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Results for “Directed self assembly”

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 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
NASA NTRS1972

The influence of radiation shielding on reusable nuclear shuttle design

Alternate reusable nuclear shuttle configurations were synthesized and evaluated. Particular attention was given to design factors which reduced tank exposure to direct and scattered radiation, increased payload-engine separation, and improved self-shielding by the LH2 propellant. The most attractive RNS concept in terms of cost effectiveness consists of a single conical aft bulkhead tank with a high fineness ratio. Launch is accomplished by the INT-21 with the tank positioned in the inverted attitude. The NERVA engine is delivered to orbit separately where final stage assembly and checkout are accomplished. This approach is consistent with NERVA definition criteria and required operating procedures to support an economically viable nuclear shuttle transportation program in the post-1980 period.

Littman, T. M.↗
DOE OSTI2024

Self-assembled reconfigurable pump architectures via magnetic colloidal swarms

Self-assembled swarms of interactive active units, which are adaptive and dynamically reconfigurable to accommodate different functionalities, represent a promising platform for the development of next-generation robotics. Here, we utilize the emergent collective behavior of active magnetic colloids confined in quasi-two-dimensional arrays of overlapping wells to demonstrate the self-organization of a colloidal swarm into a dynamic pump architecture capable of controlled transport of passive cargo particles. This dynamic architecture provides a global unidirectional looping flow pattern along the entire length of the system. We show that the flow direction of the dynamic swarm-based pump can be externally controlled by a phase shift of a driving magnetic field energizing the swarm. The experimental observations are supported by computational modeling based on phenomenological coarse-grained particle dynamics coupled to shallow-water Navier-Stokes hydrodynamics. In conclusion, our findings demonstrate how the emergent collective behavior of a swarm can be orchestrated into a desired functionality by exploiting the interplay between activity and confinement potentials.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Development of a Rhodobacter capsulatus self-reporting model system for optimizing light-dependent, [FeFe]-hydrogenase-driven H 2 production

The photosynthetic bacterium Rhodobacter capsulatus normally photoproduces H 2 as a by-product of its nitrogenase-catalyzed nitrogen-fixing activity. Such H 2 production, however, is expensive from a metabolic perspective, requiring nearly four times as many photons as the equivalent algal hydrogenase-based system. Here we report the insertion of a Clostridium acetobutylicum [FeFe]-hydrogenase and its three attendant hydrogenase assembly proteins into an R. capsulatus strain lacking its native uptake hydrogenase. Further, this strain is modified to fluoresce upon sensing H 2 . The resulting strain photoproduces H 2 and self-reports its own H 2 production through fluorescence. Furthermore, this model system represents a unique method of developing hydrogenase-based H 2 production in R. capsulatus , may serve as a powerful system for in vivo directed evolution of hydrogenases and hydrogenase-associated genes, and provides a means of screening for increased metabolic production of H 2 .

09 BIOMASS FUELS↗
DOE OSTI2014

High performance transistors via aligned polyfluorene-sorted carbon nanotubes

We evaluate the performance of exceptionally electronic-type sorted, semiconducting, aligned single-walled carbon nanotubes (s-SWCNTs) in field effect transistors (FETs). High on-conductance and high on/off conductance modulation are simultaneously achieved at channel lengths which are both shorter and longer than individual s-SWCNTs. The s-SWCNTs are isolated from heterogeneous mixtures using a polyfluorene-derivative as a selective agent and aligned on substrates via dose-controlled, floating evaporative self-assembly at densities of ∼50 s-SWCNTs μm{sup −1}. At a channel length of 9 μm the s-SWCNTs percolate to span the FET channel, and the on/off ratio and charge transport mobility are 2.2 × 10{sup 7} and 46 cm{sup 2} V{sup −1} s{sup −1}, respectively. At a channel length of 400 nm, a large fraction of the s-SWCNTs directly span the channel, and the on-conductance per width is 61 μS μm{sup −1} and the on/off ratio is 4 × 10{sup 5}. These results are considerably better than previous solution-processed FETs, which have suffered from poor on/off ratio due to spurious metallic nanotubes that bridge the channel. 4071 individual and small bundles of s-SWCNTs are tested in 400 nm channel length FETs, and all show semiconducting behavior, demonstrating the high fidelity of polyfluorenes as selective agents and the promise of assembling s-SWCNTs from solution to create high performance semiconductor electronic devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Using block-copolymer nanolithography as a tool to sensitively evaluate variation in chemical dry etching rates of semiconductor materials with sub-5 nm resolution

Ion implantation is a robust and established method to customize the electronic properties of Si. However, fabricating doped, ultrafine semiconductor nanostructures can be challenging. Ion implantation has well-established effects on the dry etch rates of Si, which becomes increasingly consequential as the target dimension shrinks below a few tens of nanometers. While dry etching arrays of block copolymer-templated nanoscale holes (pitch = 37.5 nm, diameter ~25 nm) into p-type, n-type, and undoped Si, we observed that the lateral etch rate was notably larger for the n-type regions than p-type or undoped regions. By doing image analyses on high resolution electron micrographs of the nanostructured hole arrays, we were able to extract the porosity and average radii of the holes with subnanometer sensitivity and compare the relative etch rates between different doping conditions. We found that degenerately doped n-type silicon consistently etches between approximately 17% and 27% faster in the lateral direction than p-type Si, resulting in significantly larger porosity and, consequently, less mechanical stability. Here, we demonstrate that top-down dimensional analysis of a densely packed porous nanostructure is a robust method for assessing extremely small differences in the lateral, chemical etch rate of doped Si to a degree of sensitivity that was previously unachievable. The minute, dense-packed nature of block copolymer self-assembled nanostructures is shown to be ideal for this application. This proposed method could be useful for designing fabrication processes for heterogeneous nanostructures, as slight dry etch rate variations that may be within process tolerance at the micrometer-scale appear to have nontrivial consequences at the nanometer scale.

42 ENGINEERING↗
DOE OSTI2025

Reversible Physical Gelation of Thermotropic Liquid Crystals Driven by Nanoplate Self-Assembly

Physically gelled soft materials, driven by the self-assembly of low-molecular-mass gelators (LMGs), have emerged as a platform for designing advanced gels that exhibit reversible gelation and property tunability. Liquid crystal (LC) gels are of great interest due to their supramolecular orderings as gel hosts and their enhanced electro-optical properties. In this study, we demonstrate the physical gelation of a nematic LC driven by nanoplate self-assembly, expanding the concept of gelators from small molecules to nanoparticles. These nanoplates are functionalized with promesogenic ligands and form a fibrillar network in LCs with face-to-face interplate stacking, resembling LMGs. The critical gelation volume fraction in the tilt test is only 0.14 v %, comparable to values reported for LMGs. Rheological analyses confirm viscoelastic properties characteristic of gelation. In situ small-angle X-ray scattering (SAXS) characterizes the formation of nanoplate networks in the LC with decreasing temperature, wherein LC mesogens become trapped in pores. Molecular dynamics (MD) simulations reveal that the interaction between ligand-coated nanoplates and LC-forming mesogens induces a multidomain LC structure, increasing friction between LC domains and stabilizing the gel. This study establishes direct relationships among molecular interactions, nanostructures, and mechanical properties in physically gelled LCs. In conclusion, the findings inspire the future gelator design of both LMGs and nanoplates, with potential applicability in bioscaffold engineering and liquid crystalline nanocomposites.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Laser-assisted direct ink writing of planar and 3D metal architectures

Significance The growing demand for customized electronic devices underpins the need for 3D fabrication methods that enable form factors well beyond those that are flat and rigid. A printing method is introduced for one-step fabrication of conductive and ductile metal features in planar and complex 3D shapes that combines direct ink writing with “on-the-fly” laser annealing.

42 ENGINEERING↗
DOE OSTI2016

Supramolecular Assembly of Molecular Rare-Earth–3,5-Dichlorobenzoic Acid–2,2':6',2"-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior

The syntheses and crystal structures of 16 new rare-earth (RE = La 3+ –Y 3+ )–3,5-dichlorobenzoic acid–terpyridine molecular materials characterized via single-crystal and powder X-ray diffraction are reported. These 16 complexes consist of four unique structure types ranging from molecular dimers (La 3+ and Ce 3+ ) to tetramers (Pr 3+ –Y 3+ ) as one moves across the RE 3+ series. This structural evolution is accompanied by subsequent changes in modes of supramolecular assembly (halogen bonding, halogen-π, halogen–halogen, and π–π interactions). Solid-state visible and near-infrared lifetime measurements were performed on complexes 6 (Sm 3+ ), 7 (Eu 3+ ), 9 (Tb 3+ ), 10 (Dy 3+ ), 11 (Ho 3+ ), 12 (Er 3+ ), and 14 (Yb 3+ ), and characteristic emission was observed for all complexes except 11. Lifetime data for 11, 12, and 14 suggest sensitization by the terpy antenna does occur in near-infrared systems, although not as efficiently as in the visible region. Additionally, direct current magnetic susceptibility measurements were taken for complexes 10 (Dy 3+ ) and 12 (Er 3+ ) and showed dominant ferromagnetic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Amphiphilic Baskets for Supramolecular Nanoarchitectures at Interfaces: Inverted Monolayer Formation on Water

Interfacial chemistry of molecular baskets remains poorly understood despite their promise for supramolecular applications of detection and sequestration of toxic molecules including those of illicit drugs, organophosphorus compounds, and anticancer agents. We present a fundamental investigation of the interfacial behavior of three amphiphilic supramolecular baskets (ASB 4, 8, and 12), having increasingly longer yet linear alkyl chains at the top of their bowl-shaped cavity. The studies were completed at the air−water interface to elucidate surface activity, interfacial stability, self-assembly, and monolayer organization that drive inverted monolayer formation, in which the molecular arms orient toward the aqueous phase in a configuration opposite to that typically observed for lipids. Herein, surface pressure−area isotherms of ASB 4, 8, 12, deposited on a water surface, were performed in tandem with nonequilibrium relaxation experiments to quantify surface activity, thermodynamic stability, and monolayer compressibility of the baskets’ monolayer assembly. Brewster angle microscopy enabled direct visualization of morphological evolution, aggregation, and packing at the interface. We show that systematic extension of the hydrocarbon arms, from four to 12 methylene groups, progressively modifies intermolecular packing, drives distinct two-dimensional aggregation pathways, and increases number densities at the air−water interface. Atomistic molecular dynamics simulations corroborate many of these experimentally observed trends and provide mechanistic detail on the cooperative roles of basket topology and interfacial concentration in regulating the hydration structure and dynamics within the cavities generated by surface-adsorbing baskets, consistent with observed variations in surface activity and packing. Our results establish how the topology of these unique supramolecules and their concentration govern interfacial organization and offer a rational framework for designing amphiphiles with predictable behavior at soft interfaces.

Hydrocarbons↗
DOE OSTI2018

The Making and Breaking of Lead-Free Double Perovskite Nanocrystals of Cesium Silver–Bismuth Halide Compositions

Replacing lead in halide perovskites is of great interest due to concerns about stability and toxicity. Recently, lead free double perovskites in which the unit cell is doubled and two divalent lead cations are substituted by a combination of mono- and trivalent cations have been synthesized as bulk single crystals and as thin films. In this report, we investigate stability and optical properties of all-inorganic cesium silver(I) bismuth(III) chloride and bromide nanocrystals with the double perovskite crystal structure. The cube-shaped nanocrystals are monodisperse in size with typical side lengths of 8 to 15 nm. The absorption spectrum of the nanocrystals presents a sharp peak, which we assign to a direct bismuth s-p transition and not to a quantum confined excitonic transition. Using this spectroscopic handle combined with high-resolution transmission electron microscopy (TEM) based elemental analysis, we conduct stoichiometric studies at the single nanocrystal level as well as decomposition assays in solution and observe that Ag+ diffusion and coalescence is one of the pathways by which this material degrades. Drying the nanocrystals leads to self-assembly into ordered nanocrystal solids, and these exhibit less degradation than nanocrystals in solution. Our results show that Cs 2 AgBiX 6 (X = Cl, Br) nanocrystals are a useful model system to study structure-function relationships in the search for stable nontoxic halide perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Evolution of Self-Assembled ZnTe Magic-Sized Nanoclusters

Three families of ZnTe magic-sized nanoclusters (MSNCs) were obtained exclusively using polytellurides as a tellurium precursor in a one-pot reaction by simply varying the reaction temperature and time only. Different ZnTe MSNCs exhibit different self-assembling or aggregation behavior, owing to their different structure, cluster size, and dipole-dipole interactions. The smallest family of ZnTe MSNCs (F323) does not reveal a crystalline structure and as a result assembles into lamellar triangle plates. Continuous heating of as synthesized ZnTe F323 assemblies resulted in the formation of ZnTe F398 MSNCs with wurzite structure and concomitant transformation into lamellar rectangle assemblies with the organization of nanoclusters along the < 002 > direction. Further annealing of ZnTe F398 assembled lamellar rectangles leads to full organization of MSNCs in all directions and formation of larger ZnTe F444 NCs that spontaneously form ultrathin nanowires following an oriented attachment mechanism. The key step in control over the size distribution of ZnTe ultrathin nanowires is, in fact, the growth mechanism of ZnTe F398 MSNCs; namely, the step growth mechanism enables formation of more uniform nanowires compared to those obtained by continuous growth mechanism. High yield of ZnTe nanowires is achieved as a result of the wurzite structure of F398 precursor. Transient absorption (TA) measurements show that all three families possess ultrafast dynamics of photogenerated electrons, despite their different crystalline structures.

Zhang, Jun↗
DOE OSTI2025

Abbr. Final report: Self-assembled molecular containers as artificial water channels: towards biomimetic desalination membranes

Global water scarcity demands advances in desalination technologies that can deliver more fresh water with less energy. Current reverse osmosis membranes are fundamentally limited by a trade-off between how much water they can pass and how well they block salts. To address this challenge, we developed a bottom-up strategy to design and test artificial water channels that mimic the efficiency of biological proteins but are built from robust synthetic molecules. Over two years, we synthesized and evaluated more than twenty molecular channel candidates, including supramolecular macrocycles and nanographene pores with atomically precise structures. We showed that small chemical modifications allow direct control over pore size and chemistry, which in turn govern water permeability and salt rejection. In collaboration with university partners, we reported the first experimental demonstration of water transport through a nanographene pore, bridging a long-standing gap between simulation and experiment. Several of the artificial channels we developed achieved water–salt selectivity beyond conventional polymer membranes, highlighting their potential for next-generation desalination and precision separations.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Self-Assembly and Horizontal Orientation Growth of VO 2 Nanowires

Single-crystalline vanadium dioxide (VO 2 ) nanostructures have attracted an intense research interest recently because of their unique single-domain metal-insulator phase transition property. Synthesis of these nanostructures in the past was limited in density, alignment, or single-crystallinity. The assembly of VO 2 nanowires (NWs) is desirable for a ‘‘bottom-up’’ approach to the engineering of intricate structures using nanoscale building blocks. Here, we report the successful synthesis of horizontally aligned VO 2 NWs with a dense growth mode in the [1-100] quartz direction of a polished x-cut quartz surface using a simple vapor transport method. Our strategy of controlled growth of VO 2 NWs promisingly paves the way for designing novel metal-insulator transition devices based on VO 2 NWs.

36 MATERIALS SCIENCE↗