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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Chain flexibility and glass transition temperatures of poly(n-alkyl (meth)acrylate)s: Implications of tacticity and chain dynamics

The relationship between chain microstructure and glass transition temperature (T g ) is complicated for poly(alkyl methacrylate)s and poly(alkyl acrylate)s. Despite intensive studies, relationships between the structures of these polymers and their properties, including solution characteristics and T g , are still controversial. Solution properties, chain conformations, including Flory's characteristic ratio (C ∞ ), persistence length (l p ), and chain diameters, and T g are reported for series of poly(n-alkyl acrylate)s and poly(n-alkyl methacrylate)s having alkyl side chain lengths (n) ranging from 1 to 10 carbons in length, with uniform and well-characterized tacticities. Chain flexibilities of both series of polymers decrease as n increases, reflecting increased hindrances to rotation about backbone bonds as side chains become longer. Conversely, the T g s for both series of polymers decrease substantially as n increases, reflecting the greater side chain mobilities of long alkyl substituents. For shorter alkyl chain lengths, T g s for the poly(n-alkyl acrylate)s are much lower than for the corresponding poly(n-alkyl methacrylate)s, a difference which has been attributed in the past to the presumed reduced chain flexibility of polymethacrylates due to the presence of the α-methyl substituent. However, contrary to such expectations, C ∞ and l p values for these two series of polymers are nearly identical at a given n value, except for the longest n-alkyl substituents. Instead, the differences in T g may be attributed to the differences in tacticity of the two series – almost ideally atactic for the poly(n-alkyl acrylate)s but high in syndiotacticity for the poly(n-alkyl methacrylate)s. The T g s for the two series of polymers approach that of polyethylene at longer alkyl chain lengths. In addition, the effects of tacticity and chain dynamics on C ∞ , l p , and T g of poly(methyl methacrylate) is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effect of Microstructure on Chain Flexibility and Glass Transition Temperature of Polybenzofulvene

Polybenzofulvene (PBF) is a polydiene with a very high glass transition temperature (T g ), which makes it a potential candidate for use as the hard block for high-temperature thermoplastic elastomer applications. The T g s of polydienes are known to be related to chain flexibility. However, no studies have been reported that correlate the chain flexibility to the microstructure of PBF. Herein, we present a study of solution properties of linear PBFs with narrow molecular weight dispersity and having 1,2-addition ranging from 23% to 99%. The materials were prepared by living anionic polymerization under different conditions. Specifically, the chain flexibility as defined by the Flory's characteristic ratio, , and dependence of chain flexibility on microstructure by combined measurements of intrinsic viscosity and molecular weight using triple-detector size exclusion chromatography (SEC) is studied. The persistence lengths (l p ) and chain diameters (d B ) were also estimated using the touched-bead wormlike chain model. To the best of our knowledge, the characteristic ratio of PBF is found to be the highest of all polydienes that have been reported so far.

36 MATERIALS SCIENCE↗
DOE OSTI2024

How Rigid Are Anthranilamide Molecular Electrets?

As important as molecular electrets are for electronic materials and devices, conformational fluctuations strongly impact their macrodipoles and intrinsic properties. Herein, we employ molecular dynamics (MD) simulations with the polarizable charge equilibrium (PQEq) method to investigate the persistence length (L P ) of molecular electrets composed of anthranilamide (Aa) residues. The PQEq-MD dissipates the accepted static notions about Aa macromolecules, and L P represents the shortest Aa rigid segments. The classical model with a single L P value does not describe these oligomers. Introducing multiple L P values for the same macromolecule follows the observed trends and discerns the enhanced rigidity in their middle sections from the reduced stiffness at their terminal regions. Furthermore, L P distinctly depends on solvent polarity. The Aa oligomers maintain extended conformations in nonpolar solvents with L P exceeding 4 nm, while in polar media, increased conformational fluctuations reduce L P to about 2 nm. These characteristics set key guidelines about the utility of Aa conjugates for charge-transfer systems within organic electronics and energy engineering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Understanding Solution State Conformation and Aggregate Structure of Conjugated Polymers via Small Angle X-ray Scattering

Donor-acceptor (D-A) conjugated polymers are high-performance organic electronic materials that exhibit complex aggregation behavior. Understanding the solution state conformation and aggregation of conjugated polymers is crucial for controlling morphology during thin-film deposition and the subsequent electronic performance. However, a precise multiscale structure of solution state aggregates is lacking. Here, we present an in-depth small-angle X-ray scattering (SAXS) analysis of the solution state structure of an isoindigo-bithiophene-based D-A polymer (PII-2T) in chlorobenzene and decane as our primary system. Modeling the system as a combination of hierarchical fibrillar aggregates mixed with dispersed polymers, we extract information about conformation and multiscale aggregation and also clarify the physical origin of features often observed but unaddressed or misinterpreted in small-angle scattering patterns of conjugated polymers. The persistence length of the D-A polymer extracted from SAXS agrees well with a theoretical model based on the dihedral potentials. Additionally, we show that the broad high q structure factor peak seen in scattering profiles can be attributed to lamellar stacking occurring within the fibril aggregates and that the low q aggregate scattering is strongly influenced by the polymer molecular weight. Overall, the SAXS profiles of D-A polymers in general exhibit a sensitive dependence on the co-existence of fibrillar aggregate and dispersed polymer chain populations. We corroborate our findings from SAXS with electron microscopy of freeze-dried samples for direct imaging of fibrillar aggregates. Finally, we demonstrate the generality of our approach by fitting the scattering profiles of a variety of D-A polymers based on thieno-isoindigo (PTII-2T), diketopyrrolopyrrole (DPP2T-TT, DPP-BTZ, PDPP2FT-C- 16 ), naphthalenediimide (P(NDI2OD-T2)), and a conjugated block copolymer P3HT-b-DPPT-T. The results presented here establish a picture of the D-A polymer solution state structure and provide a general method of interpreting and analyzing their scattering profiles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Uncovering Backbone Conformation for Rigid DPP-Based Donor–Acceptor Conjugated Polymer Using Deuterium Labeling and Neutron Scattering

The conjugated polymer’s backbone conformation dictates the delocalization of electrons, ultimately affecting its optoelectronic properties. Most conjugated polymers can be viewed as semirigid rods with their backbone embedded among long alkyl side chains. Thus, it is challenging to experimentally quantify the conformation of a conjugated backbone. Here, we performed contrast variation neutron scattering on rigid conjugated donor–acceptor (D–A) diketopyrrolopyrrole (DPP) polymers with selectively deuterated side chains to measure the conjugated backbone conformation. We first synthesized DPPbased polymers with deuterated side chains, confirmed by NMR and FTIR. Using contrast variation neutron scattering, we found that the DPP-based conjugated polymers are much more rigid than poly(3-alkylthiophenes), with persistence length (L p ) at 16–18 nm versus 2–3 nm. More importantly, in contrast to the relatively flexible poly(3-alkylthiophenes) whose backbone is more flexible than the whole polymer, we found that the backbone of DPP-based polymers has the same L p value compared to the whole polymer chain. This indicates that side chain interference on backbone conformation is not present for the semirigid polymer, which is further confirmed by coarse-grained molecular dynamics (CG-MD) simulations. Our work provides a novel protocol to probe polymer’s backbone conformation and paradigm-shifting understanding of the backbone conformation of semirigid conjugated polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Resonant Tender X-ray Scattering for Disclosing the Backbone Conformation of Conjugated Polymers

The backbone conformation of conjugated polymers (CPs) is essential to their performance in electronic applications. Contrast-variation small-angle neutron scattering (CV-SANS) techniques were used to assess the CP’s backbone conformation, which relies on synthesis of deuterated polymers. Such a technique has been proven mature and effective. One drawback is that deuteration labeling might subtly alter polymer’s physical properties due to structural modifications. To address these challenges, we introduce a novel approach utilizing tender Xray scattering near the sulfur K-edge to distinctly evaluate the backbone versus whole chain conformation for a low-bandgap donor−acceptor CP, poly[(5,6-difluoro- 2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3‴-dialkyl-2,2′;5′,2″;5″,2‴-quaterthiophen-5,5‴- diyl)] (PffBT4T). For PffBT4T dissolved in trimethylbenzene (TMB), the sulfur K-edge is identified at approximately 2477 eV using near-edge X-ray absorption fine structure spectroscopy (NEXAFS). Tender X-ray scattering conducted at presulfur K-edge and on-sulfur K-edge at elevated temperatures facilitated the distinction between the backbone and whole chain conformations. The results demonstrate that for highly flexible polymer, the backbone’s persistence length could be lower than that of the whole chains, suggesting a more flexible backbone. This rapid, label-free method enhances our ability to characterize CP’s backbone conformation efficiently, offering significant implications for the design and optimization of CPs for advanced electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Confinement and Processing Can Alter the Morphology and Periodicity of Bottlebrush Block Copolymers in Thin Films

Bottlebrush block copolymers (BBCPs) are intriguing architectural variations on linear BCPs with highly tunable structure. Confinement can have a significant impact on polymer assembly, giving rise to changes in morphology, assembly kinetics, and properties like the glass transition. Given that confinement leads to significant changes in the persistence length of bottlebrush homopolymers, it is reasonable to expect that BBCPs will see significant changes in their structure and periodicity relative to the bulk morphology. Understanding how confinement influences assembly will be important for designing BBCPs for thin film applications including membranes, integrated photonic structures, and potentially BCP lithography. In this work, in order to study the effects of confinement on BBCP conformation and morphology, a blade coating was used to prepare films with continuous variation in film thickness. Unlike thin films of linear BCPs, islands/holes were not observed, and instead mixtures of parallel and perpendicular morphologies emerge after annealing. The lamellar periodicity ($L_0$) of the morphologies is found to be thickness dependent, increasing $L_0$ with decreasing film thickness for blade coated films. Films coated out of tetrahydrofuran (THF) resulted in a single well-defined lamellar periodicity, verified through atomic force microscopy (AFM) and grazing incidence small-angle X-ray scattering (GISAXS), which increases dramatically from the bulk value (30.6 nm) and continues to increase as the film thickness decreases. The largest observed $L_0$ was 65.5 nm, and this closely approaches the estimated upper limit of 67 nm corresponding to a fully extended backbone in a bilayer arrangement. Films coated out of propylene glycol methyl ether acetate (PGMEA) resulted in a mixture of perpendicular lamellae and a smaller, likely cylindrical morphology. The lamellar portion of the film shows the same thickness dependence as the lamellae observed in the THF coated films. The scaling of the lamellar $L_0$ with respect to film thickness follows predictions for confined semiflexible polymers with weak excluded volume interactions and can be related to models for confinement of DNA. Spin coated films shows the same reduction in periodicity, although at very different film thicknesses. This result suggests that the material has shallow free-energy barriers to transitioning between different $L_0$ and morphologies, a property that could be taken advantage of for patterning diverse structures with a single material.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Design Principles for Using Amphiphilic Polymers To Create Microporous Water

Aqueous dispersions of microporous nanocrystals with dry, gas-accessible pores—referred to as “microporous water”—enable high densities of gas molecules to be transported through water. For many applications of microporous water, generalizable strategies are required to functionalize the external surface of microporous particles to control their dispersibility, stability, and interactions with other solution-phase components—including catalysts, proteins, and cells—while retaining as much of their internal pore volume as possible. Here, in this work, we establish design principles for the noncovalent surface functionalization of hydrophobic metal–organic frameworks with amphiphilic polymers that render the particles dispersible in water and enhance their hydrolytic stability. Specifically, we show that block co-polymers with persistence lengths that exceed the micropore aperture size of zeolitic imidazolate frameworks (ZIFs) can dramatically enhance ZIF particle dispersibility and stability while preserving porosity and >80% of the theoretical O 2 carrying capacity. Moreover, enhancements in hydrolytic stability are greatest when the polymer can form strong bonds to exposed metal sites on the external particle surface. More broadly, our insights provide guidelines for controlling the interface between polymers and metal–organic framework particles in aqueous environments to augment the properties of microporous water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Single-molecule investigations of single-chain cellulose biosynthesis

Cellulose biosynthesis in sessile bacterial colonies originates in the membrane-integrated bacterial cellulose synthase (Bcs) AB complex. We utilize optical tweezers to measure single-strand cellulose biosynthesis by BcsAB from Rhodobacter sphaeroides . Synthesis depends on uridine diphosphate glucose, Mg 2+ , and cyclic diguanosine monophosphate, with the last displaying a retention time of ∼80 min. Below a stall force of 12.7 pN, biosynthesis is relatively insensitive to force and proceeds at a rate of one glucose addition every 2.5 s at room temperature, increasing to two additions per second at 37°. At low forces, conformational hopping is observed. Single-strand cellulose stretching unveiled a persistence length of 6.2 nm, an axial stiffness of 40.7 pN, and an ability for complexes to maintain a tight grip, with forces nearing 100 pN. Stretching experiments exhibited hysteresis, suggesting that cellulose microstructure underpinning robust biofilms begins to form during synthesis. Cellohexaose spontaneously binds to nascent single cellulose strands, impacting polymer mechanical properties and increasing BcsAB activity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

The solution structures of higher-order human telomere G-quadruplex multimers

Human telomeres contain the repeat DNA sequence 5'-d(TTAGGG), with duplex regions that are several kilobases long terminating in a 3' single-stranded overhang. The structure of the single-stranded overhang is not known with certainty, with disparate models proposed in the literature. We report here the results of an integrated structural biology approach that combines small-angle X-ray scattering, circular dichroism (CD), analytical ultracentrifugation, size-exclusion column chromatography and molecular dynamics simulations that provide the most detailed characterization to date of the structure of the telomeric overhang. We find that the single-stranded sequences 5'-d(TTAGGG)n, with n = 8, 12 and 16, fold into multimeric structures containing the maximal number (2, 3 and 4, respectively) of contiguous G4 units with no long gaps between units. The G4 units are a mixture of hybrid-1 and hybrid-2 conformers. In the multimeric structures, G4 units interact, at least transiently, at the interfaces between units to produce distinctive CD signatures. Global fitting of our hydrodynamic and scattering data to a worm-like chain (WLC) model indicates that these multimeric G4 structures are semi-flexible, with a persistence length of ~34 Å. Investigations of its flexibility using MD simulations reveal stacking, unstacking, and coiling movements, which yield unique sites for drug targeting.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Exact statistics of helical wormlike chains with twist-bend coupling

Here, we present a solution for the Green's function for the general case of a helical wormlike chain with twist-bend coupling and demonstrate the applicability of our solution for evaluating general structural and mechanical chain properties. We find that twist-bend coupling renormalizes the persistence length and the force-extension curves relative to wormlike chains. Analysis of intrinsically twisted polymers shows that incorporation of twist-bend coupling results in the oscillatory behavior in principal tangent correlations that are observed in some studies of synthetic polymers. The exact nature of our solution provides a framework to evaluate the role of twist-bend coupling on polymer properties, such as DNA bound to histones and motivates the reinterpretation of existing biopolymer experimental data.

Ghosh, Ashesh [University of California, Berkeley,↗
DOE OSTI2024

LSTM-Based Data Integration to Improve Snow Water Equivalent Prediction and Diagnose Error Sources

Accurate prediction of snow water equivalent (SWE) can be valuable for water resource managers. Recently, deep learning methods such as long short-term memory (LSTM) have exhibited high accuracy in simulating hydrologic variables and can integrate lagged observations to improve prediction, but their benefits were not clear for SWE simulations. Here we tested an LSTM network with data integration (DI) for SWE in the western United States to integrate 30-day-lagged or 7-day-lagged observations of either SWE or satellite-observed snow cover fraction (SCF) to improve future predictions. SCF proved beneficial only for shallow-snow sites during snowmelt, while lagged SWE integration significantly improved prediction accuracy for both shallow- and deep-snow sites. The median Nash–Sutcliffe model efficiency coefficient (NSE) in temporal testing improved from 0.92 to 0.97 with 30-day-lagged SWE integration, and root-mean-square error (RMSE) and the difference between estimated and observed peak SWE values d max were reduced by 41% and 57%, respectively. DI effectively mitigated accumulated model and forcing errors that would otherwise be persistent. Moreover, by applying DI to different observations (30-day-lagged, 7-day-lagged), we revealed the spatial distribution of errors with different persistent lengths. For example, integrating 30-day-lagged SWE was ineffective for ephemeral snow sites in the southwestern United States, but significantly reduced monthly-scale biases for regions with stable seasonal snowpack such as high-elevation sites in California. These biases are likely attributable to large interannual variability in snowfall or site-specific snow redistribution patterns that can accumulate to impactful levels over time for nonephemeral sites. These results set up benchmark levels and provide guidance for future model improvement strategies.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1991

Hexagonal and nematic phases of chains. I - Correlation functions. II - Phase transitions

The statistical mechanics of a system of semiflexible chains, which can represent polymer liquid crystals, long-chain biomolecules, stiff wormlike micelles, or columns of discotic liquid crystals, are examined. A continuum theory is used to calculate static correlation functions in the hexagonal and nematic phases. Two correlation functions are considered: (1) the structure factor which describes fluctuations in the density; and (2) the director fluctuation spectrum, which describes fluctuations in the local optical axis. In addition, a model is developed for the phase transitions of a system of infinitely long, semiflexible chains which interact through a steric, excluded-volume repulsion. The model yields generic phase diagrams in terms of pressure or density vs. persistence length or temperature.

Selinger, Jonathan V.↗
DOE OSTI2021

Chronic arsenic increases cell migration in BEAS-2B cells by increasing cell speed, cell persistence, and cell protrusion length

Highlights: • Chronic arsenic exposure primes lung epithelial cells for enhanced cell migration. • Chronic arsenic increases cell motility in an EGFR-dependent manner. • Chronic arsenic increases cell persistence in an EGFR-independent manner. • EGFR is sufficient, but not necessary for increasing cell protrusion length in chronic arsenic treated cells. There is a strong association between arsenic exposure and lung cancer development, however, the mechanism by which arsenic exposure leads to carcinogenesis is not clear. In our previous study, we observed that when BEAS-2B cells are chronically exposed to arsenic, there is an increase in secreted TGFα, as well as an increase in EGFR expression and activity. Further, these changes were broadly accompanied with an increase in cell migration. The overarching goal of this study was to acquire finer resolution of the arsenic-dependent changes in cell migration, as well as to understand the role of increased EGFR expression and activity levels in the underlying mechanisms of cell migration. To do this, we used a combination of biochemical and single cell assays, and observed chronic arsenic treatment enhancing cell migration by increasing cell speed, cell persistence and cell protrusion length. All three parameters were further increased by the addition of TGFα, indicating EGFR activity is sufficient to enhance those aspects of cell migration. In contrast, EGFR activity was necessary for the increase in cell speed, as it was reversed with an EGFR inhibitor, AG1478, but was not necessary to enhance persistence and protrusion length. From these data, we were able to isolate both EGFR-dependent and –independent features of cell migration that were enhanced by chronic arsenic exposure.

60 APPLIED LIFE SCIENCES↗
NASA NTRS1993

Feasibility study on conducting overflight measurements of shaped sonic boom signatures using the Firebee BQM-34E RPV

A study was performed to determine the feasibility of establishing if a 'shaped' sonic boom signature, experimentally shown in wind tunnel models out to about 10 body lengths, will persist out to representative flight conditions of 200 to 300 body lengths. The study focuses on the use of a relatively large supersonic remotely-piloted and recoverable vehicle. Other simulation methods that may accomplish the objective are also addressed and include the use of nonrecoverable target drones, missiles, full-scale drones, very large wind tunnels, ballistic facilities, whirling-arm techniques, rocket sled tracks, and airplane nose probes. In addition, this report will also present a background on the origin of the feasibility study including a brief review of the equivalent body concept, a listing of the basic sonic boom signature characteristics and requirements, identification of candidate vehicles in terms of desirable features/availability, and vehicle characteristics including geometries, area distributions, and resulting sonic boom signatures. A program is developed that includes wind tunnel sonic boom and force models and tests for both a basic and modified vehicles and full-scale flight tests.

Maglieri, Domenic J.↗
NASA NTRS1985

On the structure of the turbulent vortex

The trailing vortex generated by a lifting surface, the structure of its turbulent core and the influence of axial flow within the vortex on its initial persistence and on its subsequent decay are described. Similarity solutions of the turbulent diffusion equation are given in closed form and results are expressed in sufficiently simple terms that the influence of the lifting surface parameters on the length of persistence and the rate of decay of the vortex can be evaluated.

Roberts, L.↗
NASA NTRS1976

Persistence and decay of wake vorticity

Some recent research relating to the nature of the lift-induced vortex wakes behind large aircraft was reviewed and the scaling laws that permit a comparison of results from ground facilities with those from flight test were provided. The maximum rotational velocities in the wake are shown to depend on a span loading shape parameter and on a characteristic length of persistence behind the aircraft. The effects of Reynolds number are also shown.

Roberts, L.↗
DOE OSTI2025

Many-body interference in kagome crystals

When electrons in metals act collectively, they enable emergent phenomena and electronic functionalities that transcend the behaviour of individual particles. Coherent collective charge motion has so far been observed primarily in superconductors, in which it arises with the formation of Cooper pairs. Here we report experimental evidence for coherent charge transport in the normal state of the kagome metal CsV 3 Sb 5 , indicative of a distinct collective electronic state. The signature is a set of magnetoresistance oscillations in mesoscopic crystalline pillars under in-plane magnetic fields, with a periodicity determined by the number of magnetic flux quanta h/e threading between adjacent kagome layers—effectively forming an interlayer Aharonov–Bohm interferometer. The cooperative nature of this phenomenon is evidenced by a non-analytic angular dependence characterized by abrupt transitions between discrete oscillation frequencies and its persistence over length scales that exceed the single-particle mean free path. Notably, the oscillation amplitude matches other anomalous electronic responses reported in CsV 3 Sb 5 , pointing to an underlying mechanism that establishes intrinsic coherence. These findings shed new light on the debated nature of correlated order in kagome metals and establish CsV 3 Sb 5 as a platform for realizing long-range coherent charge transport in the absence of superconductivity—opening new directions for coherence in correlated electron systems beyond conventional models.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗