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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Aqueous Polymer Modification of Cellulose Nanofibrils by Grafting‐Through a Reactive Methacrylate Group

Abstract Modifying the surface of cellulose nanofibrils (CNFs) produced by mechanical refinement with a variety of polymer functional groups in an entirely water‐based system is challenging because only surface hydroxyl groups are accessible. To address this limitation, an entirely water‐based, polymer modification scheme is developed. CNFs are functionalized with a reactive methacrylate functional group followed by subsequent grafting‐through polymerization. This modification worked with a variety of water‐soluble and water‐insoluble (meth)acrylates and (meth)acrylamides, grafting up to 45 wt% polymer on to the CNFs. The reaction conditions introducing the methacrylate functional group are adjusted to vary the degree of functionality. Soxhlet extraction of modified samples demonstrates that the reactive methacrylate group is necessary to facilitate polymer grafting. The degree of functionalization of the polymers is studied via quantitative transmission IR spectroscopy and the morphology of the resulting cellulose nanofibrils is studied via a combination of optical, scanning electron, and atomic force microscopy. High levels of polymer modification do not significantly affect the micrometer‐scale fibril morphology.

Kelly, Peter V.↗
DOE OSTI2021

Block graft copolymer binders and their use in silicon-containing anodes of lithium-ion batteries

A graft copolymer composition comprising the following structure: wherein: Ax represents a polymer backbone having a number of polymerized monomer units x; [By] represents a multiplicity of a graft polymer side chain having a number of polymerized monomer units y, and at least a portion of the monomer units in By contains a group —C(O)OM, with M independently selected from H and alkali metals; [C] represents a multiplicity of positions on the polymer backbone Ax where the graft polymer side chain B or any other graft polymer side chain is not attached; the subscript w represents a grafting density of the group By, wherein w is an integer within a range of 10-50%; and the subscript z represents a density of the group C, wherein z=(100−w) %. The invention is also directed to lithium-ion batteries in which the above-described composition is incorporated in an anode of the battery.

Saito, Tomonori↗
DOE OSTI2024

Unusual Electrical Conductivity Enhancement in Stable n‐Type Carbon Nanotube Networks

Organic molecule-doped n-type single-walled carbon nanotube (SWCNT) networks are promising candidates for advanced energy applications, such as flexible thermoelectrics and photovoltaics. Yet charge transport in n-type SWCNTs is limited by two factors: i) charge localization impeding inter-tube transport caused by disordered mesostructure of randomly oriented SWCNTs and ii) reduction of charge carrier concentration driven by oxidation. Herein, studied the relationship between the mesostructure and thermoelectric properties of n-type SWCNTs obtained by surfactant-functionalization and polymer-dopant grafting. Surprisingly, the electrical conductivity of the polymer-doped SWCNTs keeps increasing with increasing polymer content, even after the saturation of carrier concentration, resulting in 12x higher conductivity on polymer-doping compared to surfactant-functionalization. While hopping transport typically dominates in disordered systems, it is shown that a bridging effect from the polymer causes unusual band-like conduction in polymer-doped SWCNTs. Additionally, since surfactants are essential to prevent oxidation and retain n-type over a long duration, shows that SWCNTs obtained through a dual-functionalization strategy using both polymer-dopant and surfactant, demonstrates a long-term stable high n-type thermoelectric power factor, when the surfactant amount is carefully controlled. Besides thermoelectrics, the findings are of general interest to developing stable and conductive n-type SWCNTs for various energy and electronic applications.

carbon nanotubes↗
DOE OSTI2022

Depletion-Driven Assembly of Polymer-Coated Nanocrystals

Depletion-driven assembly has been widely studied for micron-sized colloids, but questions remain at the nanoscale where the governing physics are impacted by stabilizing surface ligands or wrapping polymers, whose dimensions are similar to those of the colloidal core and the depletant. Here, we probe how wrapping colloidal tin-doped indium oxide nanocrystals with polymers affects their depletion-induced interactions and assembly in solutions of polyethylene glycol. Copolymers of polyacrylic acid grafted with polyethylene oxide provide nanocrystal wrappings with different effective polymer graft densities and molecular weights. (Ultra) small angle X-ray scattering, coarse-grained molecular dynamics simulation, and molecular thermodynamic theory were combined to analyze how depletant size and polymer wrapping characteristics affect depletion interactions, structure, and phase behavior. The results show how depletant molecular weight, as well as surface density and molecular weight of polymer grafts, set thresholds for assembly. These signatures are unique to depletion-driven assembly of nanoscale colloids and mirror phase behaviors of grafted nanoparticle–polymer composites. Optical and rheological responses of depletion-driven assemblies of nanocrystals with different polymer shell architectures were probed to learn how their structural differences impact properties. Finally, we discuss how these wrinkles for depletion-driven assembly at the nanoscale may provide fresh opportunities for designing responsive depletion interactions and dynamically reconfigurable materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Aqueous Carbon Capture Using Guanidinium-Functionalized Hollow Fiber Sorbent Contactors

As part of the growing suite of technologies aimed at combatting rising temperatures, negative emissions technologies have become a powerful tool in the global effort to minimize the consequences of human-induced climate change. Among these, carbon removal from aqueous sources, which contain much higher carbon concentrations than the atmosphere, remains largely unexplored. Indeed, developing robust and efficient carbon capture materials for usage in complex aqueous environments remains a significant challenge. Here, we explore the potential of functionalizing polyvinylidene fluoride (PVDF) hollow fiber contactors grafted with a guanidinium-derived polymer sorbent for carbon removal from aqueous sources, including saline waters. Computational screening against amine-based analogs is utilized to identify guanidinium as a promising motif for bicarbonate (HCO 3 – ) ions binding. To leverage this finding, synthesis of a guanidinium polymer and subsequent covalent grafting onto PVDF hollow fibers is employed to structured polymer–sorbent–grafted hollow fiber contactors. Our prototype achieves an initial HCO 3 – removal of 34% with an increase to 98% after four cycles. The functionalized fibers demonstrate aqueous stability over 13 adsorption/desorption cycles in model NaHCO 3 solutions where regeneration is facilitated by a mild pH swing. Importantly, the system maintains selective performance in the presence of competitive chloride ions over multiple cycles; carbon removal remained above 10% even at high (10:1) NaCl/NaHCO 3 ratios. These findings demonstrate the feasibility of sorbent-based aqueous carbon removal and highlight its potential as a promising approach for negative emissions.

carbon capture↗
DOE OSTI2025

Hydration and Restructuring of Polar Polymer Interfaces: Implications in Antifouling and Responsive Materials

Manipulating polymer interfaces is crucial for understanding how structure influences function in applications spanning biofouling prevention to energy storage. Moreover, observing how polymers adapt their microscopic structure to changes in their local environment can reveal essential properties that govern their performance in such applications, providing key insights into how to design more effective interfaces. Here, in this study, a series of “grafting-from” polymer brushes with side chains varying in charge, are probed by sum frequency generation (SFG) and modeled using all-atom molecular dynamics (MD) simulations to elucidate how chemical makeup and charge mediate interfacial restructuring in dry versus hydrated states. Results show that charge, in progressing from nonpolar to cationic to zwitterionic, results in dramatic changes in interfacial structure and overall hydration. While net neutral systems, regardless of bulk phase polarity, show minimal interfacial water structuring, the cationic species exhibits strong bulk water signals from the surface potential. Meanwhile, the polymer brushes themselves restructure in water differently independent of charge, impacting the functional groups that are presented to the aqueous phase. Nonpolar and cationic species for instance undergo a change in alkyl group orientations to accommodate hydrating water molecules, whereas the zwitterionic polymer becomes completely disordered in water. Overall, the structure-based behavior trends presented herein have implications in antifouling applications and responsive material interfaces.

biointerface↗
DOE OSTI2023

Synthesis of hyperbranched polymer films via electrodeposition and oxygen-tolerant surface-initiated photoinduced polymerization

Hypothesis Hyperbranched polymers, not only possess higher functionality, but are also easier to prepare compared to dendrimers and dendric polymers. Combining electrodeposition and surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer (SI-PET-RAFT) polymerization is hypothesized to be a novel strategy for preparing hyperbranched polymer films on conductive surfaces without degassing. Experiments In this study, polymer brush grafted films with four different architectures (i.e. linear, branched, linear- block -branched, and branched- block -linear) were prepared on gold-coated glass substrates using electrodeposition, followed by SI-PET-RAFT polymerization. The resulting film structure and thickness, surface topology, absorption property, and electrochemical behavior were confirmed by spectroscopy, microscopy, microbalance technique, and impedance measurement. Findings These hyperbranched polymer brushes were capable of forming a thicker but more uniformly covered films compared to linear polymer brush films, demonstrating that hyperbranched polymer films can be potentially useful for fabricating protective polymer coatings on various conductive surfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A “Graft to” Electrospun Zwitterionic Bilayer Membrane for the Separation of Hydraulic Fracturing-Produced Water via Membrane Distillation

Simultaneous fouling and pore wetting of the membrane during membrane distillation (MD) is a major concern. In this work, an electrospun bilayer membrane for enhancing fouling and wetting resistance has been developed for treating hydraulic fracture-produced water (PW) by MD. These PWs can contain over 200,000 ppm total dissolved solids, organic compounds and surfactants. The membrane consists of an omniphobic surface that faces the permeate stream and a hydrophilic surface that faces the feed stream. The omniphobic surface was decorated by growing nanoparticles, followed by silanization to lower the surface energy. An epoxied zwitterionic polymer was grafted onto the membrane surface that faces the feed stream to form a tight antifouling hydration layer. The membrane was challenged with an aqueous NaCl solution containing sodium dodecyl sulfate (SDS), an ampholyte and crude oil. In the presence of SDS and crude oil, the membrane was stable and displayed salt rejection (>99.9%). Further, the decrease was much less than the base polyvinylidene difluoride (PVDF) electrospun membrane. The membranes were also challenged with actual PW. Our results highlight the importance of tuning the properties of the membrane surface that faces the feed and permeate streams in order to maximize membrane stability, flux and salt rejection.

omniphobic↗
DOE OSTI2024

Degradation and Upcycling of Poly(acrylic) Acid (PAA)

Poly(acrylic acid) (PAA) is a superabsorbent polymer (SAP) widely used in food, paint, textiles, and household products, such as absorbent hygiene products. Specifically, disposable diaper waste comprises a large majority of hygiene waste, in which 80% is landfilled and 20% is incinerated. This proposal describes new methods to valorize PAA to mitigate pollution and risk of large-scale release, dispersion, and accumulation of PAA into aquatic and terrestrial environments. The first strategy builds upon photoredox catalysis to oxidize PAA, which will allow for subsequent cleavage to PAA into valuable chemical feedstocks with intriguing functional groups that can readily undergo further transformations. Moreover, in conjunction with RAFT polymerization, photoredox catalysis would also lead to preparation of new graft block polymers to serve as pH-sensitive drug delivery vehicles. The second strategy invokes electrocatalysis, which can access different intermediates compared to photoredox catalysis. This method would lead to refunctionalization and repurpose of PAA into hydrogels and zwitterionic polymers that can find utilities in ion exchange, water treatment, soil conditioning, paper reinforcement, pigment retention, shampoo formulation, and drug delivery.

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

Comprehensive view of microscopic interactions between DNA-coated colloids

Abstract The self-assembly of DNA-coated colloids into highly-ordered structures offers great promise for advanced optical materials. However, control of disorder, defects, melting, and crystal growth is hindered by the lack of a microscopic understanding of DNA-mediated colloidal interactions. Here we use total internal reflection microscopy to measure in situ the interaction potential between DNA-coated colloids with nanometer resolution and the macroscopic melting behavior. The range and strength of the interaction are measured and linked to key material design parameters, including DNA sequence, polymer length, grafting density, and complementary fraction. We present a first-principles model that screens and combines existing theories into one coherent framework and quantitatively reproduces our experimental data without fitting parameters over a wide range of DNA ligand designs. Our theory identifies a subtle competition between DNA binding and steric repulsion and accurately predicts adhesion and melting at a molecular level. Combining experimental and theoretical results, our work provides a quantitative and predictive approach for guiding material design with DNA-nanotechnology and can be further extended to a diversity of colloidal and biological systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Ionic-like Superlattices by Charged Nanoparticles: A Step Toward Photonics Applications

Controlling interactions among nanoparticles is paramount to achieving assemblies vital to technologies seeking to exploit their cutting-edge collective properties. Although various techniques have been advanced, robust ones are necessary for upscaling nanoparticle assembly and crystallization. Here, we show that by grafting gold nanoparticles (AuNPs) with charge-end-group-thiolated poly(ethylene glycol), we control the charge of each AuNP. Such control facilitates the formation of various two-dimensional structures of oppositely charged binary constituents at vapor/liquid interfaces. Using surface-sensitive synchrotron X-ray diffraction techniques, we established the formation of distinct checkerboard square lattice structures at a range of pH values and molar ratios of the constituents. By regulating pH, the superlattices can transform from a square to a hexagonal lattice, or vice versa, and to a single-component superstructure at the interface. In conclusion, our recipe for the control of charges and their consequent interactions among nanoparticles can be readily exploited in the assembly of photonics and plasmonics devices in two and three dimensions.

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

Effects of crystallization on micro-mechanical behavior of polyethylene nanocomposites using Raman spectroscopy

Recent work has shown that nanoparticles can be ordered in semicrystalline polymers by controlling the crystallization rate, specifically by forcing them to migrate to the amorphous regions of the lamellar morphology. Here, we study the micromechanical behavior of neat polyethylene and silica/polyethylene nanocomposites filled with 15 nm brush-modified silica in the quenched and slow-crystallized organized state. The molecular response to loading in tension was monitored with Raman spectroscopy using the peaks associated with crystalline and amorphous regions. The addition of nanofillers dramatically reduced the shift in the amorphous peaks, indicating that in addition to carrying some load, the brush-modified nanoparticles may be acting as tie molecules that restrict amorphous deformation. The higher degree of lamellar organization and the organization of the nanoparticles also impacted the crystalline peak shifts, but more subtly.

Polyethylene↗
DOE OSTI2021

Insights into the Enhanced Oxidative Thermal Stability of Nanoparticle Organic Hybrid Materials Developed for Carbon Capture and Energy Storage

Due to the growing need for Direct Air Capture (DAC) and integrated carbon capture and conversion technologies, CO 2 capture materials that can withstand a wide range of environmental conditions, including fluctuating ambient temperatures and high concentrations of oxidizing agents (i.e., oxygen and moisture), are critically needed. Liquid-like Nanoparticle Organic Hybrid Materials (NOHMs) have been proposed as candidates for DAC and electrolyte additives enabling sustainable energy storage (i.e., integrated CO 2 capture and conversion and flow batteries). Liquid-like NOHMs functionalized with an ionic bond have been shown to display greatly enhanced oxidative thermal stability compared to the untethered polymer. However, these studies were limited in terms of reaction conditions and the detailed mechanisms of the oxidative thermal degradation were not reported. In this work, a kinetic thermal degradation analysis was performed on NOHM-I-HPE and the neat polymer, Jeffamine M2070 (HPE), in both non-oxidative and oxidative conditions. NOHM-I-HPE displayed similar thermal stability to the untethered polymer in a nitrogen environment, but interestingly, the thermal stability of the ionically tethered polymer was significantly enhanced in the presence of air. This observed enhancement of oxidative thermal stability is attributed to the orders of magnitude larger viscosity of the liquid-like NOHMs compared to untethered polymer and the bond stabilization of the ionically tethered polymer in the NOHMs canopy. Further, spectroscopic analyses of the liquid residue revealed that in the presence of oxygen, the degradation of HPE and NOHM-I-HPE occurs through the formation of trace amounts of carbonyls. This study illustrated that NOHMs can serve as functional materials for sustainable energy storage applications because of their excellent oxidative thermal stability.

25 ENERGY STORAGE↗
DOE OSTI2021

Dynamic Mixing Behaviors of Ionically Tethered Polymer Canopy of Nanoscale Hybrid Materials in Fluids of Varying Physical and Chemical Properties

An emerging area of sustainable energy and environmental research is focused on the development of novel electrolytes that can increase the solubility of target species and improve subsequent reaction performance. Electrolytes with chemical and structural tunability have allowed for significant advancements in flow batteries and CO 2 conversion integrated with CO 2 capture. Liquid-like nanoparticle organic hybrid materials (NOHMs) are nanoscale fluids that are composed of inorganic nanocores and an ionically tethered polymeric canopy. NOHMs have been shown to exhibit enhanced conductivity making them promising for electrolyte applications, though they are often challenged by high viscosity in the neat state. In this study, a series of binary mixtures of NOHM-I-HPE with five different secondary fluids, water, chloroform, toluene, acetonitrile, and ethyl acetate, were prepared to reduce the fluid viscosity and investigate the effects of secondary fluid properties (e.g., hydrogen bonding ability, polarity, and molar volume) on their transport behaviors, including viscosity and diffusivity. We report our results revealed that the molecular ratio of secondary fluid to the ether groups of Jeffamine M2070 ($λ_{\text{SF}}$) was able to describe the effect that secondary fluid has on transport properties. Our findings also suggest that in solution, the Jeffamine M2070 molecules exist in different nanoscale environments, where some are more strongly associated with the nanoparticle surface than others, and the conformation of the polymer canopy was dependent on the secondary fluid. This understanding of the polymer conformation in NOHMs can allow for the better design of an electrolyte capable of capturing and releasing small gaseous or ionic species.

25 ENERGY STORAGE↗
DOE OSTI2022

Mechanistic Study of Controlled Zinc Electrodeposition Behaviors Facilitated by Nanoscale Electrolyte Additives at the Electrode Interface

Nanoparticle organic hybrid materials (NOHMs) are liquid-like materials composed of an inorganic core to which a polymeric canopy is ionically tethered. NOHMs have unique properties including negligible vapor pressure, high oxidative thermal stability, and the ability to bind to reactive species of interest due to the tunability of their polymeric canopy. This makes them promising multifunctional materials for a wide range of energy and environmental technologies, including electrolyte additives for electrochemical energy storage (e.g., flow batteries) and the electrochemical conversion of CO 2 to chemicals and fuels. Due to their unique transport behaviors in fluid systems, an understanding of the near-electrode surface behavior of NOHMs in electrolyte solutions and their effect on electrochemical reactions is still lacking. In this work, the complexation of zinc (Zn) by NOHMs with an ionically tethered polyetheramine canopy (HPE) (NOHM-I-HPE) was studied using attenuated total reflectance Fourier transform infrared and Carbon-13 nuclear magnetic resonance spectroscopy. Additionally, various electrochemical techniques were employed to discern the role of NOHM-I-HPE during zinc electrodeposition, and the results were compared to those of the electrochemical system containing untethered HPE polymers. Our findings confirmed that NOHM-I-HPE and HPE reversibly complex zinc in the aqueous electrolyte. NOHM-I-HPE and HPE were found to block some of the electrode active sites, reducing the overall current density during electrodeposition, while facilitating the formation of smooth zinc deposits, as revealed by surface imaging and diffraction techniques. Observed variations in the current density responses and the degree of passivation created by the NOHM-I-HPE and HPE adsorbed on the electrode surface revealed that their different packing behaviors at the electrode–electrolyte interface influence the zinc deposition mechanism. The presence of the nanoparticle and ordering offered by the NOHMs as well as the structured conformation of the polymeric canopy allowed the formation of void spaces and free volumes for enhanced transport behaviors. Furthermore, these findings provided insights into how structured electrolyte additives such as NOHMs can allow for advancements in electrolyte design for controlled deposition of metal species from energy-dense electrolytes or for other electrochemical reactions.

25 ENERGY STORAGE↗
NASA NTRS2003

Mirrors Containing Biomimetic Shape-Control Actuators

Curved mirrors of a proposed type would comprise lightweight sheets or films containing integral, biologically inspired actuators for controlling their surface figures. These mirrors could be useful in such applications as collection of solar energy, focusing of radio beams, and (provided sufficient precision could be achieved) imaging. These mirrors were originally intended for use in outer space, but it should also be possible to develop terrestrial versions. Several prior NASA Tech Briefs articles have described a variety of approaches to the design of curved, lightweight mirrors containing integral shape-control actuators. The primary distinction between the present approach and the prior approaches lies in the actuator design concept, which involves shapes and movements reminiscent of those of a variety of small, multi-armed animals. The shape and movement of an actuator of this type can also be characterized as reminiscent of that of an umbrella. This concept can be further characterized as a derivative of that of multifinger grippers, the fingers of which are bimorph bending actuators (see Figure 1). The fingers of such actuators can be strips containing any of a variety of materials that have been investigated for use as actuators, including such electroactive polymers as ionomeric polymer/metal composites (IPMCs), ferroelectric polymers, and grafted elastomers. A mirror according to this proposal would be made from a sheet of one of the actuator composites mentioned above. The design would involve many variables, including the pre-curvature and stiffness of the mirror sheet, the required precision of figure control, the required range of variation in focal length (see Figure 2), the required precision of figure control for imaging or non-imaging use, the bending and twisting moments needed to effect the required deformations, and voltage-tomoment coefficients of the actuators, and the voltages accordingly required for actuation. A typical design would call for segmentation of the electrodes on the actuators so that voltages could be applied locally to effect local bending for fine adjustment of the surface figure.

Bar-Cohen, Yoseph↗