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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 595 records · Page 33
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Effect of the filler morphology on the crystallization behavior and dielectric properties of the polyvinylidene fluoride‐based composite

Abstract Ceramic/polymer composites can be chemically stable, mechanically strong, and flexible, which make them candidates for electric devices, such as pressure or temperature sensors, energy storage or harvesting devices, actuators, and so forth. Depending on the application, various electrical properties are of importance. Polymers usually have low dielectric permittivity, but increased dielectric permittivity can be achieved by the addition of the ceramic fillers with high dielectric constant. With the aim to enhance dielectric properties of the composite without loss of flexibility, 5 wt% of BaTiO 3 ‐Fe 2 O 3 powder was added into a polyvinylidene fluoride matrix. The powder was prepared by different synthesis conditions to produce core/shell structures. The effect of the phase composition and morphology of the BaTiO 3 ‐Fe 2 O 3 core/shell filler on the structure and lattice dynamics of the polymer composites was investigated. Based on the results of the thermal analysis, various parameters of ceramic/polymer composites were determined. Differences in the phase composition and morphology of the filler have an influence on the formation of various polyvinylidene fluoride allomorphs and the degree of crystallinity. Furthermore, the dielectric performances of pure polyvinylidene fluoride and the polymer/ceramic composites were measured.

Polymer Science↗
DOE OSTI2026

Electrospinning of ultra-high molecular weight polymers into aligned nanofibers and their application in chemical separations

Ultra-high molecular weight (UHMW, >10 6 g mol −1 ) vinyl polymers are increasingly accessible through photoiniferter polymerization, yet their behavior in electrospinning has received comparatively little attention. Here, we explore the electrospinning of UHMW poly(methyl acrylate), poly(methyl methacrylate), poly(N,N-dimethylacrylamide), and poly(styrene-co-pentafluorostyrene) synthesized by photoiniferter polymerization, with number-average molecular weights (M n ) greater than 1000 kDa and dispersities below 1.4. UHMW polymers form stable Taylor cones and discrete fibers at solution concentrations as low as 0.5 wt% due to their large number of entanglements, a threshold unachievable with low molecular weight (M n = 20–54 kDa) polymers of the same chemistry. Using poly(methyl methacrylate) and poly(styrene-co-pentafluorostyrene) as model systems, we demonstrate that fiber diameter can be tuned from 350 nm to 20 μm through systematic variation of polymer concentration (0.01 to 4 wt%) and flow rate (0.5 to 10 mL h −1 ). Additionally, we find that collector rotation rate governs fiber alignment, with highly aligned mats obtained with drum rotation speeds of 1000 RPM. Reversing the polarity of the electric field during electrospinning reorients the surface chemistry of these fiber mats without altering their microscale morphology, shifting the water contact angle by 7° (89° to 96°) and providing a two-fold binding capacity enhancement in cationic dye uptake. These results show that the high entanglement densities of UHMW vinyl polymers shift the accessible electrospinning window to dilute solutions and that electric-field polarity is a useful lever to control the surface chemistry in the resulting fibers.

Marquez, Joshua D. [University of Florida, Gainesv↗
DOE OSTI2022

Additive manufacturing: Frameworks for chemical understanding and advancement in vat photopolymerization

Abstract Three-dimensional printing, or additive manufacturing (AM), is a broad term for a wide range of fabrication methods utilizing materials such as small-molecule, polymer, and metal feedstocks. Each method requires different chemical, physical, and engineering needs to be successful. This article will discuss some of the considerations for polymer-based AM methods. Ultimately, we focus on the chemistries of vat photopolymerization, in which light is used to cure a resin from liquid to solid, to provide an example of how chemical advancements have led to increased speed, resolution, and multimaterial printing capabilities not previously possible. Graphical abstract

36 MATERIALS SCIENCE↗
DOE OSTI2023

A comparison of mechanical properties from natural and process-induced interfaces in filament extrusion AM of polymer blends

Polymer blends are commonly tuned for specific applications to achieve desired properties otherwise inaccessible or prohibitively expensive to obtain via homopolymers. The interfacial characteristics of the polymer A-polymer B interface and resultant domain sizes govern key performance properties. Micro- and meso-scale morphology forms through the interplay of surface forces between the polymers and between each polymer and the surrounding atmosphere. Analogously, the layer-layer and road-road interfaces of material extrusion (MEX) additive manufacturing (AM) govern key performance properties of printed parts. This work explores the effect of layer height on the thermomechanical performance of polystyrene (PS)-polycarbonate (PC) blends. Filament is prepared from a 50/50 weight ratio of the two polymers and compared against dual-nozzle printing where every layer alternates between PS or PC homopolymer forming a part with an overall 50/50 polymer ratio. Typical indicators of polymer blend compatibility are also studied.

Chatham, Camden A.↗
DOE OSTI2023

Temporally Stable Supramolecular Polymeric Salts Enabling High-Performance 3D All-Aromatic Polyimide Lattices

Vat photopolymerization (VP) Additive Manufacturing (AM), in which UV light is selectively applied to cure photo-active polymers into complex geometries with micron-scale resolution, has a limited selection of aliphatic thermoset materials that exhibit relatively poor thermal performance. Ring-opening dianhydrides with acrylate-containing nucleophiles yielded diacrylate ester-dicarboxylic acids that enabled photo-active polyimide (PI) precursors, termed polysalts, upon neutralization with an aromatic diamine in solution. In situ FTIR spectroscopy coupled with a solution and photo-rheological measurements revealed a previously unknown time-dependent instability of 4,4'-oxydianiline (ODA) polysalts due to an aza-Michael addition. Replacement of the electron-donating ether-containing diamine with an electron withdrawing sulfone-containing monomer, e.g., 4,4'-diaminodiphenyl sulfone (DDS), prohibited the aza-Michael addition of the aromatic amine to the activated acrylate double bond. Novel DDS polysalt photocurable solutions are similarly analyzed and validated long-term stability, which enabled reproducible printing of polyimide organogel intermediates. Subsequent VP AM afforded 3-dimensional (3D) structures of intricate complexity and excellent surface finish, as demonstrated with scanning electron microscopy. In addition, the novel PMDA-HEA/DDS solution enabled the production of the first beam latticed architecture comprised of all-aromatic polyimide. Finally, the versatility of a polysalt platform for multi-material printing is further demonstrated by printing parts with alternating polysalt compositions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Selective One-Dimensional 13 C– 13 C Spin-Diffusion Solid-State Nuclear Magnetic Resonance Methods to Probe Spatial Arrangements in Biopolymers Including Plant Cell Walls, Peptides, and Spider Silk

Two-dimensional (2D) and 3D through-space 13 C– 13 C homonuclear spin-diffusion techniques are powerful solid-state nuclear magnetic resonance (NMR) tools for extracting structural information from 13 C-enriched biomolecules, but necessarily long acquisition times restrict their applications. In this work, we explore the broad utility and underutilized power of a chemical shift-selective one-dimensional (1D) version of a 2D 13 C– 13 C spin-diffusion solid-state NMR technique. The method, which is called 1D dipolar-assisted rotational resonance (DARR) difference, is applied to a variety of biomaterials including lignocellulosic plant cell walls, microcrystalline peptide fMLF, and black widow dragline spider silk. 1D 13 C– 13 C spin-diffusion methods described here apply in select cases in which the 1D 13 C solid-state NMR spectrum displays chemical shift-resolved moieties. Furthermore, this is analogous to the selective 1D nuclear Overhauser effect spectroscopy (NOESY) experiment utilized in liquid-state NMR as a faster (1D instead of 2D) and often less ambiguous (direct sampling of the time domain data, coupled with increased signal averaging) alternative to 2D NOESY. Selective 1D 13 C– 13 C spin-diffusion methods are more time-efficient than their 2D counterparts such as proton-driven spin diffusion (PDSD) and dipolar-assisted rotational resonance. The additional time gained enables measurements of 13 C– 13 C spin-diffusion buildup curves and extraction of spin-diffusion time constants TSD, yielding detailed structural information. Specifically, selective 1D DARR difference buildup curves applied to 13 C-enriched hybrid poplar woody stems confirm strong spatial interaction between lignin and acetylated xylan polymers within poplar plant secondary cell walls, and an interpolymer distance of ~0.45–0.5 nm was estimated. Additionally, Tyr/Gly long-range correlations were observed on isotopically enriched black widow spider dragline silks.

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

Modular Approach for the Synthesis of Bottlebrush Diblock Copolymers from Poly(Glycidyl Methacrylate)-block-Poly(Vinyldimethylazlactone) Backbones

A strategy that enables the facile synthesis of bottlebrush block copolymers with flexible backbones was developed. A demonstration of the strategy’s utility was carried out by grafting end-functionalized polymethylmethacrylate (PMMA) and polystyrene (PS) to the dually reactive block copolymer, poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone) (PGMA-b-PVDMA). Five different bottlebrush diblock copolymers were investigated by size-exclusion chromatography (SEC), 1H NMR, Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), X-ray scattering methods, atomic force microscopy (AFM), rheology and computational simulations using molecular dynamics (MD), and self-consistent field theory (SCFT). A relationship between the glass transition temperature and the fraction of chain ends was demonstrated by DSC and highlights the potential of this synthetic method to tailor polymer properties. All five samples were found to be in a disordered phase exhibiting multiscale structures revealed by two broad peaks in small-angle X-ray scattering (SAXS) that can be attributed to graft-to-graft and backbone-to-backbone density correlations using MD simulations. The SCFT-based simulations justify the observation of a disordered phase due to its stabilization by the grafts. Additionally, this modular approach can be easily extended to other grafts, including responsive, conducting, and charged polymers with the prerequisite end groups. The versatility and ease of assembling these functional bottlebrushes constitute a powerful “toolbox” method for the rapid and scalable synthesis of novel bottlebrush block copolymers with desired properties.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Synthesis of Hyperbranched Polymers via PET-RAFT Self-Condensing Vinyl Polymerization in a Flow Reactor

Photoinduced polymerization techniques have been used in preparing various polymeric materials as they share several advantages with thermally-triggered processes using mild conditions, low catalyst concentrations, and easy-to-perform experimental conditions. By combining photoinduced eletrotransfer reversible addition–fragmentation chain transfer (RAFT) polymerization with self-condensing vinyl polymerization (SCVP), in this work, a series of hyperbranched polymers is prepared in a flow reactor. Considered to be an alternative powerful method in improving scalability, reliability, and efficiency, the use of a flow reactor allowed us to synthesize hyperbranched poly(poly(ethylene glycol methyl ether)acrylate) (PPEGMEA) under extremely mild conditions–room temperature, open vessel, and use of LED light and water/methanol mixed solutions. Finally, the method also demonstrates considerable controllability in molecular weight and branching density by adjusting the feeding ratio of monomer to transmer, leading to the synthesis of block copolymers.

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

Head on Comparison of Self- and Nano-Assemblies of Gamma Peptide Nucleic Acid Amphiphiles

Peptide nucleic acids (PNAs) are nucleic acid analogs with hybridization properties and enzymatic stability superior to that of DNA. In addition to gene targeting applications, PNAs have garnered significant attention as bio-polymers due to the Watson–Crick-based molecular recognition and flexibility of synthesis. Here, in this work, PNA amphiphiles are engineered using chemically modified gamma PNA (8 mer in length) containing hydrophilic diethylene glycol units at the gamma position and covalently conjugated lauric acid (C12) as a hydrophobic moiety. Gamma PNA ($\gamma$PNA) amphiphiles self-assemble into spherical vesicles. Further, nano-assemblies (NA) are formulated using the amphiphilic $\gamma$PNA as a polymer via ethanol injection-based protocols. Comprehensive head-on comparison of the physicochemical and cellular uptake properties of PNA derived self- and NA is performed. Small-angle neutron and X-ray scattering analysis reveal ellipsoidal morphology of $\gamma$PNA NA that results in superior cellular delivery compate to the spherical self-assembly. Next, the functional activities of $\gamma$PNA self-and NA in lymphoma cells via multiple endpoints, including gene expression, cell viability, and apoptosis-based assays are compared. Overall, it is established that $\gamma$PNA amphiphile is a functionally active bio-polymer to formulate NA for a wide range of biomedical applications.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Spin-Dependent Electrochemistry

Recent experiments that use spin polarized electron currents to improve the selectivity and enantioselectivity of electrochemical reactions are described. Electrochemical studies with both chiral working electrodes and with magnetic working electrodes are used to generate spin polarized electron currents. Studies with chiral electrodes, which are formed through the adsorption of chiral molecules and through the growth of chiral oxide films, are shown to improve the efficiency and selectivity of the oxygen evolution reaction and oxygen reduction reaction. These improvements are attributed to the exploitation of spin selection rules (triplet vs. singlet pathways) in the reaction mechanism. Studies with magnetic electrodes, which are formed through ferromagnetic/Au thin film electrodes, are reported to initiate enantioselective chemical transformations, and three different cases are discussed here (enantioresolution of a racemic mixture, enantioselective polymer grafting on electrode surfaces, and the generation of achiral carbon centers). The addition of spin control to the conventional control over charge currents provides an added dimension to electrochemistry and electrosynthesis.

Waldeck, David H↗
DOE OSTI2021

Influence of fixed charge concentration and water uptake on ion sorption in AMPS/PEGDA membranes

Water content and charge density strongly influence ion sorption in charged membranes. However, isolating the individual effect of each parameter on ion sorption can be difficult due to experimental challenges associated with independently controlling these two variables during membrane synthesis. This frustrates development and validation of fundamental models and structure/property relationships. In this study, three series of uncharged and negatively charged hydrogel membranes were prepared using poly(ethylene glycol) diacrylate (PEGDA) as a cross-linker and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as an ionic monomer. Here, water content and charge density were controlled by varying AMPS content and PEGDA chain length. Ion sorption in these materials was measured using aqueous NaCl solutions at concentrations ranging from 0.01 to 1.0 M. At constant charge density, salt sorption increased as water content increased. At fixed water content, salt sorption decreased as charge density increased. Salt sorption in membranes with the highest water content and charge density was predicted using the Donnan/Manning model, which accounts for solution and membrane phase thermodynamic non-idealities. However, this approach could not predict sorption in weakly charged and uncharged membranes, presumably due to additional membrane phase thermodynamic non-idealities associated with ion solvation and uncharged polymer segments.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Investigating the effect of heterogeneities across the electrode|multiphase polymer electrolyte interfaces in high-potential lithium batteries

Polymer electrolytes hold great promise for safe and high-energy batteries comprising solid or semi-solid electrolytes. Multiphase polymer electrolytes, consisting of mobile and rigid phases, exhibit fast ion conduction and desired mechanical properties. However, fundamental challenges exist in understanding and regulating interactions at the electrode|electrolyte interface, especially when using high-potential layered oxide active materials at the positive electrode. Here we demonstrate that depletion of the mobile conductive phase at the interface contributes to battery performance degradation. Molecular ionic composite electrolytes, composed of a rigid-rod ionic polymer with nanometric mobile cations and anions, serve as a multiphase platform to investigate the evolution of ion conductive domains at the interface. Chemical and structural characterizations enable the visualization of concentration heterogeneity and spatially resolve the interfacial chemical states over a statistically significant field of view for buried interfaces. We report that concentration and chemical heterogeneities prevail at electrode|electrolyte interfaces, leading to phase separation in polymer electrolytes. In conclusion, understanding the hidden roles of interfacial chemomechanics in polymer electrolytes enables us to design an interphase tailoring strategy based on electrolyte additives to mitigate the interfacial heterogeneity and improve battery performance.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Advances in vat photopolymerization: early-career researchers shine light on a path forward

Vat photopolymerization (VP) has emerged as a promising additive manufacturing technique to allow rapid light-based fabrication of 3D objects from a liquid resin. Research in the field of vat photopolymerization spans across multiple disciplines from engineering and materials science to applied chemistry and physics. This perspective brings together early-career researchers from various disciplines in academia and national laboratories around the world to summarize the most recent advancements with special emphasis on the research highlighted as part of the Gordon Research Conference (GRC) 2024 meeting on Additive Manufacturing of Soft Materials. We provide an outlook on next-generation polymer processing methods from synthesis of novel materials to multimodality manufacturing and performance engineering. Further, this article combines the ideas of many of these junior researchers to present a vision for the future of the field by highlighting the challenges and opportunities that lie ahead.

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

InAs sidewall tunnel diodes enabled by surface states

Negative differential resistance (NDR), where the device current decreases with increasing bias voltage, is a representative phenomenon where quantum mechanics induces counterintuitive physical behavior and offers promising applications such as high-frequency oscillators, amplifiers, and multilevel logic circuits. While the NDR behavior has been extensively studied in various materials and devices, the role of surface properties in NDR, particularly in InAs-based diodes, remains underexplored. In this work, we report the observation of NDR in vertically structured InAs p + n diodes that exhibit a peak-valley current ratio of ∼6, which is suitably high for applications. Circumference-normalized current–voltage characterization revealed that the NDR originates from band-to-band tunneling between the valence band of p + -InAs and the conduction band of an n + -InAs surface, where the n + surface is due to surface states on otherwise n − -InAs. In addition, by comparing devices with various surface passivation methods (without intentional passivation, benzocyclobutene polymer, and silicon nitride), we found that the surface termination significantly affects the NDR characteristics. We present an equivalent circuit model to explain the observed device behavior. These findings offer insights into surface-enabled NDR phenomena and present new knobs for engineering NDR devices.

Circuit theorems↗
DOE OSTI2020

2020 Vehicle Technology Office Annual Progress Report from Jianchao Ye

Traditional batteries are composed of two-dimensional films that are stacked and/or rolled. Thin film batteries display high power density while their thick film counterparts show good energy density, but it has proven difficult to concurrently achieve both within these planar form factors. In addition, conventional Li-ion batteries based on liquid organic electrolytes or gel polymer electrolytes have raised severe safety concerns due to the intrinsic flammable properties of the organic electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2020

Stainless Steel Coating Test Report

A process was developed to coat 316L stainless steel pieces having very low levels of fixed contamination on their surface (~100 dpm/100 cm²). The coating process served to significantly decrease the likelihood of any fixed contamination becoming loose contamination due to physical shocks. Prior to coating, the stainless steel was etched with a commercial methane sulfonic acid (MSA) solution in a heated ultrasonic bath, rinsed with deionized water, cleaned with a basic detergent solution, and then rinsed with deionized water. The MSA etched the surface of the stainless-steel pieces, creating a more favorable surface on which the coating could adhere. Due to the short timeline of the project, only commercially available clear coating products were considered. The clear coating had to be wear-resistant, shock resistant, radiation resistant, and have high adhesion to the surface of the stainless steel. Adhesion of coatings to stainless steel is notoriously difficult. A commercial, high molecular weight polymer coating was found that met these requirements. The adhesion properties of this coating to stainless steel are very good, and are significantly improved by the etching process. The etching process results in a higher surface area that is free of debris and other residues, making the surface much more wetable, and at the same time creating a favorable surface topography for adhesion. The polymer in its uncured form is a low viscosity liquid. It can be applied by brush or pipette, and it cures in air alone, but heat is required to speed up curing and attain the highest performance of the cured polymer. As the project progressed, the project team became interested in the composition of the selected commercial polymer coating, and in ways that this polymer coating could be made more wear resistant and potentially more radiation resistant. Nano-particle addition was chosen as the preferred way to achieve higher performance. Therefore, a series of tests were planned and performed. This report summarizes these tests, and presents the results.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Carbonyl Identification and Quantification Uncertainties for Oxidative Polymer Degradation

The most revealing indicator for oxidative processes or state of degraded plastics is usually carbonyl formation, a key step in materials degradation as part of the carbon cycle for man-made materials. Hence, the identification and quantification of carbonyl species with infrared spectroscopy have been the method of choice for generations, thanks to their strong absorbance and being an essential intermediate in carbon oxidation pathways. Despite their importance, precise identification and quantification can be challenging and rigorous fully traceable data are surprisingly rare in the existing literature. An overview of the complexity of carbonyl quantification is presented by the screening of reference compounds in solution with transmission and polymer films with ATR IR spectroscopy, and systematic data analyses. Significant variances in existing data and their past use have been recognized. Guidance is offered how better measurements and data reporting could be accomplished. Experimental variances depend on the combination of uncertainty in exact carbonyl species, extinction coefficient, contributions from neighboring convoluting peaks, matrix interaction phenomena and instrumental variations in primary IR spectral acquisition (refractive index and penetration depth for ATR measurements). In addition, diverging sources for relevant extinction coefficients may exist, based on original spectral acquisition. For common polymer degradation challenges, a relative comparison of carbonyl yields for a material is easily accessible, but quantification for other purposes, such as degradation rates and spatially dependent interpretation, requires thorough experimental validation. All variables featured in this overview demonstrate the significant error margins in carbonyl quantification, with exact carbonyl species and extinction coefficients already being major contributors on their own.

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

Application of GO anchored mediator in a polymer electrolyte membrane for high-rate solid-state supercapacitors

Here, we synthesized a novel polymer electrolyte membrane by combining poly (vinylidene fluoride) (PVDF) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) with graphene oxide (GO) nanosheets and a lithium salt of tungstosilicic acid (Li 4 SiW 12 O 40 , hereafter, referred to SiWLi). The impact of the addition of GO/SiWLi on the microstructure and morphology of the membrane were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). We found that adding the GO/SiWLi to the PVDF/LiTFSI polymer electrolyte membrane significantly reduced the pore size. Furthermore, the addition of the GO/SiWLi resulted in not only an increase of the ionic conductivity from 0.87 $\times$ 10 –2 to 3.12 $\times$ 10 –2 Scm –1 but also an increase in the lithium-ion transference number from 0.52 to 0.87. The polymer electrolyte membranes with and without GO/SiWLi were utilized to fabricate solid-state supercapacitors. The supercapacitors fabricated with the membrane containing GO/SiWLi displayed 37.2% lower equivalent series resistance and 88.2% greater specific capacitance than those fabricated using the membrane without GO/SiWLi at 200mVs –1 .

42 ENGINEERING↗