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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 19 records

Mechanically and Thermally Enhanced 3D-Printed Photocurable Polymer Nanocomposites Containing Functionalized Chitin Nanowhiskers by Stereolithography

Additive manufacturing, or simply 3D printing (3DP), where objects are built through layer-wise material deposition, has gained significant academic and industrial attention as a result of the development of advanced and functional materials requiring rapid, customized, and flexible solutions. In the context of green manufacturing, diversifying environmentally and economically sustainable material portfolios is an essential endeavor for the success of 3DP technology that uses widely available, highly valuable, and renewable materials. Here, we used stereolithography (SLA) for processing methacrylate-based photocurable resins containing crab shell-derived chitin nanowhiskers (CNWs), which are surface-functionalized by reactive acrylate groups. Results from full spectral, thermal, structural, and topological analyses corroborate not only the surface functionalization of CNWs but also indicate the presence of these photocurable CNW (pCNW) fillers in the 3D-printed nanocomposites. Owing to the strong interfacial bond induced by the physical and chemical crosslinking between the pCNW and methacrylate (MA) polymer matrix, the internally formulated nanocomposites displayed enhanced thermomechanical properties (e.g., storage modulus and glass transition temperature) compared to those of commercially available pure SLA resins. For instance, the inclusion of 0.5 wt % pCNW improved the tensile strength and stiffness to up to 78 and 71%, respectively, without compromising the toughness and ductility of the printed material. Accordingly, this result also evidences the compatibility between the filler and resin materials. Consequently, the formation of a crosslinked network in the nanocomposite structure results in a higher thermal stability and activation energy (i.e., up to ~79%) for all the hybrid materials than the pristine MA. Finally, the high-resolution SLA print features, dimensional accuracy, and enhanced mechanical performance of our microstructure-forming functionalized chitin-based nanocomposites make them promising materials for a wide range of robust and high-performance industrial applications.

36 MATERIALS SCIENCE↗

Recent Advances in Vertically Aligned Nanocomposites with Tunable Optical Anisotropy: Fundamentals and Beyond

Developing reliable and tunable metamaterials is fundamental to next-generation optical-based nanodevices and computing schemes. In this review, an overview of recent progress made with a unique group of ceramic-based functional nanocomposites, i.e., vertically aligned nanocomposites (VANs), is presented, with the focus on the tunable anisotropic optical properties. Using a self-assembling bottom-up deposition method, the as-grown VANs present great promise in terms of structural flexibility and property tunability. Such broad tunability of functionalities is achieved through VAN designs, material selection, growth control, and strain coupling. The as-grown multi-phase VAN films also present enormous advantages, including wafer scale integration, epitaxial quality, sharp atomic interface, as well as designable materials and geometries. This review also covers the research directions with practical device potentials, such as multiplex sensing, high-temperature plasmonics, magneto-optical switching, as well as photonic circuits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrafast Preparation of Nonequilibrium FeNi Spinels by Magnetic Induction Heating for Unprecedented Oxygen Evolution Electrocatalysis

Carbon-supported nanocomposites are attracting particular attention as high-performance, low-cost electrocatalysts for electrochemical water splitting. These are mostly prepared by pyrolysis and hydrothermal procedures that are time-consuming (from hours to days) and typically difficult to produce a nonequilibrium phase. Herein, for the first time ever, we exploit magnetic induction heating-quenching for ultrafast production of carbon-FeNi spinel oxide nanocomposites (within seconds), which exhibit an unprecedentedly high performance towards oxygen evolution reaction (OER), with an ultralow overpotential of only +260 mV to reach the high current density of 100 mA cm -2 . Experimental and theoretical studies show that the rapid heating and quenching process (ca. 10 3 K s -1 ) impedes the Ni and Fe phase segregation and produces a Cl-rich surface, both contributing to the remarkable catalytic activity. Results from this study highlight the unique advantage of ultrafast heating/quenching in the structural engineering of functional nanocomposites to achieve high electrocatalytic performance towards important electrochemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photocatalytic Generation of Singlet Oxygen by Graphitic Carbon Nitride for Antibacterial Applications

Carbon-based functional nanocomposites have emerged as potent antimicrobial agents and can be exploited as a viable option to overcome antibiotic resistance of bacterial strains. In the present study, graphitic carbon nitride nanosheets are prepared by controlled calcination of urea. Spectroscopic measurements show that the nanosheets consist of abundant carbonyl groups and exhibit apparent photocatalytic activity under UV photoirradiation towards the selective production of singlet oxygen. Therefore, the nanosheets can effectively damage the bacterial cell membranes and inhibit the growth of bacterial cells, such as Gram-negative Escherichia coli, as confirmed in photodynamic, fluorescence microscopy, and scanning electron microscopy measurements. The results from this research highlight the unique potential of carbon nitride derivatives as potent antimicrobial agents.

36 MATERIALS SCIENCE↗

Additive Manufacturing of Controlled Porous Elastomeric Nanocomposites for Enhanced Sensing Function

Sensors manufactured using piezoresistive elastomeric nanocomposites have a wide range of applications in many fields such as structural health monitoring, robotics, and biomedical industries. Additive manufacturing of these sensors, achieved using Direct Ink Writing (DIW), has provided numerous advantages including increased sensitivity and the fabrication of complex geometry. However, solid sensors manufactured either additively or using conventional methods, display a greater level of hysteresis, especially at strains higher than 10%, which limits their sensitivity. The solid sensors also display a greater level of piezoresistive relaxation where the resistance change with time either in a static or dynamic loading environment. Porosity can be introduced in the form of varying infill patterns and densities to reduce bulk material effects. In this paper, a lattice structure with four infill densities are investigated, and the samples are printed using a grid infill pattern. The fabricated samples are characterized using a scanning electron microscope (SEM) to validate the microstructural features and layer bonding. The pressure-sensing capability of each sensor is investigated using cyclic compression loading at various strain levels. Sensing results show that an increase in sensitivity, as well as a decrease in hysteresis with an increase in porosity, compared to solid samples (100% in-fill). The highest porosity was measured to be 62.3% with a corresponding 112% increase in the gauge factor compared to the solid bulk. These results indicate that introducing porosity using DIW is a sensible strategy to improve the piezoresistive performance of nanocomposites and to allow for the tunability of sensing capacity in pressure sensors

Sukati, Musa↗

Polymer Zwitterions for Stabilization of CsPbBr 3 Perovskite Nanoparticles and Nanocomposite Films

Functional polymers with sulfobetaine or phosphorylcholine zwitterions as pendent groups are demonstrated as both ligands and host matrices for CsPbBr 3 perovskite nanoparticles (PNPs). These polymers produce nanocomposite films with excellent NP dispersion, optical transparency, and impressive resistance to NP degradation upon exposure to water. Multidentate interactions of the zwitterion-containing copolymers with the PNPs induce dispersed or weakly aggregated nanocomposite morphologies, depending on the extent of zwitterionic functionality in the polymer. Incorporating additional functionality into the polymers, such as benzophenone pendent groups, yields lithographically patternable films, while time-resolved photoluminescence measurements provide insight into the electronic impact of PNPs in zwitterionic polymer matrices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ionizing Radiation Sensing with Functionalized and Copper-Coated SWCNT/PMMA Thin Film Nanocomposites

This paper studies the ionizing radiation effects on functionalized single-walled carbon nanotube (SWCNT)/poly(methyl methacrylate) (PMMA) thin-film nanocomposites [SWNT/PMMA]. The functionalized thin-film devices are made of ferrocene-doped SWCNTs, SWCNTs functionalized with carboxylic acid (COOH), and SWCNTs coated/ modified with copper. The nanocomposite was synthesized by the solution blending method and the resulting nanocomposite was spin-cast on interdigitated electrodes (IDEs). A 160 kV X-ray source was used to irradiate the thin film and changes in the electrical resistance of the nanocomposites due to X-rays were measured using a semiconductor device analyzer. Carboxylic acid functionalized and copper-coated SWCNT/PMMA nanocomposite showed a reduced response to X-rays compared to unfunctionalized SWCNT/PMMA nanocomposite. Ferrocene-doped SWCNT showed a higher sensitivity to X-rays at lower dose rates. This is in contrast to a previous study that showed that similar nanocomposites using functionalized multi-walled CNTs (MWCNTs) had demonstrated an improved response to X-rays ionizing radiation compared to unfunctionalized MWCNTs for all dose rates. Electrical measurements were also performed using the Arduino Nano microcontroller. The result showed that a relatively economical, lightweight-designed prototype radiation sensor based on SWCNT/PMMA thin-film devices could be produced by interfacing the devices with a modest microcontroller. This work also shows that by encapsulating the SWCNT/PMMA thin-film device in a plastic container, the effect of ambient humidity can be reduced and the device can still be used to detect X-ray radiation. This study further shows that the sensitivity of SWCNT to X-rays was dependent on both the functionalization of the SWCNT and the dose rate.

36 MATERIALS SCIENCE↗

A pathway to desired functionalities in vertically aligned nanocomposites and related architectures

Epitaxial vertically aligned nanocomposites (VANs) and their related architectures have shown many intriguing features that are not available from conventional two-dimensional planar multilayers and heterostructures. The ability to control constituent, interface, microstructure, strain, and defects based on VANs has enabled the multiple degrees of freedom to manipulate the optical, magnetic, electrochemical, electronic, ionic, and superconducting properties for specific applications. This field has rapidly expanded from the interest in oxide:oxide to oxide:metal, metal:nitride and nitride:nitride systems. To achieve unparalleled properties of the materials, three-dimensional super-nanocomposites based on a hybrid of VAN and multilayer architectures have been recently explored as well. The challenges and opportunities of VAN films are also discussed in this article.

36 MATERIALS SCIENCE↗

Covalently integrated silica nanoparticles in poly(ethylene glycol)-based acrylate resins: thermomechanical, swelling, and morphological behavior

Nanocomposites integrate functional nanofillers into viscoelastic matrices for electronics, lightweight structural materials, and tissue engineering. Herein, the effect of methacrylate-functionalized (MA-SiO 2 ) and vinyl-functionalized (V-SiO 2 ) silica nanoparticles on the thermal, mechanical, physical, and morphological characteristics of poly(ethylene glycol) (PEG) nanocomposites was investigated. The gel fraction of V-SiO 2 composites decreases upon addition of 3.8 wt% but increases with further addition (>7.4 wt%) until it reaches a plateau at 10.7 wt%. The MA-SiO 2 induced no significant changes in gel fraction and both V-SiO 2 and MA-SiO 2 nanoparticles had a negligible impact on the nanocomposite glass transition temperature and water absorption. The Young's modulus and ultimate compressive stress increased with increasing nanoparticle concentration for both nanoparticles. Due to the higher crosslink density, MA-SiO 2 composites reached a maximum mechanical stress at a concentration of 7.4 wt%, while V-SiO 2 composites reached a maximum at a concentration of 10.7 wt%. Scanning electron microscopy, transmission electron microscopy, and small-angle X-ray scattering revealed a bimodal size distribution for V-SiO 2 and a monomodal size distribution for MA-SiO 2 . Although aggregates were observed for both nanoparticle surface treatments, V-SiO 2 dispersion was poor while MA-SiO 2 were generally well-dispersed. Finally, these findings lay the framework for silica nanofillers in PEG-based nanocomposites for advanced manufacturing applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer Zwitterions for Stabilization of CsPbBr 3 Perovskite Nanoparticles and Nanocomposite Films

Abstract Functional polymers with sulfobetaine or phosphorylcholine zwitterions as pendent groups are demonstrated as both ligands and host matrices for CsPbBr 3 perovskite nanoparticles (PNPs). These polymers produce nanocomposite films with excellent NP dispersion, optical transparency, and impressive resistance to NP degradation upon exposure to water. Multidentate interactions of the zwitterion‐containing copolymers with the PNPs induce dispersed or weakly aggregated nanocomposite morphologies, depending on the extent of zwitterionic functionality in the polymer. Incorporating additional functionality into the polymers, such as benzophenone pendent groups, yields lithographically patternable films, while time‐resolved photoluminescence measurements provide insight into the electronic impact of PNPs in zwitterionic polymer matrices.

Kim, Hyunki↗

Fabrication, thermal analysis, and heavy ion irradiation resistance of epoxy matrix nanocomposites loaded with silane-functionalized ceria nanoparticles

This paper describes a detailed understanding of how nanofillers function as radiation barriers within the polymer matrix, and how their effectiveness is impacted by factors such as composition, size, loading, surface chemistry, and dispersion. Here, we designed a comprehensive investigation of heavy ion irradiation resistance in epoxy matrix composites loaded with surface-modified ceria nanofillers, utilizing tandem computational and experimental methods to elucidate radiolytic damage processes and relate them to chemical and structural changes observed through thermal analysis, vibrational spectroscopy, and electron microscopy. A detailed mechanistic examination supported by FTIR spectroscopy data identified the bisphenol A moiety as a primary target for degradation reactions. Results of computational modeling by the Stopping Range of Ions in Matter (SRIM) Monte Carlo simulation were in good agreement with damage analysis from surface and cross-sectional SEM imaging. All metrics indicated that ceria nanofillers reduce the damage area in polymer nanocomposites, and that nanofiller loading and homogeneity of dispersion are key to effective damage prevention. The results of this study represent a significant pathway for engineered irradiation tolerance in a diverse array of polymer nanocomposite materials. Numerous areas of materials science can benefit from utilizing this facile and effective method to extend the reliability of polymer materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solution combustion synthesis of iron-based alumina catalysts for dehydrogenation of fossil fuels

Microwave-assisted thermocatalytic dehydrogenation of fossil fuels has been proposed as a method for hydrogen production with no CO2 emissions. The byproduct is carbon, which has a commercial value. Iron-based alumina nanocomposites are promising catalysts for this process as they both absorb microwave radiation and catalyze the dehydrogenation. In addition, they may have magnetic properties, which could be used for their separation from the carbon byproduct. Solution combustion synthesis (SCS) is an attractive technique for the fabrication of iron-based alumina nanocomposites because it can produce high specific surface area oxides in a facile manner. However, the effects of the heating mode, the fuel, and the iron/aluminum ratio on the combustion synthesis behavior and the product properties have not been studied yet. In the present work, the iron-based alumina nanocomposites were obtained by SCS using a hotplate, a muffle furnace, and a microwave oven. The initial mixtures were aqueous solutions of iron nitrate, aluminum nitrate, and an organic fuel. The concentrations of the two nitrates were varied in proportion to Fe:Al molar ratios of 1:2, 1:1, and 2:1. Two fuels were tested: citric acid and glycine. The combustion was less vigorous when citric acid was used as the fuel, which is explained by the lower exothermicity of the reaction. X-ray diffraction analysis of the products confirmed the formation of complex oxides of Fe and Al, specifically it detected hercynite and magnetite phases. Brunauer-Emmett-Teller surface area analysis has shown that the powders obtained using citric acid have specific surface areas as high as 276 m2/g, significantly higher than those obtained using glycine. Muffle furnace and hotplate heating led to comparable specific surface areas, while microwave heating resulted in significantly lower specific surface areas. The magnetic properties of the products increase with increasing the Fe/Al molar ratio from 1:2 (no response to a magnetic field) to 1:1 (weak response) and 2:1 (strong response).

solution combustion synthesis, nanoscale oxides, f↗

Making the most of your electrons: Challenges and opportunities in characterizing hybrid interfaces with STEM

Inspired by the unique architectures composed of hard and soft materials in natural and biological systems, synthetic hybrid structures and associated hard-soft interfaces have recently evoked significant interest. Soft matter is typically dominated by structural fluctuations even at room temperature, while hard matter is governed by rigid mechanical behavior. This dichotomy offers considerable opportunities to leverage the disparate properties offered by these components across a wide spectrum spanning from basic science to engineering insights with significant technological overtones. Such hybrid structures, which include polymer nanocomposites, DNA functionalized nanoparticle superlattices, and metal organic frameworks to name a few, have delivered promising insights into the technologically relevant applications such as catalysis, environmental remediation, optoelectronics, and medicine. The interfacial structure between the hard and soft phases demonstrates features across a variety of length scales and often strongly influence the functionality of hybrid systems. While scanning/transmission electron microscopy (S/TEM) has proven to be a valuable tool for acquiring intricate molecular and nanoscale details of these interfaces, the unusual nature of hybrid composites presents a suite of challenges that make assessing or establishing structure–property relationships especially difficult. There are additional considerations at all stages of sample analysis from preparing electron-transparent samples to obtaining sufficient contrast to resolve the interface between dissimilar materials given the dose sensitivity of soft materials. Here, we discuss each of these challenges and supplement a review of recent developments in the field with additional experimental investigations and simulations to present solutions for attaining a nano or molecular-level understanding of these interfaces. These solutions present a host of opportunities for investigating the role interfaces play in this unique class of functional materials.

36 MATERIALS SCIENCE↗

Polymer-Grafted Nanoparticles as All-in-One Nanoplatforms

Polymer-grafted nanoparticles (PGNPs) represent a versatile class of hybrid nanomaterials, in which nanoparticle cores and tethered polymer coronas are integrated into structurally programmable building blocks. Rapid advances in nanoparticle surface functionalization and surface-initiated polymerization have enabled increasingly precise control over the nanoparticle core composition and brush architecture, greatly expanding the accessible structural and functional landscape of PGNPs. This review summarizes recent progress in the modular design and structural regulation of PGNPs, with an emphasis on nanoparticle platforms and associated surface functionalization strategies, polymer brush synthesis and architectural control, and the structure−property relationships that govern PGNP behavior. Emerging applications are further highlighted, including additive manufacturing, self-healing materials, membrane-based gas separations, and battery-related systems, where PGNPs provide unique opportunities to couple nanoscale interfacial design with macroscopic performance. Finally, future opportunities are discussed for extending PGNP concepts to increasingly complex, multifunctional, and application-oriented hybrid materials.

functional nanocomposites↗

Magnetic functionalization and catalytic behavior of magnetic nanoparticles during laser photochemical graphitization of polyimide

We report laser-assisted photochemical graphitization of polyimides (PIs) into functional magnetic nanocomposites using laser irradiation of PI in the presence of magnetite nanoparticles (MNPs). PI Kapton sheets covered with MNP were photochemically treated under ambient conditions using a picosecond pulsed laser (1064 nm) to obtain an electrically conductive material. Scanning electron microscopy of the treated material revealed a layered magnetic nanoparticle/graphite (MNP/graphite) nanocomposite structure. Four probe conductivity measurements indicated that the nanocomposite has an electrical conductivity of 1550 ± 60 S/m. Superconducting quantum interference device magnetometer-based magnetic characterization of the treated material revealed an anisotropic ferromagnetic response in the MNP/graphite nanocomposite compared to the isotropic response of MNP. Raman spectroscopy of the MNP/graphite nanocomposite revealed a fourfold improvement in graphitization, suppression in disorder, and decreased nitrogenous impurities compared to the graphitic material obtained from laser treatment of just PI sheets. X-ray photoelectron spectroscopy, x-ray diffraction, and energy-dispersive x-ray spectroscopy were used to delineate the phase transformations of MNP during the formation of MNP/graphite nanocomposite. Post-mortem characterization indicates a possible photocatalytic effect of MNP during MNP/graphite nanocomposite formation. Under laser irradiation, MNP transformed from the initial Fe 3 O 4 phase to γ-Fe 2 O 3 and Fe 5 C 2 phases and acted as nucleation spots to catalyze the graphitization process of PI.

36 MATERIALS SCIENCE↗

Reducing leakage current and enhancing polarization in multiferroic 3D super-nanocomposites by microstructure engineering

Abstract Multiferroic materials have generated great interest due to their potential as functional device materials. Nanocomposites have been increasingly used to design and generate new functionalities by pairing dissimilar ferroic materials, though the combination often introduces new complexity and challenges unforeseeable in single-phase counterparts. The recently developed approaches to fabricate 3D super-nanocomposites (3D‐sNC) open new avenues to control and enhance functional properties. In this work, we develop a new 3D‐sNC with CoFe 2 O 4 (CFO) short nanopillar arrays embedded in BaTiO 3 (BTO) film matrix via microstructure engineering by alternatively depositing BTO:CFO vertically-aligned nanocomposite layers and single-phase BTO layers. This microstructure engineering method allows encapsulating the relative conducting CFO phase by the insulating BTO phase, which suppress the leakage current and enhance the polarization. Our results demonstrate that microstructure engineering in 3D‐sNC offers a new bottom–up method of fabricating advanced nanostructures with a wide range of possible configurations for applications where the functional properties need to be systematically modified.

36 MATERIALS SCIENCE↗

Enhanced upconversion and photoconductive nanocomposites of lanthanide-doped nanoparticles functionalized with low-vibrational-energy inorganic ligands

Upconverting nanoparticles (UCNPs) convert near-infrared (IR) light into higher-energy visible light, allowing them to be used in applications such as biological imaging, nano-thermometry, and photodetection. It is well known that the upconversion luminescent efficiency of UCNPs can be enhanced by using a host material with low phonon energies, but the use of low-vibrational-energy inorganic ligands and non-epitaxial shells has been relatively underexplored. Here, we investigate the functionalization of lanthanide-doped NaYF4 UCNPs with low-vibrational-energy Sn2S64- ligands. Raman spectroscopy and elemental mapping are employed to confirm the binding of Sn2S64- ligands to UCNPs. This binding enhances upconversion efficiencies up to a factor of 16, consistent with an increase in the luminescent lifetimes of the lanthanide ions. Annealing Sn2S64--capped UCNPs results in the formation of a nanocomposite comprised of UCNPs embedded within an interconnected matrix of SnS2, enabling each UCNP to be electrically accessible through the semiconducting SnS2 matrix. This facilitates the integration of UCNPs into electronic devices, which we demonstrate through the fabrication of a UCNP-SnS2 photodetector that detects UV and near-IR light. Our findings show the promise of using inorganic capping agents to enhance the properties of UCNPs while facilitating their integration into optoelectronic devices.

Pan, Jia-Ahn↗