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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 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Enhanced carrier collection efficiency and reduced quantum state absorption by electron doping in self-assembled quantum dot solar cells

Reduced quantum dot (QD) absorption due to state filling effects and enhanced electron transport in doped QDs are demonstrated to play a key role in solar energy conversion. Reduced QD state absorption with increased n-doping is observed in the self-assembled In{sub 0.5}Ga{sub 0.5}As/GaAs QDs from high resolution below-bandgap external quantum efficiency (EQE) measurement, which is a direct consequence of the Pauli exclusion principle. We also show that besides partial filling of the quantum states, electron-doping produces negatively charged QDs that exert a repulsive Coulomb force on the mobile electrons, thus altering the electron trajectory and reducing the probability of electron capture, leading to an improved collection efficiency of photo-generated carriers, as indicated by an absolute above-bandgap EQE measurement. The resulting redistribution of the mobile electron in the planar direction is further validated by the observed photoluminescence intensity dependence on doping.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Expected total counts for the Self-Interrogation Neutron Resonance Densitometry measurements of spent nuclear fuel

The Self-Interrogation Neutron Resonance Densitometry (SINRD) is a passive neutron technique that aims at a direct quantification of {sup 239}Pu in spent fuel assemblies by measuring the attenuation of the neutron flux in the energy region close to the 0.3 eV resonance of {sup 239}Pu. The {sup 239}Pu mass is estimated by calculating the SINRD signature, that is the ratio between the neutron counts in the fast energy region and around the 0.3 eV resonance region. The SINRD measurement approach in this study consisted in introducing a small neutron detector in the central guide tube of a PWR 17x17 fuel assembly. In order to measure the neutron flux in the energy regions defined in the SINRD signature, different detector types were used. The response of a bare {sup 238}U fission chamber is considered for the determination of the fast neutron flux, while other thermal-epithermal detectors wrapped in neutron absorbers are envisaged to measure the neutron flux around the resonance region. This paper provides an estimation of the total neutron counts that can be achieved with the detector types proposed for the SINRD measurement. In the first section a set of detectors are evaluated in terms of total neutron counts and sensitivity to the {sup 239}Pu content, in order to identify the optimal measurement configuration for each detector type. Then a study is performed to increase the total neutron counts by increasing the detector size. The study shows that the highest total neutron counts are achieved by using either {sup 3}He or {sup 10}B proportional counters because of the high neutron efficiency of these detectors. However, the calculations indicate that the biggest contribution to the measurement uncertainty is due to the measurement of the fast neutron flux. Finally, similar sensitivity to the {sup 239}Pu content is obtained by using the different detector types for the measurement of the neutron flux close to the resonance region. Therefore, the total neutron counts associated to each detector type will play a major role in the selection of the detector types used for the SINRD measurement. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2015

Expected count rate for the Self- Interrogation Neutron Resonance Densitometry measurements of spent nuclear fuel

The Self-Interrogation Neutron Resonance Densitometry (SINRD) is a passive neutron technique that aims at a direct quantification of {sup 239}Pu in the fuel assemblies by measuring the attenuation of the neutron flux in the energy region close to the 0.3 eV resonance of {sup 239}Pu. The {sup 239}Pu mass is estimated by calculating the SINRD signature, that is the ratio between the neutron flux integrated over the fast energy region and around the 0.3 eV resonance region. The SINRD measurement approach considered in this study consists in introducing a small neutron detector in the central guide tube of a PWR 17x17 fuel assembly. In order to measure the neutron flux in the energy regions defined in the SINRD signature, different detector types are used. The response of a bare {sup 238}U fission chamber is considered for the determination of the fast neutron flux, while other thermal-epithermal detectors wrapped in neutron absorbers are envisaged to measure the neutron flux around the resonance region. This paper provides an estimation of the count rate that can be achieved with the detector types proposed for the SINRD measurement. In the first section a set of detectors are evaluated in terms of count rate and sensitivity to the {sup 239}Pu content, in order to identify the optimal measurement configuration for each detector type. Then a study is performed to increase the count rate by increasing the detector size. The study shows that the highest count rate is achieved by using either {sup 3}He or {sup 10}B proportional counters because of the high neutron efficiency of these detectors. However, the calculations indicate that the biggest contribution to the measurement uncertainty is due to the measurement of the fast neutron flux. Finally, similar sensitivity to the {sup 239}Pu content is obtained by using the different detector types for the measurement of the neutron flux close to the resonance region. Therefore, the count rate associated to each detector type will play a major role in the selection of the detector types used for the SINRD measurement. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Bioinspired Design of Dissipative Self-Assembly of Active Materials (Final Technical Report)

The major objective of this DOE-funded research program was to establish general, experimentally validated design principles for dissipative, out-of-equilibrium self-assembly of synthetic active materials. In living systems, structures such as actin filaments and microtubules are maintained far from thermodynamic equilibrium through continuous energy consumption. This persistent nonequilibrium operation enables functions including adaptability, self-healing, directed motion, and force generation—properties that are largely absent in traditional equilibrium soft materials.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Tuning crystallization pathways through sequence engineering of biomimetic polymers

Two-step nucleation pathways in which disordered, amorphous, or dense liquid states precede the appearance of crystalline phases have been reported for a wide range of materials, but the dynamics of such pathways are poorly understood. Moreover, whether these pathways are general features of crystallizing systems or a consequence of system-specific structural details that select for direct versus two-step processes is unknown. Using atomic force microscopy to directly observe crystallization of sequence-defined polymers, we show that crystallization pathways are indeed sequence dependent. When a short hydrophobic region is added to a sequence that directly forms crystalline particles, crystallization instead follows a two-step pathway that begins with the creation of disordered clusters of 10–20 molecules and is characterized by highly non-linear crystallization kinetics in which clusters transform into ordered structures that then enter the growth phase. The results shed new light on non-classical crystallization mechanisms and have implications for the design of self-assembling polymer systems.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Mechanisms of Biomolecular Self-Assembly Investigated Through In Situ Observations of Structures and Dynamics

Biomolecular self-assembly of hierarchical materials is a precise and adaptable bottom-up approach to synthesizing across scales with considerable energy, health, environment, sustainability, and information technology applications. To achieve desired functions in biomaterials, it is essential to directly observe assembly dynamics and structural evolutions that reflect the underlying energy landscape and the assembly mechanism. This report will summarize the current understanding of biomolecular assembly mechanisms based on in situ characterization and discuss the broader significance and achievements of newly gained insights. In addition, we will also introduce how emerging deep learning/machine learning-based approaches, multiparametric characterization, and high-throughput methods can boost the development of biomolecular self-assembly. The objective of this review is to accelerate the development of in situ characterization approaches for biomolecular self-assembly and to inspire the next generation of biomimetic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Mechanisms of Biomolecular Self–Assembly Investigated Through In Situ Observations of Structures and Dynamics

Biomolecular self-assembly of hierarchical materials is a precise and adaptable bottom-up approach to synthesizing across scales with considerable energy, health, environment, sustainability, and information technology applications. To achieve desired functions in biomaterials, it is essential to directly observe assembly dynamics and structural evolutions that reflect the underlying energy landscape and the assembly mechanism. This review will summarize the current understanding of biomolecular assembly mechanisms based on in situ characterization and discuss the broader significance and achievements of newly gained insights. In addition, we will also introduce how emerging deep learning/machine learning-based approaches, multiparametric characterization, and high-throughput methods can boost the development of biomolecular self-assembly. Furthermore, the objective of this review is to accelerate the development of in situ characterization approaches for biomolecular self-assembly and to inspire the next generation of biomimetic materials.

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

Post-Modification of Crystalline Peptoid Nanomembranes with Active Nanoparticles for Efficient Photooxidation of a Mustard Gas Simulant

Peptoids (or poly-N-substituted glycines) hold immense potential for assembling into hierarchically structured functional materials via controlled molecular interactions. To create self-assembled materials with tailored functionalities, peptoid sequences are often conjugated with reactive or recognition motifs to enable applications including specific binding, biomimetic catalysis, and fluorescence imaging. However, the direct integration of bulky functional motifs into peptoid sequences can disrupt assembly processes and structural outcomes. Herein, we present a post-modification strategy for functionalizing pre-formed 2D crystalline assemblies. Through introducing clickable active sites, such as azide, alkyne, or thiol groups into a peptoid sequence, site-specific conjugation is achieved post-assembly via efficient “click”-type reactions. This strategy enables the ordered alignment of functional groups and gold nanoparticles (Au NPs) on the surface of 2D peptoid nanomaterials with controlled density, while preserving their high crystallinity and structural integrity. Furthermore, we demonstrated that nanomembranes functionalized with both Au NPs and porphyrins enhance the efficiency and selectivity of the photooxidation of 2-chloroethyl ethyl sulfide, a simulant of sulfur mustard. This innovative strategy lays the groundwork for advancing peptoid-based functional materials across diverse applications, from catalysis to biomedicine.

Chemistry↗
DOE OSTI2020

Self‐Assembled NiO Nanocrystal Arrays as Memristive Elements

Abstract Memristive switching, a nonlinear current–voltage ( I – V ) characteristic, has seen a tremendous surge in interest as an approach to achieve implementation of synaptic functions. The memristive switching behavior of self‐assembled NiO nanocrystals is investigated via scanning probe microscopy, based on first‐order reversal curve current–voltage spectroscopy. Synaptic switching is clearly observed as a direct consequence of filament growth (i.e., gradually increased conductance) in the nanocrystals. A spatial dependency of the conduction in the nanocrystals suggests that there is a localization of the switching filament. The current understanding of this localization ignores features related to local lateral variation current, which can generate an excessive local heat and temperature such as electrical dissipation. The observation of low electrical dissipation at the edge of the nanocrystals shows that less energy is wasted as heat such that the bias applied can be utilized more efficiently to assist the nucleation of the filament and thus reduces the power consumption. Electrical power dissipation is also found to scale with nanocrystal height and has spatial dependence within the nanocrystals. The combination of synaptic switching and high density of the nanocrystals demonstrate that it is feasible to exploit them to create a basic architecture for neuromorphic memory devices.

Kurnia, Fran↗
DOE OSTI2014

Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-coordinate Silicon Alcoholate Complexes

The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. Here the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes through a novel transesterification mechanism is reported. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building units (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na+O2- ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na+ counter-ions as a result of unique atomic arrangement in its structure. However, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7m(2)g(-1) for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal-organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity.

Li, XS↗
NASA NTRS2009

Very Long Single and Few-Walled Boron Nitride Nanotubes via the Pressurized Vapor/Condenser Method

A new method for producing long, small diameter, single and few-walled, boron nitride nanotubes (BNNTs) in macroscopic quantities is reported. The pressurized vapor/condenser (PVC) method produces, without catalysts, highly crystalline, very long, small diameter, BNNTs. Palm-sized, cotton-like masses of BNNT raw material were grown by this technique and spun directly into centimeters-long yarn. Nanotube lengths were observed to be 100 times that of those grown by the most closely related method. Self-assembly and growth models for these long BNNTs are discussed.

Smith, Michael W.↗
DOE OSTI2019

Supramolecular Tessellations by a Rigid Naphthalene Diimide Triangle

Tessellation of organic polygons though [π···π] and charge-transfer (CT) interactions offers a unique opportunity to construct supramolecular organic electronic materials with 2D topologies. Our approach to exploring the 3D topology of 2D tessellations of a naphthalene diimide-based molecular triangle (NDI-Δ) reveals that the 2D molecular arrangement is sensitive to the identity of the solvent and solute concentrations. Utilization of nonhalogenated solvents, combined with careful tailoring of the concentrations, results in NDI-Δ self-assembling though [π···π] interactions into 2D honeycomb triangular and hexagonal tiling patterns. Cocrystallization of NDI-Δ with tetrathiafulvalene (TTF) leads systematically to the formation of 2D tessellations as a result of superstructure-directing CT interactions. Different solvents lead to different packing arrangements. Using MeCN, CHCl 3 , and CH 2 Cl 2 , we identified three sets of cocrystals, namely CT-A, CT-B, and CT-C, respectively. Here, solvent modulation plays a critical role in controlling not only the NDI-Δ:TTF stoichiometric ratios and the molecular arrangements in the crystal superstructures, but also prevents the inclusion of TTF guests inside the cavities of NDI-Δ. Confinement of TTF inside the NDI-Δ cavities in the CT-A superstructure enhances the CT character with the observation of a broad absorption band in the NIR region. In the CT-B superstructure, the CHCl 3 lattice molecules establish a set of [Cl···Cl] and [Cl···S] intermolecular interactions, leading to the formation of a hexagonal grid of solvent in which NDI-Δ forms a triangular grid. In the CT-C superstructure, three TTF molecules self-assemble, forming a supramolecular isosceles triangle TTF-Δ, which tiles in a plane alongside the NDI-Δ, producing a 3 + 3 honeycomb tiling pattern of the two different polygons. Solid-state spectroscopic investigations on CT-C revealed the existence of an absorption band at 2500 nm, which on the basis of TDDFT calculations, was attributed to the mixed-valence character between two TTF • + radical cations and one neutral TTF molecule.

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

Photocatalytic oxidation of the organic monolayers on TiO{sub 2} surface investigated by in-situ sum frequency generation spectroscopy

In-situ vibrational sum frequency generation (SFG) spectroscopy has been employed to investigate the photocatalytic oxidation of two types of well-ordered organic monolayers, namely, an arachidic acid (AA) monolayer prepared by the Langmuir-Blodgett method and an octadecyltrichlorosilane (OTS) monolayer prepared by the self-assembling method, on a TiO{sub 2} surface under ultraviolet (UV) irradiation. The extremely high sensitivity and unique selectivity of the SFG spectroscopy enabled us to directly probe the structural changes in these monolayers during the surface photocatalytic oxidation and further elucidate their reaction mechanisms at a molecular level. It was revealed that the ordering of the monolayers during the photocatalytic reaction is strongly dependent on their interaction with the substrate; the AA monolayer maintains its ordered conformation until the final oxidation stage, while the OTS monolayer shows a large increase in disordering during the initial oxidation stage, indicating a different photocatalytic reaction mechanism of the two monolayers on the TiO{sub 2} surface.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Dynamic control of polarization-inverted modes in three-dimensionally trapped multiple nanogaps

We propose a guiding principle for the dynamic control of polarization-inverted modes in multiple nanogaps for unconventional optical transitions of molecules at arbitrary three-dimensional spatial positions. Based on our developed self-consistent theory for the optical assembly of nanoparticles (NPs), we clarified that spherical silver NPs can be optically trapped and aligned in the light-propagating direction via longitudinally polarized light; they form a rod-like nano-composite with multiple nanogaps. During trapping, there is a possibility that an additional irradiation of linearly polarized far-field light may excite the bonding and anti-bonding dark plasmon modes with low radiative decay rate of several meV via cancellation of inverted polarization. Our finding reveals that not only the steep change in the enhanced intensity of light field but also the phase inversion of light field between the dynamically formed nanogaps will pave the way to the highly sensitive sensors for molecules, the unconventional chemical reactions, and so on.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Gelation of plasmonic metal oxide nanocrystals by polymer-induced depletion attractions

Significance Self-supported gelation of optically active nanocrystals offers a modular pathway to harness optoelectronic functionality in multiscale materials by directly controlling volume fraction, bonding, and structure during assembly. We combine depletion attractions that emerge from the incorporation of small polymer chains and electrostatic repulsions to induce the gelation of isotropic metal oxide nanocrystals. We develop a theoretical model to assess our experimental fluid-to-gel-phase progression observations. By preventing nanocrystal fusion during network assembly, we achieve gels with a strong near-infrared absorption, reminiscent of the inherent near-infrared localized surface plasmon resonance of the nanocrystal building blocks.

Saez Cabezas, Camila A.↗
DOE OSTI2013

A molecular design principle of lyotropic liquid-crystalline conjugated polymers with directed alignment capability for plastic electronics

Conjugated polymers with a one-dimensional p-orbital overlap exhibit optoelectronic anisotropy. Their unique anisotropic properties can be fully realized in device applications only when the conjugated chains are aligned. Here, we report a molecular design principle of conjugated polymers to achieve concentration-regulated chain planarization, self-assembly, liquid-crystal-like good mobility and non-interdigitated side chains. As a consequence of these intra- and intermolecular attributes, chain alignment along an applied flow field occurs. This liquid-crystalline conjugated polymer was realized by incorporating intramolecular sulphur–fluorine interactions and bulky side chains linked to a tetrahedral carbon having a large form factor. By optimizing the polymer concentration and the flow field, we could achieve a high dichroic ratio of 16.67 in emission from conducting conjugated polymer films. Two-dimensional grazing-incidence X-ray diffraction was performed to analyse a well-defined conjugated polymer alignment. Thin-film transistors built on highly aligned conjugated polymer films showed more than three orders of magnitude faster carrier mobility along the conjugated polymer alignment direction than the perpendicular direction.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Natural selection in the colloid world: active chiral spirals

We present a model system in which to study natural selection in the colloid world. In the assembly of active Janus particles into rotating pinwheels when mixed with trace amounts of homogeneous colloids in the presence of an AC electric field, broken symmetry in the rotation direction produces spiral, chiral shapes. Locked into a central rotation point by the centre particle, the spiral arms are found to trail rotation of the overall cluster. To achieve a steady state, the spiral arms undergo an evolutionary process to coordinate their motion. Because all the particles as segments of the pinwheel arms are self-propelled, asymmetric arm lengths are tolerated. Reconfiguration of these structures can happen in various ways and various mechanisms of this directed structural change are analyzed in detail. Here, we introduce the concept of VIP (very important particles) to express that sustainability of active structures is most sensitive to only a few particles at strategic locations in the moving self-assembled structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗