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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Biomolecular Films for Direct Air Capture of CO 2

Efficient utilization of CO 2 is amongst the most critical cost drivers in algal biomass production in open pond systems. CO 2 delivery costs represent approximately 20% of the final biomass selling price in algal mass cultivation systems. Technologies that enable direct air capture (DAC) of atmospheric CO 2 to decouple algae cultivation from CO 2 point sources thus present an opportunity to improve the economics and resource potential of algal biomass. Current DAC technologies typically employ amine- or caustic-based absorption, demanding significant water and/or energy inputs and incurring substantial capital expenditures. Conversely, bio-based approaches to DAC offer a means to bypass conventional technoeconomic and sustainability hurdles. We integrate recent advances in computational metabolic modeling, algal genetic engineering, algal cultivation, and algal biomass upgrading to enable directed localization and self-assembly of carbonic anhydrase molecular films to gas-liquid interfaces for enhanced CO 2 capture and conversion.

09 BIOMASS FUELS↗
DOE OSTI2022

Unveiling mechanism of surface-guided platinum nanowire growth

We report surface-guided growth of non-planar nanowires on functional substrates offers the new opportunity to precisely control their diameter, length, density and alignment, which will greatly benefit their direct integration into practical devices for large-scale applications. However, control of noble metal nanowires growth and arrangement remains a great challenge, and the mechanistic understanding is still limited. Herein, we choose Pt as a model material system to study the synthesis conditions required to control the in situ growth of aligned Pt nanowires on flat titanium substrate via a one-step and room-temperature green chemical synthesis process in aqueous solution. Most importantly, it is for the first time discovered that ordered nanoarrays and self-assembled nanoflowers can be directly grown on flat Ti substrate by merely adjusting the reaction times, without use of any soft/hard templates, surfactants and organic solvents. The proposed surface-guided growth mechanisms for nanoarray and nanoflower formation in this study may shed light on understanding of oriented arrangement/assembly of one-dimensional Pt nanowires into desirable morphologies for a variety of practical device applications.

Pt nanoflower↗
DOE OSTI2020

Functional Nanomaterials with Tunable Plasmonic and Emittive Properties (Final Project Report)

The goal of the project is on understanding the principles of non-covalent assembling of tunable functional materials with various nanocrystals in order to control light-matter interactions by changing localized interfacial refractive properties, coupling parameters, or the ionic environment of surrounding media. We explore novel soft functional matrices with controlled physical properties via the application of light, mechanical stresses, ionic environment, and electrical potential. These functional matrices is used in conjunction with novel anisotropic inorganic nanostructures such as noble metal/metal alloy anisotropic nanostructures with complex optical properties (multiple LSPR modes) and quantum dots with light-emissive or absorbing properties in a broad spectral range from the UV to the NIR for efficient solar energy absorption and light conversion.

36 MATERIALS SCIENCE↗
DOE OSTI2024

High Temperature, Isothermal Growth Promotes Close Packing and Thermal Stability in DNA-Engineered Colloidal Crystals

Here, we report a strategy to accelerate the synthesis and increase the crystallinity of colloidal crystals engineered with DNA. Specifically, by holding the DNA-modified Au particle building blocks above the T m of the individual nanoparticle building blocks, but slightly below the T m of the anticipated colloidal crystal during the assembly process, crystallinity is increased, and enthalpically-favored phases with high degrees of facet registration are observed. We studied the utility of this approach with systems for which the commonly adopted slow-cooling approach yielded primarily amorphous aggregates. In particular, we used it to synthesize high-volume fraction colloidal crystals from large (80 nm) anisotropic nanoparticles (cubes and rhombic dodecahedra) with short (<14 nm) DNA designed to restrict the degrees of freedom for the DNA bonds and maintain the anisotropy of the particle building block. Small-angle X-ray scattering and electron microscopy studies show that the crystalline phases synthesized via this method are more thermally stable than their corresponding aggregate phases, likely due to an increased number of DNA-DNA bonds between particles. Crystal size tunability (between 0.5 and 15 µm edge lengths) and epitaxial growth were demonstrated using this strategy by modulating the NaCl concentration in tandem with previously synthesized colloidal crystal nuclei. Taken together, this isothermal strategy provides a route to deliberately crystallize a wide variety of anisotropic colloidal materials and expands the phase space accessible to nanoparticles modified with DNA.

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

Effect of Molecular Weight and Layer Thickness on Dielectric Breakdown Strength of Neat and Homopolymer Swollen Lamellar Block Copolymer Films

Designing next-generation lightweight pulsed power devices hinges on understanding the factors influencing the energy storage performance of dielectric materials. Polymer dielectric films have a quadratic dependence of energy storage on the voltage breakdown strength and strategies to enhance the breakdown strength are expected to yield a path toward high energy storage densities. Highly stratified lamellar block copolymer (L-BCP) films of model polystyrene-b-polymethylmethacrylate (PS-b-PMMA) exhibited as much as ~50% enhancement in breakdown voltage (E BD ), (225 % increase in stored energy density, U~ E BD 2 ), compared to unordered as-cast L-BCP films. Such an energy density using amorphous polymer is on par with industry-standard semi-crystalline biaxially oriented polypropylene (BOPP), and as such a notable development in the field. This work develops a deeper understanding of the molecular mechanisms of E BD enhancement in L-BCP films, due to combination of interface formation and spatial isolation of the chain ends into segregated zones. We further confirm the role of chain ends in the breakdown process blending a low M n L-BCP with matched M n homopolymers to attain same layer spacing as neat L-BCP of higher M n . E BD shows a significant decrease at low homopolymer fractions due to increased net chain end density within swollen ordered L-BCP domains in wet-brush regime, followed by increased E BD due to layer thickness increase via segregated “interphase layer” formation by excess homopolymers. Notably, E BD of homopolymer swollen L-BCPs is always lower than neat L-BCP of the same domain spacing, due to overall adverse chain ends contribution from homopolymers. These findings provide important selection rules for L-BCPs for designing next-generation flexible electronics with high energy density solid-state BCP film capacitors.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Inline Rolling Shear Alignment: Deposition and Long-Range Order of Block Polymer Templates in a Fast, Single-Step Process

We report the first demonstration of a rapid, single-step technique to align block polymer, thin-film nanostructures that is amenable to continuous speeds ≥10 mm/s. This method, termed Inline Rolling Shear Alignment (IRSA), uses an elastomeric roller coupled with an electric hysteresis brake to shear films before the casting solvent fully evaporates, and it can enable high throughput, large-area manufacturing of patterns such as nanowire templates. IRSA is adaptable to various polymer systems including diblock and triblock polymers, and a post-shear annealing step can yield high-quality nanostructures with orientation parameters >0.99 and defect densities as low as 5 defect-pairs/μm 2 . To demonstrate the effectiveness of IRSA, platinum nanowires were produced from this rapid deposition and alignment approach using poly(styrene-b-2-vinylpyridine), followed by open-air, atmospheric-pressure plasma etching. Furthermore, this integrated concept, with 50x faster operation than existing processes, could be leveraged for cost-effective manufacturing of macroscopically aligned nanostructures in roll-to-roll systems.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Synthetic Band Structure Engineering of Graphene Using Block Copolymer-Templated Dielectric Superlattices

Engineering the electronic band structure of two-dimensional (2D) materials by imposing spatially periodic superlattice (SL) potentials opens a pathway to unconventional electronics. Nanopatterning the gate electrode or surface dielectric near 2D crystals provides a powerful strategy for realizing electrostatically tunable “remote” SLs with flexibility in lattice design. Here, we demonstrate the effectiveness of block copolymer (BCP)-templated dielectric nanopatterns for fabricating etch-free high-grade metal oxide SLs. Alumina (AlO x ) nanopatterns with hexagonal symmetry and a 38 nm SL wavelength are produced as a model material by directly converting a self-assembled BCP film via block-selective vapor phase infiltration. Despite micrometer-scale rotational disorder inherent to BCP self-assembly, electronic transport measurements of graphene reveal replica Dirac points at zero field and Hofstadter mini-gaps under finite magnetic fields. These results indicate the successful formation of remote SL potentials in graphene resulting from optimized AlO x nanopattern fabrication to achieve consistent lattice symmetry and periodicity at a macroscopic scale. The findings of this study, combined with the versatile, scalable, and cost-effective nature of BCP nanopatterning, highlight the potential of BCP-templated nanostructures for remote SL engineering in 2D crystals.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Organic Modulators Enable Morphological Diversity in Colloidal Crystals Engineered with DNA

Colloidal crystal engineering with DNA is a powerful way of generating a wide variety of crystals spanning over 90 different symmetries. However, in many cases, crystals with well-defined habits are difficult, if not impossible, to make, in part due to rapid crystal defect formation and propagation. This is especially true in the case of face-centered cubic (FCC) structures. Herein, we report a strategy that uses formamide as a chemical modulator to slow down colloidal crystal growth, which decreases defect formation and yields higher-quality crystals. Formamide forms hydrogen bonds with DNA bases and destabilizes the DNA duplex; in the context of colloidal crystallization, formamide leads to the disassembly of undercoordinated particles (defect architectures) and facilitates their reassembly into structures with the maximum number of nearest-neighbor contacts and DNA bonds. Here, when targeting an FCC lattice comprised of DNA-modified spherical 20 nm particles, formamide promotes the formation of its Wulff polyhedron (a truncated octahedron), never observed before in colloidal crystal engineering with DNA. Importantly, kinetic habits, including tetrahedra, octahedra, icosahedra, and decahedra, are also observed depending on formamide concentration.

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

Harnessing Peptide Binding to Capture and Reclaim Phosphate

With rising consumer demands, society is tapping into wastewater as an innovative source to recycle depleting resources. Novel reclamation technologies have been recently explored for this purpose, including several that optimize natural biological processes for targeted reclamation. However, this emerging field has a noticeable dearth of synthetic material technologies that are programmed to capture, release, and recycle specified targets; and of the novel materials that do exist, synthetic platforms incorporating biologically inspired mechanisms are rare. We present here a prototype of a materials platform utilizing peptide amphiphiles that has been molecularly engineered to sequester, release, and reclaim phosphate through a stimuli-responsive pH trigger, exploiting a protein-inspired binding mechanism that is incorporated directly into the self-assembled material network. This material is able to harvest and controllably release phosphate for multiple cycles of reuse, and it is selective over nitrate and nitrite. We have determined by simulations that the binding conformation of the peptide becomes constrained in the dense micelle corona at high pH such that phosphate is expelled when it otherwise would be preferentially bound. However, at neutral pH, this dense structure conversely employs multichain binding to further stabilize phosphate when it would otherwise be unbound, opening opportunities for higher-order conformational binding design to be engineered into this controllably packed corona. With this work, we are pioneering a new platform to be readily altered to capture other valuable targets, presenting a new class of capture and release materials for recycling resources on the nanoscale.

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

Real-time mass spectrometric characterization of the solid–electrolyte interphase of a lithium-ion battery

Solid-electrolyte interphase (SEI) is a key component that dictates the performance of most electrochemical devices, but the understanding of its chemistry and structure has been limited by the lack of in-situ tools. In this work, we report SEI live-formation in Li-ion battery under operando condition with liquid secondary ion mass spectrometry (SIMS), which, in combination with molecular dynamics (MD) simulation, presents the first dynamic picture with molecular-accuracy about this key component. Before any interphasial chemistry occurs during the initial charging, an electric double layer forms at the electrode-electrolyte interface via the self-assembly of solvent molecules directed by both Li+ and potential of the electrified surface. Such double layer structure predicts the eventual interphasial chemistries formed from the electrolytes, where the negatively-charged electrode surface repels salt anions from the inner-Helmholtz layer and results in an inner SEI that is thin, dense and inorganic in nature but LiF-depleted. It was this dense layer that exercises the major functions of an interphase, i.e., conducting Li+ but insulating electrons. An outer layer that is electrolyte-permeable and organic-rich appears after formation of the inner SEI. In highly-concentrated electrolyte, the presence of LiF in the inner-SEI is raised due to the high population of salt anions in the double layer. These real-time observations at nano-scale reveal in general sense how an interphase inherits chemistry from inner-Helmholtz layer structure, and establish guidelines in engineering desirable interphases for the future battery chemistries.

Zhou, Yufan↗
DOE OSTI2021

Nucleation and growth of blue phase liquid crystals on chemically-patterned surfaces: a surface anchoring assisted blue phase correlation length

In condensed matter, the correlation length is an essential parameter which describes the distance over which a material maintains its structural properties. In liquid crystals, for the orientational order parameter this characteristic length is of the order of nanometers, while in solid crystals it can extend to macroscopic length scales. Here, we report the measurement of the correlation length, or persistence length, of the crystallographic orientation of blue phases (BPs)—chiral liquid crystals with long-range 3D-crystalline structures and submicron-sized lattice-parameters. These materials exhibit phase transformations that have been identified as the liquid analog of crystal-crystal martensitic transformations. In this work, we use liquid epitaxial growth to achieve spontaneous BP-crystal nucleation and subsequent growth. Specifically, we design patterned substrates made of a binary array of regions with different liquid crystal anchoring, which facilitate a uniform nucleation and growth of BP-crystals with (100)-lattice orientation and a simple cubic symmetry. Furthermore, our results indicate that this simple cubic BP, the so-called blue phase II (BPII), forms first on the patterned surface, thereby propagating the growth of domains in directions parallel or perpendicular to the patterned regions. These results are used to understand the emergence of a surface anchoring assisted BPII-correlation length, taken as the distance over which the BP preserves its lattice orientation, as a function of time and pattern characteristics. We found that BPII single crystals can be achieved on patterned regions whose lateral dimensions are equal to or larger than 10 μm, consistent with our measurements of the BPII-correlation length. This newly acquired understanding of the role of surfaces on the formation of BPs is then used to design processes that permit formation of macroscopically large mono-domain, single-crystal BPs by relying on significantly reduced patterned areas (only part of the area is patterned), a feature that could benefit the applications of this intriguing class of materials.

correlation length↗
DOE OSTI2020

Mechanism of efficient double-strand break repair by a long non-coding RNA

Mechanistic studies in DNA repair have focused on roles of multi-protein DNA complexes, so how long non-coding RNAs (lncRNAs) regulate DNA repair is less well understood. Yet, lncRNA LINP1 is over-expressed in multiple cancers and confers resistance to ionizing radiation and chemotherapeutic drugs. Here, we unveil structural and mechanistic insights into LINP1’s ability to facilitate non-homologous end joining (NHEJ). We characterized LINP1 structure and flexibility and analyzed interactions with the NHEJ factor Ku70/Ku80 (Ku) and Ku complexes that direct NHEJ. LINP1 self-assembles into phase-separated condensates via RNA–RNA interactions that reorganize to form filamentous Ku-containing aggregates. Structured motifs in LINP1 bind Ku, promoting Ku multimerization and stabilization of the initial synaptic event for NHEJ. Significantly, LINP1 acts as an effective proxy for PAXX. Collective results reveal how lncRNA effectively replaces a DNA repair protein for efficient NHEJ with implications for development of resistance to cancer therapy.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Building Neutron Scattering Infrastructure in Louisiana for Advanced Materials (Final Report)

The main objective of the Louisiana Consortium for Neutron Scattering (LaCNS) is to build a major neutron scattering infrastructure capable of treating both soft and hard materials. The goal is to create a sustainable effort having the quality, breadth, and depth necessary to produce competitive proposals including collaborative and center type proposals. Our scientific aim is to understand the role of coupling in emergent complex materials and its impact on the structure/property relationship and to explore how to tune the key couplings to guide the design of materials with the desired properties. This naturally includes building a base of users of the Spallation Neutron Source (SNS) and the High Flux Isotope Reactor (HFIR) in Louisiana; to train highly talented graduate and post-doctoral students in synthesis, neutron scattering, and simulation and modeling techniques, thereby helping to produce the next generation of scientist who use neutron scattering techniques as a crucial part of their research. The goal of our hard matter program is to understand the interplay between spin, charge, orbital, and lattice degrees of freedom in carefully selected complex materials. We have made considerable progress on number of complex systems including the oxide Sr3(Ru1-xMnx)2O7 where short-range magnetic ordering with anisotropic spin texture is initiated at the metal-insulator transition that clearly indicates a strong spin-charge coupling. Another critical area is in quantum materials. For example, in the topological semimetal BaMnSb2, we found a 3D canted antiferromagnetic Weyl semimetal with a 2D electronic structure and a nontrivial Berry phase. In addition, in the hexagonal chiral Mn1/3NbS2 system, we found soliton/soliton and soliton/antisoliton domain walls where the application of small fields or small currents can be used to control nanoscopic magnetic domains where the control of domain walls is crucially important for information storage. In addition, chemical transformation investigations were performed on the VISION instrument at Spallation Neutron Source (SNS). The soft matter effort was focused on understanding the role of non-covalent interactions on the structure and dynamics of fluid-based soft matter. One key focus was on sequence-defined (SD) amphiphilic peptoid polymers that allow encoding of molecular interactions and thereby systematic investigations of how charge directs the solution self-assembly of amphiphilic polymers in water. Another important area was on the dynamics of lipids self-assembled into membranes for exploring the permeability and mechanical using both neutron spin echo (NSE) spectroscopy and quasielastic neutron scattering (QENS) to distinguished between viscoelasticity and permeability at the molecular scale. Overall, the LaCNS project was quite successful, generating 145 publications and 245 presentations. Our graduate and post-doctoral students were well trained resulting in positions in national laboratories (Oak Ridge National Laboratory (ORNL), Argonne National Laboratory and Los Alamos National Laboratory), major research universities, and industry. We also developed a uniaxial pressure cell along with ORNL for SNS. A critical goal of this project was to establish a foundation for competing nationally in federally funded research programs. To this end, we were quite successful in generating over twenty-two federally and non-federally funded grants including awards from NSF, DOE, and DOD, and two early career awards. Equally important, we were able to secure a key major piece of instrumentation via a large ARO grant for a state-of-the-art electron microscope.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Role of the Solvent–Surfactant Duality of Ionic Liquids in Directing Two-Dimensional Particle Assembly

Nanoparticle self-assembly plays a key role in formation of superlattices, which exhibit remarkable physical and chemical properties. However, controlling assembly remains a challenge partly due to a lack of understanding of the assembly dynamics and the difficulty in linking interfacial solution properties to interparticle forces. In this study, using liquid-cell transmission electron microscopy, self-assembly of gold nanoparticles (NPs) into superlattices in mixtures of water and ionic liquid (IL) was visualized, revealing a dual role of the IL in the assembly process. At intermediate concentrations, the IL acts as a surfactant stabilizing the particles at a well-defined equilibrium separation corresponding to the length of hydrogen bonded IL cations adsorbed onto neighboring NPs. Analysis of the interparticle forces reveals attractive long-range interactions of a van der Waals nature. At separations of 1-3 nm, interactions are dominated by attractive ion correlation and repulsive hydration forces giving rise to an energy minimum at 1.5 nm separation. The superlattice is further stabilized by hydrogen bonding, which shifts the equilibrium interparticle distance to 1.1 nm. In contrast, at higher concentrations, IL accumulates and forms a structured network in the gap between nanoparticles, where it acts as a solvent that eliminates the repulsive barrier and thus promotes particle coalescence. This solvent-surfactant duality of IL opens new opportunities for their use in directing particle assembly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Dye Nanoaggregate Structures in MK-2, N3, and N749 Dye···TiO 2 Interfaces That Represent Dye-Sensitized Solar Cell Working Electrodes

The working electrode of a dye-sensitized solar cell (DSSC) consists of dye molecules adsorbed onto nanoparticles of a semiconductor such as TiO 2 . A reliable prediction of the DSSC photovoltaic performance of a given dye requires in-depth knowledge about the precise structure of the dye···TiO 2 interface. In this work, X-ray reflectometry (XRR) and grazing-incidence small-angle X-ray scattering (GISAXS) are employed to determine the dye···TiO 2 interfacial structure and associated dye aggregation behavior of three high-performance DSSC dyes, i.e., a metal-free organic dye, MK-2, and the two archetypal ruthenium-based organometallic dyes, N3 and N749 (Black Dye). Results show that all three dyes form nanoaggregates in dye···TiO 2 interfaces. We determine the dye nanoaggregate separations, sizes, distribution densities, and the extent of short-range order within each dye self-assembly in the longitudinal and lateral directions. Dye···TiO 2 composites fabricated using dye solutions of varying concentrations are analyzed. We find that nanoaggregates of the three dyes are separated by several hundred nanometers (158-203 nm) in dye···TiO 2 interfaces that have been fabricated using concentrated dye solutions (0.5 mM or 1.0 mM). MK-2 and N749 dyes also display smaller interparticle separations. Dye nanoparticle diameters are of the order of 156-198 nm, sizes that are comparable to the largest interparticle separations. Thus, no extraneous dye particles can be fitted into gaps between particles, so the dye self-assembly is saturated. Self-assemblies of all three dyes exhibit both lateral and longitudinal short-range order; N3 displays a particularly short coherence length along the TiO 2 surface, with extensive structured disorder along the longitudinal direction. The operation of DSSC working electrodes would therefore seem to be dependent on a dye self-assembly that may exhibit several levels of structural granularity and dye aggregation effects.

14 SOLAR ENERGY↗
DOE OSTI2021

Mutations in artificial self-replicating tiles: A step toward Darwinian evolution

Significance In nature, mutation is the first step of evolution, where it provides the genetic variation for the natural selection to act. Here we take a system of artificial self-replicating tiles, DNA origami, that exhibit templated reproduction. We can generate a small fraction of mutations by introducing a mismatch in hybridization between parent and daughter. We can modify the origami functionality to affect the growth rate of the mutated species, giving it less or more evolutionary advantage, and to become dominant in several generations. The introduction of mutations into an artificial self-replicating system provides new directions for research into self-assembly processes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Hierarchical Chiral Self-Assembly of Nanocylinders Composed of Sequence-Defined Mesogenic Dimers

Chiral ensembles can arise through supramolecular curvature that resolves geometric frustrations in the packing of bent, achiral molecular or colloidal building blocks. Here, we leverage orthogonal protection−deprotection click chemistry to create sequence-defined mesogenic heterodimers exhibiting emergent chirality. We compare the hierarchical self-assembly of the synthesized asymmetric, achiral heterodimers, which differ only in the position of a methyl substituent. Both dimers form chiral spherulites composed of nanocylinders. However, the detailed arrangement of nanocylinders depends on the position of the methyl substituent and the crystallization conditions. Despite the chemical similarity, in one dimer, two crystalline forms are optically active. They form conglomerates of dextrorotatory and levorotatory spherulites. The other dimer forms more highly anisotropic spherulites that mask circular birefringence arising from the misorientation of nanocylinders, while mapping of nanocylinder directors reveals a sense at the spherulite surface. We propose that differences in nanocylinder arrangements may arise from changes in nanocylinder curvature and dimensions dictated by the methyl substituent position, inducing chirality. These results demonstrate multiscale hierarchical assembly relevant to dense systems of tubular structures and highlight the role of sequence and molecular design in directing the bottom-up hierarchical self-assembly and chirality of mesogenic systems.

Alkyls↗