SEARCH · Search NASA

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.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 469 records · Page 26

All sources NASA NTRS DOE OSTI

DOE OSTI2012

Skutterudite Unicouple Characterization for Energy Harvesting Applications

Skutterudites are enticing thermoelectric materials due to their high figure of merit, ZT, and good thermomechanical properties. Our work reports the effective figure of merit, ZT eff , and the efficiency of skutterudite legs and a unicouple working under a large temperature difference. The p- and n-type legs are fabricated with electrodes sintered directly to the skutterudite during a hot pressing process. CoSi 2 is used as the electrode for the n-type skutterudite (Yb 0.35 Co 4 Sb 12 ) and Co2Si for the p-type skutterudite (NdFe 3.5 Co 0.5 Sb 12 ). A technique is developed to measure the ZT eff of individual legs and the efficiency of a unicouple. An ZT eff of 0.74 is determined for the n-type legs operating between 52 and 595 °C, and an ZT eff of 0.51 for the p-type legs operating between 77 and 600 °C. The efficiency of the p–n unicouple is determined to be 9.1% operating between ~70 and 550 °C.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2021

Self-similar mesocrystals form via interface-driven nucleation and assembly

Crystallization by particle attachment (CPA) is a frequently occurring mechanism of colloidal crystallization that results in hierarchical morphologies. CPA has been exploited to create nanomaterials with unusual properties and is implicated in the development of complex mineral textures. Oriented attachment–a form of CPA in which particles align along specific crystallographic directions–produces mesocrystals that diffract as single crystals do, although the constituent particles are still discernible. The conventional view of CPA is that nucleation provides a supply of particles that aggregate via Brownian motion biased by attractive interparticle potentials. However, mesocrystals often exhibit regular morphologies and uniform sizes. Although many crystal systems form mesocrystals and individual attachment events have been directly visualized10, how random attachment events lead to well defined, self-similar morphologies remains unknown, as does the role of surface-bound ligands, which are ubiquitous in nanoparticle systems. Attempts to understand mesocrystal formation are further complicated in many systems by the presence of precursor nanoparticles with a phase distinct from that of the bulk. Some studies propose that such particles convert before attachment, whereas others attribute conversion to the attachment process itself and yet others conclude that transformation occurs after the mesocrystals exceed a characteristic size. Here we investigate mesocrystal formation by iron oxides, which are important colloidal phases in natural environments and classic examples of systems forming ubiquitous precursor phases and undergoing CPA accompanied by phase transformations. Combining in situ transmission electron microscopy (TEM) at 80 degrees Celsius with ‘freeze-and-look’ TEM, we tracked the formation of haematite (Hm) mesocrystals in the presence of oxalate (Ox), which is abundant in soils, where iron oxides are common. In this work, we find that isolated Hm particles rarely appear, but once formed, interfacial gradients at the Ox-covered surfaces drive Hm particles to nucleate repeatedly about two nanometres from the surfaces, to which they then attach, thereby generating mesocrystals. Comparison to natural and synthetic systems suggests that interface-driven pathways are widespread.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Cellular Delivery of Nanoparticles Revealed with Combined Optical and Isotopic Nanoscopy

Synthetic drug-carrying nanomaterials offer great potential as targeted cellular delivery vehicles. Typically, their size, morphology, surface chemistry and stability are optimized in order to control their effect on drug release kinetics, cellular uptake pathways, efficiency and site of action. However, methods to track the carriers and their cargo independently at the micro- and nanoscale have been severely underutilized preventing the correlation between structure and function. Here we show that by using combined optical and isotopic nanoscopy we can track the uptake in cancer cells and subsequent drug release of a Pt(II)-loaded anticancer nanoparticle (NP) system. We found that by directly polymerizing an oxaliplatin analogue containing a norbornyl moiety amenable to polymerization via ring opening metathesis polymerization (ROMP) we could generate amphiphiles in one pot. Spontaneous self-assembly of the drug-containing polymers in aqueous solution led to well-defined NPs in a reproducible manner. Our results demonstrate that the covalently loaded NPs are equipotent with free oxaliplatin and are taken up intact via endocytic pathways before release of the cytotoxic cargo. This was confirmed by super resolution fluorescence structured illumination microscopy (SIM) and nanoscale secondary ion mass spectrometry (NanoSIMS). We anticipate that this type of multimodal cellular tracking of NP and drug will bridge the knowledge gap between particle structure and performance for the vast array of currently generalizable systems in the literature. Furthermore, the use of covalently loaded NP drug systems should allow development of more stable, reproducible and site specific nanodelivery agents.

Environmental Molecular Sciences Laboratory↗

DOE OSTI2012

Pushing The Sample-Size Limit Of Infrared Vibrational Nano-Spectroscopy: From Monolayer Towards Single molecule sensitivity

While scattering-scanning near-field optical microscopy (s-SNOM) has demonstrated its potential to extend infrared (IR) spectroscopy into the nanometer scale, it has not yet reached its full potential in terms of spectroscopic sensitivity. We combine broadband femtosecond mid-IR excitation with an optimized spectral irradiance of 2 W/cm2/ cm–1 (power/area/bandwidth) and a combination of tip- and substrate enhancement to demonstrate single-monolayer sensitivity with exceptional signal-to-noise ratio. Using interferometric time domain detection, the near-field IR s-SNOM spectral phase directly reflects the molecular vibrational resonances and their intrinsic line shapes. We probe the stretching resonance of 1000 carbonyl groups at 1700 cm–1 in a self-assembled monolayer of 16-mercaptohexadecanoic acid (MHDA) on an evaporated gold substrate with spectroscopic contrast and sensitivity of 100 vibrational oscillators. From these results we provide a roadmap for achieving true single-molecule IR vibrational spectroscopy in s-SNOM by implementing optical antenna resonant enhancement, increased spectral pump power, and improved detection schemes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Rate Enhancement of Acid-Catalyzed Alcohol Dehydration by Supramolecular Organic Capsules

The presence of a (sub)nanometric environment has been demonstrated to enhance the rate of homogeneous acid-catalyzed reactions. Conventionally, such catalysts are constructed by directly embedding a catalytically active acid site into the structure of a porous material, linking the acid properties with the properties of the embedding solid. Here, a holoenzyme mimicking approach was used, in which a self-assembled hexameric resorcinarene capsule (1.4 nm 3 cavity) acts like an apoenzyme that transforms into a catalytically active site by hosting hydrated HCl as a cofactor. This capsule binds the hydronium ion together with cyclohexanol (CyOH) and catalyzes the dehydration to cyclohexene with enhanced rates that are 2 orders of magnitude higher than those in the unconstrained environment. Kinetic analysis shows that cyclohexanol dehydration proceeds via an E2 mechanism on hydrated HCl in the unconstrained environment, while the constrained environment of the active capsule induces the stabilization of an ionic intermediate, allowing an E1 mechanism to dominate. By comparison with the reaction in zeolite environments, we show that the direct chemical environment of the capsule or a zeolite wall exerts only a minor direct influence. The volume constraint increases the reaction rate by inducing a larger activation entropy, indicating the stabilization of a later transition state in the E1 mechanism, as well as a higher reaction space of the carbenium ion constituting the transition state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Colloidal self assembly of non-magnetic particles in magnetic nanofluid

Here we present a technique using magnetic nanofluid to induce bidispersed suspension of nonmagnetic particles to assemble into colloidal chain, triangle, rectangle, ring-flower configurations. By changing the amplitude and direction of the magnetic field, we could tune the structure of nonmagnetic particles in magnetic nanofluid. The structures are assembled using magneto static interactions between effectively nonmagnetic particles dispersed in magnetizable magnetic nanofluid. The assembly of complex structures out of simple colloidal building blocks is of practical interest in photonic crystals and DNA biosensors.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Modeling the self-assembly of ordered nanoporous materials

This report describes progress on a collaborative project on the multiscale modeling of the assembly processes in the synthesis of nanoporous materials. Such materials are of enormous importance in modern technology with application in the chemical process industries, biomedicine and biotechnology as well as microelectronics. The project focuses on two important classes of materials: i) microporous crystalline materials, such as zeolites, and ii) ordered mesoporous materials. In the first case the pores are part of the crystalline structure, while in the second the structures are amorphous on the atomistic length scale but where surfactant templating gives rise to order on the length scale of 2 - 20 nm. We have developed a modeling framework that encompasses both these kinds of materials. Our models focus on the assembly of corner sharing silica tetrahedra in the presence of structure directing agents. We emphasize a balance between sufficient realism in the models and computational tractibility given the complex many-body phenomena. We use both on-lattice and off-lattice models and the primary computational tools are Monte Carlo simulations with sampling techniques and ensembles appropriate to specific situations. Our modeling approach is the first to capture silica polymerization, nanopore crystallization, and mesopore formation through computer-simulated self assembly.

36 MATERIALS SCIENCE↗

DOE OSTI2012

Lateral Spectrum Splitting Concentrator Photovoltaics: Direct Measurement of Component and Submodule Efficiency

To achieve high energy conversion efficiency, a solar module architecture called lateral spectrum splitting concentrator photovoltaics (LSSCPV) is being developed. LSSCPV can concentrate available sunlight and laterally split a single beam into bands with different spectra for absorption by different solar cells with band gaps matched to the split spectrum. Test assemblies of a sample LSSCPV architecture were constructed, each of which contains four p-n junctions and two optical pieces. Independent experiments or simulations had been implemented on the components but by using optimal assumptions. In order to examine the actual performances of all the components, which are dependent on each other and the light source, direct outdoor measurements were made. A set of self-consistent efficiency definitions was articulated and a test bed was developed to measure the parameters required by the efficiency calculation. By comparing the component efficiency items derived from the outdoor measurement and the expected values based on independent simulations, the potential opportunities for efficiency improvement are determined. In the outdoor measurement at the University of Delaware, the optical component demonstrated 89.1% efficiency. Additional assemblies were tested at the National Renewable Energy Laboratory. One assembly demonstrated 36.7% submodule efficiency, which compares favorably with the 32.6% previously reported verified submodule efficiency.

14 SOLAR ENERGY↗

DOE OSTI2024

Phase segregation of a composite air electrode unlocks the high performance of reversible protonic ceramic electrochemical cells

One breakthrough in developing highly efficient air electrodes for reversible protonic ceramic electrochemical cells (R-PCECs) is optimizing the sluggish oxygen reduction and water oxidation reactions. Here, we present a novel composite material with a nominal formula of high-entropy Ce 0.2 Ba 0.2 Sr 0.2 La 0.2 Ca 0.2 CoO 3–δ (CBSLCC) that spontaneously self-assembles to three-phase electrocatalysts composed of deficient Ce 0.2–y Ba 0.2 Sr 0.2–x La 0.2–x Ca 0.2 CoO 3–δ (CD-CBSLCC), CeO 2 , and La 0.5 Sr 0.5 CoO 3–δ (LSC). Mechanistic studies corroborate that oxygen reduction may occur on entire air electrode surfaces, followed by water formation preferentially at or near CD-CBSLCC. The CeO 2 phase could provide or consume protons to facilitate the oxygen evolution/reduction kinetics in R-PCECs. The developed electrodes demonstrate a record-high electrochemical performance in dual modes of fuel cells and electrolysis cells, delivering a peak power density of 1.66 W cm –2 at 600 °C and a current density of –1.76 A cm –2 at 1.3 V and 600 °C. Finally, excellent operational stabilities of the fuel cell (200 h at 600 °C), electrolysis cell (200 h at 600 °C), and reversible cycling (548 h at 550 °C) provide a promising and reliable step towards realizing the commercialization of R-PCECs.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2018

Supramolecular Assemblies on Surfaces: Nanopatterning, Functionality, and Reactivity

Understanding how molecules interact to form large-scale hierarchical structures on surfaces holds promise for building designer nanoscale constructs with defined chemical and physical properties. Here, we describe early advances in this field and highlight upcoming opportunities and challenges. Both direct intermolecular interactions and those that are mediated by coordinated metal centers or substrates are discussed. These interactions can be additive, but they can also interfere with each other, leading to new assemblies in which electrical potentials vary at distances much larger than those of typical chemical interactions. Earlier spectroscopic and surface measurements have provided partial information on such interfacial effects. In the interim, scanning probe microscopies have assumed defining roles in the field of molecular organization on surfaces, delivering deeper understanding of interactions, structures, and local potentials. Furthermore, self-assembly is a key strategy to form extended structures on surfaces, advancing nanolithography into the chemical dimension and providing simultaneous control at multiple scales. In parallel, the emergence of graphene and the resulting impetus to explore 2D materials have broadened the field, as surface-confined reactions of molecular building blocks provide access to such materials as 2D polymers and graphene nanoribbons. In this Review, we describe recent advances and point out promising directions that will lead to even greater and more robust capabilities to exploit designer surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2012

Superstructure of self-aligned hexagonal GaN nanorods formed on nitrided Si(111) surface

We present here the spontaneous formation of catalyst-free, self-aligned crystalline (wurtzite) nanorods on Si(111) surfaces modified by surface nitridation. Nanorods grown by molecular beam epitaxy on bare Si(111) and non-stoichiometric silicon nitride interface are found to be single crystalline but disoriented. Those grown on single crystalline Si{sub 3}N{sub 4} intermediate layer are highly dense c-oriented hexagonal shaped nanorods. The morphology and the self-assembly of the nanorods shows an ordered epitaxial hexagonal superstructure, suggesting that they are nucleated at screw dislocations at the interface and grow spirally in the c-direction. The aligned nanorod assembly shows high-quality structural and optical emission properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2015

Super-Joule heating in graphene and silver nanowire network

Transistors, sensors, and transparent conductors based on randomly assembled nanowire networks lean on multi-component percolation for unique and distinctive applications in flexible electronics, biochemical sensing, and solar cells. Although conduction models for 1-D and 1-D/2-D networks have been developed, typically assuming linear electronic transport and self-heating, the model has not been validated by direct high-resolution characterization of coupled electronic pathways and thermal response. In this letter, we show the occurrence of nonlinear “super-Joule” self-heating at the transport bottlenecks in networks of silver nanowires and silver nanowire/single layer graphene hybrid using high resolution thermoreflectance (TR) imaging. TR images at the microscopic self-heating hotspots within nanowire network and nanowire/graphene hybrid network devices with submicron spatial resolution are used to infer electrical current pathways. The findings encourage a fundamental reevaluation of transport models for network-based percolating conductors.

42 ENGINEERING↗

DOE OSTI2021

Hydrogen Bonding Stiffens Peptide Amphiphile Supramolecular Filaments by Aza-Glycine Residues

Peptide amphiphiles (PAs) are a class of molecules comprised of short amino acid sequences conjugated to hydrophobic moieties that may exhibit self-assembly in water into supramolecular structures. Here, we investigate here how mechanical properties of hydrogels formed by PA supramolecular nanofibers are affected by hydrogen bond densities within their internal structure by substituting glycine for aza-glycine (azaG) residues. We found that increasing the number of PA molecules that contain azaG up to 5 mol% in PA supramolecular nanofibers increases their persistence length fivefold and decreases their diffusion coefficients as measured by fluorescence recovery after photobleaching. When these PAs are used to create hydrogels, their bulk storage modulus (G') was found to increase as azaG PA content in the supramolecular assemblies increases up to a value of 10 mol% and beyond this value a decrease was observed, likely due to diminished levels of nanofiber entanglement in the hydrogels as a direct result of increased supramolecular rigidity. Interestingly, we found that the bioactivity of the scaffolds toward dopaminergic neurons derived from induced pluripotent stem cells can be enhanced directly by persistence length independently of storage modulus. We hypothesize that this is due to interactions between the cells and the extracellular environment across different size scales: from filopodia adhering to individual nanofiber bundles to cell adhesion sites that interact with the hydrogel as a bulk substrate. Fine tuning of hydrogen bond density in self-assembling peptide biomaterials such as PAs provides an approach to control nanoscale stiffness as part of an overall strategy to optimize bioactivity in these supramolecular systems. supramolecular biomaterials.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Structure and Conductivity of Semiconducting Polymer Hydrogels

Poly(fluorene-alt-thiophene) (PFT) is a conjugated polyelectrolyte that self-assembles into rod-like micelles in water, with the conjugated polymer backbone running along the length of the micelle. At modest concentrations (-10 mg/mL in aqueous solutions), PFT forms hydrogels, and this work focuses on understanding the structure and intermolecular interactions in those gel networks. The network structure can be directly visualized using cryo electron microscopy. Oscillatory rheology studies further tell us about connectivity within the gel network, and the data are consistent with a picture where polymer chains bridge between micelles to hold the network together. Addition of tetrahydrofuran (THF) to the gels breaks those connections, but once the THF is removed, the gel becomes stronger than it was before, presumably due to the creation of a more interconnected nanoscale architecture. Small polymer oligomers can also passivate the bridging polymer chains, breaking connections between micelles and dramatically weakening the hydrogel network. Fits to solution-phase small-angle X-ray scattering data using a Dammin bead model support the hypothesis of a bridging connection between PFT micelles, even in dilute aqueous solutions. Finally, time-resolved microwave conductivity measurements on dried samples show an increase in carrier mobility after THF annealing of the PFT gel, likely due to increased connectivity within the polymer network.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2013

Lead Slowing Down Spectrometer Research Plans

The MPACT-funded Lead Slowing Down Spectrometry (LSDS) project has been evaluating the feasibility of using LSDS techniques to assay fissile isotopes in used nuclear fuel assemblies. The approach has the potential to provide considerable improvement in the assay of fissile isotopic masses in fuel assemblies compared to other non-destructive techniques in a direct and independent manner. The LSDS collaborations suggests that the next step to in empirically testing the feasibility is to conduct measurements on fresh fuel assemblies to understand investigate self-attenuation and fresh mixed-oxide (MOX) fuel rodlets so we may better understand extraction of masses for 235 U and 239 Pu. While progressing toward these goals, the collaboration also strongly suggests the continued development of enabling technology such as detector development and algorithm development, which could provide significant performance benefits.

Lead slowing down spectrometry↗

DOE OSTI2013

How to Store Energy Fast

Representing the Molecularly Engineered Energy Materials (MEEM), this document is one of the entries in the Ten Hundred and One Word Challenge. As part of the challenge, the 46 Energy Frontier Research Centers were invited to represent their science in images, cartoons, photos, words and original paintings, but any descriptions or words could only use the 1000 most commonly used words in the English language, with the addition of one word important to each of the EFRCs and the mission of DOE energy. The mission of MEEM, using inexpensive custom-designed molecular building blocks, aims to create revolutionary new materials with self-assembled multi-scale architectures that will enable high performing energy generation and storage applications.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2013

Self-assembled cabbage-like NaInS{sub 2} microstructures with efficient visible light photocatalytic performance

Cabbage-like NaInS{sub 2} microstructures have been synthesized by reacting In(NO{sub 3}){sub 3} with the alkaline sulfur aqueous solution of NaOH in a simple hydrothermal process without any shape-directing surfactants. The cabbage-like NaInS{sub 2} architectures are monodispersed in large quantities. The cabbage-like morphologies depend strongly on the different ratios of S powder to NaOH, the reaction temperature and reaction time. The possible growth mechanism for the formation of cabbage-like NaInS{sub 2} architectures is discussed. The cabbage-like NaInS{sub 2} architectures exhibit the superiority of photocatalytic performance for the photodegradation of RhB irradiation under visible light irradiation. It is believed that the photocatalytic superiority of the cabbage-like NaInS{sub 2} architectures is mainly due to their special surface areas and inner interconnected structural features. - Graphical abstract: Cabbage-like NaInS{sub 2} microstructures were facilely synthesized via simple hydrothermal reaction. The cabbage-like NaInS{sub 2} architectures exhibit the superiority of photocatalytic performance for the photodegradation of RhB irradiation under visible light irradiation. - Highlights: • Cabbage-like NaInS{sub 2} microstructures were facilely synthesized via a hydrothermal reaction. • Influencing parameters on the NaInS{sub 2} morphologies have been discussed in detail. • The cabbage-like NaInS{sub 2} architectures hold efficient photocatalytic performance. • The photocatalytic superiority is mainly due to their special structural features.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

ATRP Enhances Structural Correlations In Polymerization–Induced Phase Separation**

Synthetic methods to control the structure of materials at sub–micron scales are typically based on the self–assembly of structural building blocks with precise size and morphology. On the other hand, many living systems can generate structure across a broad range of length scales in one step directly from macromolecules, using phase separation. Here, we introduce and control structure at the nano– and microscales through polymerization in the solid state, which has the unusual capability of both triggering and arresting phase separation. In particular, we show that atom transfer radical polymerization (ATRP) enables control of nucleation, growth, and stabilization of phase–separated poly–methylmethacrylate (PMMA) domains in a solid polystyrene (PS) matrix. ATRP yields durable nanostructures with low size dispersity and high degrees of structural correlations. Furthermore, we demonstrate that the length scale of these materials is controlled by the synthesis parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗