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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Bottlebrush Polymers at Liquid Interfaces: Assembly Dynamics, Mechanical Properties, and All-Liquid Printed Constructs

Bottlebrush polymer surfactants (BPSs), formed by the interfacial interactions between bottlebrush polymers (BPs) with poly(acrylic acid) side chains dissolved in an aqueous phase and amine-functionalized ligands dissolved in the oil phase, assemble and bind strongly to the fluid-fluid interface. The ratio between N BB (backbone degree of polymerization) and N SC (side chain degree of polymerization) defines the initial assembly kinetics, interface packing efficiency, and stress relaxation. The equilibrium interfacial tension (γ) increases when N BB < N SC , but decreases when N BB $\gg$ N SC , correlating to a pronounced change in the effective shape of the BPs from being spherical to worm-like structures. The apparent surface coverage (ASC), i.e., the interfacial packing efficiency, decreases as N BB increases. The dripping-to-jetting transition of an injected polymer solution, as well as fluorescence recovery after photobleaching experiments, revealed faster initial assembly kinetics for BPs with higher N BB . Furhter, Euler buckling of BPS assemblies with different N BB values was used to characterize the stress relaxation behavior and bending modulus. The stress relaxation behavior was directly related to the ASC, reflecting the strong influence of macromolecular shape on packing efficiency. The bending modulus of BPSs decreases for N BB < N SC , but increased when N BB $\gg$ N SC , showing the effect of molecular architecture and multisite anchoring. All-liquid printed constructs with lower N BB BPs yielded more stable structured liquids, underscoring the importance of macromolecular packing efficiency at fluid interfaces. Overall, this work elucidates fundamental relationships between nanoscopic structures and macroscopic properties associated with various bottlebrush polymer architectures, which translate to the stabilization of all-fluidic printed constructs.

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

Enhancing Chemical Stability and Suppressing Ion Migration in CH 3 NH 3 PbI 3 Perovskite Solar Cells via Direct Backbone Attachment of Polyesters on Grain Boundaries

Organic–inorganic halide perovskites feature excellent optoelectronic properties but poor chemical stability. While passivating perovskite grain boundary (GB) by polymers shows prospects on long-term performance of perovskite solar cells (PSCs), its detailed impact on the ion migration phenomenon, which largely deteriorates the PSC stability, remains less probed. In this work, we introduce a new polar polymer, polycaprolactone (PCL), to passivate GBs of methylammonium lead triiodide (MAPbI 3 ) perovskite with only 1–2 polymer monolayers via direct backbone attachment. The PSCs with passivated MAPbI 3 , using a classic but less stable Spiro-OMeTAD (2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene) hole transport layer (HTL), exhibit improved power conversion efficiencies up to 20.1%, with 90% of the initial PCE being preserved after 400 h ambient storage, and 80% even after 100 h, 85 °C aging. The improved PSC stability indicates critical roles of PCL GB passivation in retarding moisture-induced decomposition and suppressing ion migration within the perovskite. Furthermore, time-of-flight secondary ion mass spectrometry reveals that I– ions can actively migrate into the electrode, HTL, and their interface in nonpassivated PSCs, even without an externally applied electric field, while such migration is significantly mitigated in PCL-passivated PSCs. This effective GB passivation by PCL suggests an important potential of polymer additives toward the development of stable high-performance PSCs.

36 MATERIALS SCIENCE↗
NASA NTRS1982

Space environmental effects on materials

Research efforts at NASA-Langley to characterize the durability of composite materials which are candidates for use as components on various space hardware systems are reviewed. The material applications include large space structures, antennas, cables, thermal control coatings, solar reflectors, and satellite power systems. Simulation facilities have been built to study radiation effects on polymer matrix composites, and the dimensional stability of the matrix composites and tension stabilized cables. Numerical models are being developed for radiation effects on the mechanical, physical, and optical properties. Additionally, chemical and microstructural analyses are performed to identify damage mechanisms and the limits of effectiveness of accelerating life tests. It is noted that no residual strength reduction has been detected in polymer films after dosages of 5 billion rads of electron radiation.

Tenney, D. R.↗
NASA NTRS1990

Thermally stable, low dielectric polyquinolines for aerospace and electronics applications

Four new high molecular weight, linear chain polyquinolines have been synthesized and fabricated into high quality free standing films. These polymers are characterized by moderate to high glass transition temperatures, excellent thermal and thermooxidative stability, extremely low dielectric constants and good planarizing characteristics. The polymers absorb very low quantities of moisture. As a consequence, the dielectric constant of one new polyquinoline has been shown to be quite insensitive to exposure to warm/wet conditions. Isothermal aging of one new derivative in air has been carried out at elevated temperatures (250 C to 345 C). The results demonstrate truly outstanding thermooxidative stability. Additional characterizations include molecular weight determinations, solubilities and film-forming characteristics, density measurements, and UV-Vis spectroscopy. The data acquired to date suggest that the polymers may find use as refractive films and coatings and as interlevel planarizers in microelectronics applications.

Hendricks, Neil H.↗
DOE OSTI2023

Porous bipolar polymers as organic cathodes for sustainable sodium/potassium-ion batteries

Redox-active porous polymers are becoming promising organic electrode materials for alkali-ion batteries because of their tunable pore size, flexible chemical structure, and high thermal stability. This work presents various porous bipolar polymers as cathodes in Na-ion batteries (NIBs) and K-ion batteries (KIBs). Two structural units containing carbonyl and amine active centers, respectively, were introduced into the repeating units of the polymers by the polycondensation of N,N,N',N'-tetrakis(4-aminophenyl)-1,4-phenylenediamine (TAP) and various dianhydrides. Here, the resulting bipolar polymers undergo multi-electron redox reactions involving both cations and anions during battery charge and discharge. The impacts of extended conjugation structures and porosity on the electrochemical performances were investigated by tuning the conjugation structures in the dianhydride monomers. The bipolar polymers with extended conjugation structures and small pore size exhibit superior electrochemical performance in NIBs and KIBs in terms of high redox potentials, long cycle life, and fast-charging capability, demonstrating great promise as organic cathode materials for alkali-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Halide perovskite-polymer composite film for bright and stable light-emitting devices

Stability is the primary hindrance for the application of halide perovskite material in light-emitting devices, solar cells, and other devices. In this work, halide perovskite and polymer composite film have been prepared for stable and bright light-emitting devices. Pure-phase Cs4PbBr6 crystals have been synthesized, and their photoluminescence (PL) properties and fluorescence lifetimes have been investigated. The Cs 4 PbBr 6 crystals exhibited high uniformity but underwent rapid photodegradation under light irradiation. To address this issue, we prepared bright light-emitting devices using composite of Cs 4 PbBr 6 crystals and polyethylene oxide (PEO) as the emission layer. The aim was to improve the optical and physical properties of halide perovskites, such as photodegradation and stability. PEO, with its excellent film-forming ability, created a uniform and dense film on the halide perovskite surface, filling microscopic defects and providing a protective barrier. FTIR, morphology, and PL analyses confirmed the protective role of the halide perovskite and polymer composite film. The composite film light-emitting devices demonstrated improved stability and higher PL brightness, with a peak brightness approaching 3 × 10 8 cd/m 2 , which was approximately 75% higher than the pure halide perovskite devices.

Composite film↗
DOE OSTI2022

Mesoscale Polymer Surfactants: Photolithographic Production and Localization at Droplet Interfaces

Stabilization of fluid droplets, classically as oil-in-water or water-in-oil emulsions, is typically conducted using molecular surfactants or small particulates that localize at oil-water interfaces. In this paper, we describe a method whereby thin polymer films are converted photolithographically to ribbon-like mesoscale objects, which in turn adsorb to fluid inter-faces where they extend as appendages, or arms, from the droplet surface. These “mesoscale polymer surfactants”, or MPSs, were prepared from thin polymer films containing reactive functional moieties, including coumarin for photo-crosslinking, triphenylsulfonium for photoacid generation, and tert-butyl ester for solubility switching. The resultant MPSs, prepared initially on Si substrates, were released into water to reveal an exquisite shape sensitivity (forming straight, bent, or helical structures) and affinity for droplet interfaces based on their preparation conditions and the properties of the surrounding liquid. Notably, the lithographic techniques employed were amenable to differentiating the wettability of MPS segments, affording access to diblock-like MPSs which adhered to dispersed droplets via their hydrophobic segments, allowing their hydrophilic segments to extend into the continuous phase.

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

Amphiphilic Polyphosphazene for Fluorocarbon Emulsion Stabilization

High internal phase emulsions (HIPEs) have been of great interest for fabricating fluorinated porous polymers having controlled pore structures and excellent physicochemical properties. However, it remains a challenge to prepare stable fluorocarbon HIPEs, due to the lack of suitable surfactants. By randomly grating hydrophilic and fluorophilic side chains to polyphosphazene (PPZ), a comb-like amphiphilic PPZ surfactant with biodegradability is designed and synthesized for stabilizing water/fluorocarbon oil-based emulsions. The hydrophilic–lipophilic balance of PPZs can be controlled by tuning the grating ratio of the two side chains, leading to the preparation of stable water-in-oil HIPEs and oil-in-water emulsions, and the production of fluorinated porous polymers and particles by polymerizing the oil phase. Finally, these fluorinated porous polymers show excellent thermal stability and, due to the hydrophobicity and porous structure, applications in the field of oil/water separation can be achieved.

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

Characterizing the Influence of Organic Polymers on the Specific Reactivity of Particulate Remedial Amendments

Commercially available particulate amendments demonstrate high reactivity for effective treatment of water soluble organic and inorganic contaminants in laboratory studies; however, transport of these particles is constrained in the subsurface. In many field applications, particulate amendments are mixed with organic polymers to enhance mobility for direct push applications or stabilize suspensions for high mass loadings. As such, the interactions between particulate amendments, organic polymers and contaminant species need to be systematically investigated to properly understand mechanistic processes that facilitate predictive performance metrics for specific applications in situ . In this study, batch experiments were conducted to quantify the effects of organic polymers (xanthan gum, guar gum, and sodium alginate), polymer concentration (800 and 4,000 mg/L), and aging (up to 28 days) on chromate treatment rate and capacity by two classes of amendments: reductants [granular zero-valent iron (gZVI), micron-ZVI (mZVI), sulfur modified iron (SMI)], and an adsorbent (bismuth sub-nitrate). When particulate amendments were suspended in polymer solutions, reductants retained between 84–100% of the amendment treatment capacity. Conversely, the adsorbent maintained 63–97% relative treatment capacity of the no-polymer control. Polymer solutions had a more pronounced impact on the rate of chromate removal; first order rates of chemical reduction decreased by as much as 70% and adsorption by up to 81% relative to the no-polymer controls. Polymer–amendment aging experiments also showed decreased Cr(VI) treatment capacity; reductants decreased by as much as 24% and adsorption decreased by as much as 44% after 28 days of incubation. While polymer suspensions are needed to aid the injection of particulate amendments into the subsurface, the results from this study indicate potential losses of treatment capacity and a decrease in the rate of remedial performance due to the physical and chemical interactions between polymer suspensions and reactive particulate amendments. Simple batch systems provide baseline characterization of tripartite interactions for the removal of Cr(VI). Additional work is needed to quantify the full impact of polymers on remedial outcomes under site relevant conditions at field scale.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Manipulation of amorphous precursors to enhance zeolite nucleation

Crystallization in media comprised of amorphous precursors is becoming a more common phenomenon for numerous synthetic, biological, and natural materials that grow by a combination of classical and nonclassical pathways. Amorphous phases can exhibit a wide range of physicochemical properties that may evolve during the course of nucleation and crystal growth. This creates challenges for establishing causal relationships between amorphous precursor properties and their effect(s) on the selection of mechanistic pathways of crystallization and ultimately the properties of the crystalline product. In this study, we examine ways to manipulate the composition and colloidal stability of amorphous (alumino)silicate precursors that are prevalent in nanoporous zeolite syntheses. Changes in the amorphous precursor properties are evaluated on the basis of their ability to enhance rates of crystal formation. Here, we use fumed silica as the primary silicon source and examine the effects of infusing the source or growth medium with additional alkali metal, which serves as an inorganic structure-directing agent to facilitate the formation of porous crystal structures. We also assess the impact of adding a polymer additive, which reduces the colloidal stability of precursors, wherein we posit that the confined pockets of solution within the interstitial spaces of the precursor aggregates play an important role in regulating the rate of zeolite crystallization. Three commercially relevant zeolites (mordenite, SSZ-13, and ZSM-5) were selected for this study based on their diverse frameworks and methods of preparation. Here our findings reveal that alkali infusion significantly reduces the crystallization times for mordenite and SSZ-13, but has little impact on ZSM-5 synthesis. Conversely, we find that polymer addition markedly enhanced the rates of crystallization among all three zeolites, suggesting that this method may be a general approach to reduce zeolite synthesis times. Given the relatively high costs associated with commercial zeolite production, identifying new methods to improve the efficiency of hydrothermal syntheses can have significant practical implications beyond the fundamental benefits of developing new routes to tailor nonclassical crystallization.

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

Exploring Phosphonium‐Based Anion Exchange Polymers for Moisture Swing Direct Air Capture of Carbon Dioxide

This study explores the performance and stability of ammonium and phosphonium-based polymeric ionic liquids (PILs) with methyl and butyl substituents in moisture-swing direct air capture of CO 2 . The polymers are synthesized with chloride counterions, followed by ion exchange to the bicarbonate ion, and tests for CO 2 capture capacity and stability under cyclic wet–dry conditions. The phosphonium polymer with methyl substituents [PVBT-MeP] demonstrates the highest CO 2 capture capacity at ≈510 µmol g⁻¹, attributed to minimal steric hindrance and stronger ion pairing with bicarbonate. However, oxidative degradation is detected by 31 P NMR spectroscopy after the moisture swing experiment, with the appearance of a phosphine oxide peak at 61.28 ppm, which indicates phosphorus oxidation as the primary degradation pathway. In contrast, the ammonium polymer with butyl substituents [PVBT-BuN] exhibits the highest stability, showing no degradation over five moisture swing cycles. Additional stability experiments in 0.5 m KHCO 3 solutions reveal no degradation for any PIL, suggesting that oxidative degradation is driven by dynamic acid-base reactions during the moisture swing cycles in the air. Furthermore, these findings reveal the potential of phosphonium-based PILs for moisture-swing direct air capture, achieving high capacity while highlighting the need for optimized stability through counterion and structural design.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Improving Thermal Stability of Perovskite Solar Cells by Suppressing Ion Migration Using Copolymer Grain Encapsulation

Thermal stability of organic–inorganic hybrid perovskites (OIHPs) remains as one of the critical challenges against the stable operation of perovskite solar cells (PSCs) in direct sunlight with elevated temperatures. Here, we show that the addition of a polystyrene-co-polyacrylonitrile (SAN) copolymer can significantly enhance thermal stability of OIHPs and improve the stability of the corresponding PSCs by suppressing the migration of organic cations in OHIP. The methylammonium lead iodide (MAPI) with SAN incorporated within the perovskite layer featured a superior thermal stability compared to pure MAPI without SAN, only displaying an average of 5–15% decrease in PCE even after continuous thermal aging for 24 h at 100 °C. The secondary ion mass spectrometry revealed that the thermal degradation of the pure MAPI was largely associated with MA+ out-migration. Conducting atomic force microscopy analysis further indicated that the incorporated SAN led to a suppression of ionic currents present at the grain boundaries of the perovskite film, which was understood by high immiscibility between SAN and MA+ components as confirmed by the experimentally estimated Flory–Huggins parameter between them. This study newly identifies a potential of using polymer grain encapsulation for enhancing thermal stability of OIHPs and their solar cell performance by suppressing the out-diffusion of cationic organic components.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A scalable and autoclavable oxygen nanosensor platform for metabolic monitoring of Saccharomyces cerevisiae in a bioreactor and other in situ systems

Polymer-encapsulated dye nanoparticle sensors are a valuable approach to achieving in situ analyte measurements with luminescence; however, typical emulsion-based nanosensors are poorly suited for large-scale biological samples due to limitations of synthesis scalability and stability. Branched polyethylenimine (PEI) is a versatile polymer scaffold ideal for constructing nanoparticles with various covalently conjugated moieties due to their high density of reactive primary amines, high water solubility, and biological stability. In this work, we used branched polyethylenimine as a scaffold-based approach for making a stable and scalable ratiometric oxygen sensor. Pt (II) tetracarboxyporphine was used as an oxygen-sensing dye and coumarin 343 as a reference dye, all covalently linked to the PEI scaffold producing a product that could withstand sterilization procedures and easily be scaled. To minimize toxicity from the PEI scaffold, we conjugated it with 2000 MW PEG. The applicability of the sensors was demonstrated in a 200 mL Saccharomyces cerevisiae yeast culture, using orthogonal luminescent and electrochemical oxygen measurements to validate sensor response and measure the metabolic activity of the yeast in our culture. Further, this approach was able to match the sensitivity of our electrochemical measurements while improving upon drawbacks of other luminescent methods of oxygen detection, demonstrating effective monitoring for at least 20 h. Our scaffold-based approach is a modular and easily translatable technology that could be useful in various biotechnological applications.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Impact of DMP-30 catalyst concentration on the degradation and kinetics of bisphenol A epoxy thermosets cured with linear amine hardener

Epoxy thermosets are a crucial component in carbon-fiber composites, serving as the organic binding matrix. Catalysts are commonly used in prepolymer formulations to accelerate curing of the thermosets. However, the impact of catalysts on the thermal stability, degradation pathways, and kinetics of the final thermoset is poorly understood. Here, in this work, Product-Specific Kinetics (PSK) analysis was utilized with isoconversional kinetics to provide a first look into the degradation kinetics of major pyrolysis pathways in bisphenol A (BPA) epoxy resins and determine the impact of altering catalysis concentrations on these kinetic pathways. Results revealed new insights into previously identified degradation pathways, provided evidence of multiple degradation pathways for some products, and showed that use of excess catalyst results in polymer network alterations and reduced thermal stability of the thermosets.

Bisphenol A↗
DOE OSTI2022

Study on Emulsification/Demulsification Behavior and Mechanism of Produced Liquid from Polymer Flooding on Alaska North Slope

Heavy oil reservoirs on Alaska North Slope (ANS) are unconsolidated and contain abundant clay minerals, where the first-ever field pilot is currently implemented to validate the use of polymer floods for heavy oil enhanced oil recovery (EOR). The polymer molecules and/or fine clay particles carried with the produced liquid could potentially affect the oil/water separation, which is one of the major concerns for field operators. This dissertation aims to investigate the emulsification behavior of produced liquid, understand the emulsifying mechanism, and seek an adaptive and cost-effective method to treat the produced liquid from polymer flooding. Emulsions were prepared by mechanically mixing the actual heavy oil and the produced water from the pilot site, of which the stability was investigated by bottle test method or multiple light scattering method. Drop size distribution and interfacial properties were measured via microscope and pendant drop technique to probe the stability mechanism further. Results showed that oil-continuous or water-continuous emulsion could be generated depending on the water cut, clay types, clay concentration, and polymer concentration. In the crude oil/water system, the increasing water cut triggered the phase inversion of oil-continuous emulsion to water-continuous emulsion, resulting in faster separation and lower emulsion stability. Whereas, clay particles, no matter added to the oil or water phase, resulted in an unfavorable phase inversion from the loose water-continuous emulsion to the tight oil-continuous emulsion as clay concentration increased. For all four types of clay except Ca-montmorillonite, clay particles added to water led to an earlier phase inversion and higher emulsion stability than that added to the oil. The dual function of polymer on emulsion stability was observed. On the one hand, both sheared and unsheared polymer tended to convert the oil-continuous emulsion formed in either crude oil/water system or complex crude oil/water/clay particle system to the water-continuous emulsion, acting as a weak demulsifier to accelerate the oil/water separation. On the other hand, the addition of polymer to the water-continuous emulsion could result in enhanced emulsion stability, which is primarily attributed to the increased viscosity of the continuous phase and the decreased drop size of the dispersed oil phase. Particularly, the sheared polymer had a weaker ability to stabilize the o/w emulsion than the unsheared polymer due to the lower viscosity of the sheared polymer solution resulting from the breakdown of the polymer macromolecules. As for the chemical demulsification tests, the performance of demulsifiers showed a complex dependency upon the water cut, the shearing intensity, demulsifier type and dosage, and the polymer concentration. A compound emulsion breaker, E12+E18, exhibited the most satisfactory demulsification performance despite the varied test conditions. For severe water-continuous emulsions that might require a multi-fold dosage of demulsifier, a less expensive electrolyte, KCl, was proposed to be used in combination with demulsifier E12+E18 to improve the demulsification performance. In the proposed demulsifier formula, the effectiveness of the commercial demulsifier relied on its destructive effect on the interfacial film, while the efficacy of KCl was mainly dependent on its viscosity reduction effect on the continuous phase. This dissertation illustrates that intermediate layer elimination and water clarification are the major challenges for produced liquid treatment from polymer flooding. It also provides practical and theoretical guidance in advance for the demulsification strategy of the produced liquid from the ongoing first-ever polymer flooding pilot on ANS.

Chang, Hongli↗
NASA NTRS1982

Polymer materials research at NASA Ames Research Center

Polymers that provide significant improvements in both efficiency and safety for civilian transport aircraft and military combat aircraft were developed. High strength to weight structures such as carbon fiber composites with long term durability are requirements common to both classes of aircraft. Aircraft safety improvements in fire resistance and crashworthiness of primary and secondary structures are long term objectives for transport aircraft. Void filler ballistic foams, intumescent coatings, and radiation-resistant transparent plastics contribute to vulnerability reduction in combat military aircraft. Low and high velocity impact tolerance, fire resistance, thermal stability, and long term durability of polymers and components are emphasized.

J. A. Parker↗
DOE OSTI2023

Reactive Extrusion of Waste Plastics with Compatibilizer and Lightly Pyrolyzed Crumb Rubber for Asphalt Modification

Modifying asphalt is a potentially high-value application for reusing waste plastics because of the high-volume usage of asphalt in highway construction. However, simply blending hot plastics and asphalt encounters difficulties related to the poor solubility of polymers, which limits the formation of a swollen network with asphalt molecules. The polymer phases also tend to coalesce and separate from asphalt during high-temperature storage in static conditions. The present study developed an innovative process to stabilize waste plastics in asphalt and improve binder storage stability by using lightly pyrolyzed crumb rubber together with a chemical compatibilizer. Both polymers were extruded to produce a thermoplastic elastomer (TPE) for asphalt modification. The mechanical performance and chemical reactions of TPEs were characterized via tension test and Fourier transform infrared spectroscopy. The storage stability and rheological properties of modified binder blends were evaluated through laboratory asphalt stability test and dynamic shear rheometer test. Polymer phases and network structures were characterized through optical microscopy. It was found that the pyrolyzed and reactive extrusion process improved the rubber solubility and polymer interaction, and therefore the storage stability of modified binder blends. The co-existence of rigid plastic and soft rubbery regimes in an entangled network provided a promising pathway to improve the mechanical performance of asphalt binders in both high- and low-temperature domains.

Ma, Yuetan↗