematic studies on optical and electrical properties and photovoltaic performance in experiments, as well as numerical modeling, quantitatively describe the optimal design rules for ultrathin, nanostructured GaAs solar cells and their integrated modules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Synthesis of One-Dimensional SiC Nanostructures from a Glassy Buckypaper

A simple and scalable synthetic strategy was developed for the fabrication of one-dimensional SiC nanostructures - nanorods and nanowires. Thin sheets of single-walled carbon nanotubes (SWNTs) were prepared by vacuum filtration and were washed repeatedly with sodium silicate (Na₂SiO₃) solution. The resulting “glassy buckypaper” was heated at 1300 - 1500 °C under Ar/H₂ to allow a solid state reaction between C and Si precursors to form a variety of SiC nanostructures. The morphology and crystal structures of SiC nanorods and nanowires were characterized using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), energy dispersive xray spectroscopy (EDX), electron diffraction (ED) and x-ray diffraction (XRD) techniques. Furthermore, electrical conductance measurements were performed on SiC nanorods, demonstrating their potential applications in high-temperature sensors and control systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2012

Reactive Ballistic Deposition of Nanostructured Model Materials for Electrochemical Energy Conversion and Storage

Finely structured, supported thin films offer a host of opportunities for fundamental and applied research. Nanostructured materials often exhibit physical properties which differ from their bulk counterparts due to the increased importance of the surface in determining the thermodynamics and behavior of the system. Thus, control of the characteristic size, porosity, morphology, and surface area presents opportunities to tailor new materials which are useful platforms for elucidating the fundamental processes related to energy conversion and storage. The ability to produce high purity materials with direct control of relevant film parameters such as porosity, film thickness, and film morphology is of immediate interest in the fields of electrochemistry, photocatalysis, and thermal catalysis. Studies of various photoactive materials have introduced questions concerning the effects of film architecture and surface structure on the performance of the materials, while recent work has demonstrated that nanostructured, mesoporous, or disordered materials often deform plastically, making them robust in applications where volumetric expansion and phase transformations occur, such as in materials for lithium-ion batteries. Moreover, renewed emphasis has been placed on the formation of semi-conductive electrodes with controlled pore-size and large surface areas for the study and application of pseudo-capacitance and cation insertion processes for electrical energy storage. Understanding how the performance of such materials depends on morphology, porosity, and surface structure and area requires a synthesis technique which provides for incremental variations in structure and facilitates assessment of the performance with the appropriate analytical tools, preferably those that provide both structural information and kinetic insight into photoelectrochemical processes.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2014

High Yield Synthesis of Mesoscopic Conductive and Dispersible Carbon Nanostructures via Ultrasonication of Commercial Precursors

The need to produce large quantities of graphenic materials displaying excellent conductivity, thermal resistance, and tunable properties for industrial applications has spurred interest in new techniques for exfoliating graphite. In this paper, sonication-assisted exfoliation of graphitic precursors in the presence of chloroform is shown to produce chemically and structurally unique exfoliated graphitic materials in high yields. These exfoliated graphites, referred to as mesographite and mesographene, respectively, exhibit unique properties which depend on the number of layers and exfoliation conditions. Structural characterization of mesographene reveals the presence of nanoscale two-dimensional graphene layers, and threedimensional carbon nanostructures sandwiched between layers, similar to those found in ball-milled and intercalated graphites. The conductivities of mesographite and mesographene are 2700 and 2000 S/m, respectively, indicating high conductivity despite flake damage. Optical absorption measurements of mesographite sonicated in various solvents showed significant changes in dispersion characteristics, and also indicated significant changes to mesoscopic colloidal behavior. A mechanism for functionalization and formation of capped carbon nanostructures is proposed by integrating the chemical and structural characterization in relation to the various carbon structures observed by electron microscopy. Composites based on common polymers were prepared by solution processing, and changes in thermal properties indicate improved dispersion of mesographite in polar polymers.

Srivastava, Vikram K↗
DOE OSTI2020

Phase-Selective Epitaxial Growth of Heterophase Nanostructures on Unconventional 2H-Pd Nanoparticles

Heterostructured, including heterophase, noble-metal nanomaterials have attracted much interest due to their promising applications in diverse fields. However, great challenges still remain in the rational synthesis of well-defined noble-metal heterophase nanostructures. Furthermore, we report the preparation of Pd nanoparticles with an unconventional hexagonal close-packed (2H type) phase, referred to as 2H-Pd nanoparticles, via a controlled phase transformation of amorphous Pd nanoparticles. Impressively, by using the 2H-Pd nanoparticles as seeds, Au nanomaterials with different crystal phases epitaxially grow on the specific exposed facets of the 2H-Pd, i.e., face-centered cubic (fcc) Au (fcc-Au) on the (002)h facets of 2H-Pd while 2H-Au on the other exposed facets, to achieve well-defined fcc-2H-fcc heterophase Pd@Au core–shell nanorods. Moreover, through such unique facet-directed crystal-phase-selective epitaxial growth, a series of unconventional fcc-2H-fcc heterophase core–shell nanostructures, including Pd@Ag, Pd@Pt, Pd@PtNi, and Pd@PtCo, have also been prepared. Impressively, the fcc-2H-fcc heterophase Pd@Au nanorods show excellent performance toward the electrochemical carbon dioxide reduction reaction (CO 2 RR) for production of carbon monoxide with Faradaic efficiencies of over 90% in an exceptionally wide applied potential window from –0.9 to –0.4 V (versus the reversible hydrogen electrode), which is among the best reported CO 2 RR catalysts in H-type electrochemical cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Kinetic Monte Carlo Study of Ambipolar Lithium Ion and Electron–Polaron Diffusion into Nanostructured TiO2

Nanostructured titania (TiO2) polymorphs have proved to be promising electrode materials for next generation lithium-ion batteries. However, there is still a lack of understanding of the fundamental microscopic processes that control charge transport in these materials. Here we present microscopic simulations of the collective dynamics of lithium-ion (Li+) and charge compensating electron polarons (e-) in rutile TiO2 nanoparticles in contact with idealized conductive matrix and electrolyte. Kinetic Monte Carlo simulations are used, parameterized by molecular dynamics-based predictions of activation energy barriers for Li+ and e- diffusion. Simulations reveal the central role of electrostatic coupling between Li+ and e- on their collective drift diffusion at the nanoscale. They also demonstrate that high contact area between conductive matrix and rutile nanoparticles leads to undesirable coupling-induced surface saturation effects during Li+ insertion, which limits the overall capacity and conductivity of the material. These results help provide guidelines for design of nanostructured electrode materials with improved electrochemical performance.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2013

Dynamic Defrosting on Nanostructured Superhydrophobic Surfaces

Water suspended on chilled superhydrophobic surfaces exhibits delayed freezing; however, the interdrop growth of frost through subcooled condensate forming on the surface seems unavoidable in humid environments. It is therefore of great practical importance to determine whether facile defrosting is possible on superhydrophobic surfaces. Here in this paper, we report that nanostructured superhydrophobic surfaces promote the growth of frost in a suspended Cassie state, enabling its dynamic removal upon partial melting at low tilt angles (<15°). The dynamic removal of the melting frost occurred in two stages: spontaneous dewetting followed by gravitational mobilization. This dynamic defrosting phenomenon is driven by the low contact angle hysteresis of the defrosted meltwater relative to frost on microstructured superhydrophobic surfaces, which forms in the impaled Wenzel state. Dynamic defrosting on nanostructured superhydrophobic surfaces minimizes the time, heat, and gravitational energy required to remove frost from the surface, and is of interest for a variety of systems in cold and humid environments.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Graphene-modified nanostructured vanadium pentoxide hybrids with extraordinary electrochemical performance for Li-ion batteries

The long-standing issues of low intrinsic electronic conductivity, slow lithium-ion diffusion and irreversible phase transitions on deep discharge prevent the high specific capacity/energy (443 mAh g -1 and 1,550 Wh kg -1 ) vanadium pentoxide from being used as the cathode material in practical battery applications. Here we develop a method to incorporate graphene sheets into vanadium pentoxide nanoribbons via the sol–gel process. The resulting graphene-modified nanostructured vanadium pentoxide hybrids contain only 2 wt. % graphene, yet exhibits extraordinary electrochemical performance: a specific capacity of 438 mAh g -1 , approaching the theoretical value (443 mAh g -1 ), a long cyclability and significantly enhanced rate capability. Such performance is the result of the combined effects of the graphene on structural stability, electronic conduction, vanadium redox reaction and lithium-ion diffusion supported by various experimental studies. Finally, this method provides a new avenue to create nanostructured metal oxide/graphene materials for advanced battery applications.

25 ENERGY STORAGE↗
DOE OSTI2022

Hydrophilic nanoparticles that kill bacteria while sparing mammalian cells reveal the antibiotic role of nanostructures

To dissect the antibiotic role of nanostructures from chemical moieties belligerent to both bacterial and mammalian cells, here we show the antimicrobial activity and cytotoxicity of nanoparticle-pinched polymer brushes (NPPBs) consisting of chemically inert silica nanospheres of systematically varied diameters covalently grafted with hydrophilic polymer brushes that are non-toxic and non-bactericidal. Assembly of the hydrophilic polymers into nanostructured NPPBs doesn’t alter their amicability with mammalian cells, but it incurs a transformation of their antimicrobial potential against bacteria, including clinical multidrug-resistant strains, that depends critically on the nanoparticle sizes. The acquired antimicrobial potency intensifies with small nanoparticles but subsides quickly with large ones. We identify a threshold size (d silica ~ 50 nm) only beneath which NPPBs remodel bacteria-mimicking membrane into 2D columnar phase, the epitome of membrane pore formation. This study illuminates nanoengineering as a viable approach to develop nanoantibiotics that kill bacteria upon contact yet remain nontoxic when engulfed by mammalian cells.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Defect-mediated ripening of core-shell nanostructures

Abstract Understanding nanostructure ripening mechanisms is desirable for gaining insight on the growth and potential applications of nanoscale materials. However, the atomic pathways of nanostructure ripening in solution have rarely been observed directly. Here, we report defect-mediated ripening of Cd-CdCl 2 core-shell nanoparticles (CSN) revealed by in-situ atomic resolution imaging with liquid cell transmission electron microscopy. We find that ripening is initiated by dissolution of the nanoparticle with an incomplete CdCl 2 shell, and that the areas of the Cd core that are exposed to the solution are etched first. The growth of the other nanoparticles is achieved by generating crack defects in the shell, followed by ion diffusion through the cracks. Subsequent healing of crack defects leads to a highly crystalline CSN. The formation and annihilation of crack defects in the CdCl 2 shell, accompanied by disordering and crystallization of the shell structure, mediate the ripening of Cd-CdCl 2 CSN in the solution.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Enhancing Modulation of Thermal Conduction in Vanadium Dioxide Thin Film by Nanostructured Nanogaps

Efficient thermal management at the nanoscale is important for reducing energy consumption and dissipation in electronic devices, lab-on-a-chip platforms and energy harvest/conversion systems. For many of these applications, it is much desired to have a solid-state structure that reversibly switches thermal conduction with high ON/OFF ratios and at high speed. We describe design and implementation of a novel, all-solid-state thermal switching device by nanostructured phase transformation, i.e., modulation of contact pressure an d area between two poly-silicon surfaces activated by microstructural change of a vanadium dioxide (VO 2 ) thin film. Our solid-state devices demonstrate large and reversible alteration of cross-plane thermal conductance as a function of temperature, achieving a conductance ratio of at least 2.5. This new approach using nanostructured phase transformation provides new opportunities for applications that require advanced temperature and heat regulations.

36 MATERIALS SCIENCE↗