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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

Compounds and composition for preparation of lithium-loaded plastic scintillators

A scintillator material includes a polymer matrix, a primary dye in the polymer matrix, the primary dye being a fluorescent dye; a secondary dye, and a Li-containing compound in the polymer matrix, where the Li-containing compound is a Li salt of a short-chain aliphatic acid. In addition, the scintillator material exhibits an optical response signature for thermal neutrons that is different than an optical response signature for fast neutrons.

Zaitseva, Natalia P.↗

Stretchable Photodiodes with Polymer-Engineered Semiconductor Nanowires for Wearable Photoplethysmography

Healthcare systems worldwide have been stressed to provide sufficient resources to serve the increasing and aging population in our society. The situation became more challenging at the time of pandemic. Technology advancement, especially the adoption of wearable health monitoring devices, has provided an important supplement to current clinical equipment. Most health monitoring devices are rigid, however, human tissues are soft. Such a difference has prohibited intimate contact between the two and jeopardized wearing comfortableness, which hurdles measurement accuracy especially during longtime usage. Here, in this work, we report a soft and stretchable photodiode that can conformally adhere onto the human body without any pressure and measure cardiovascular variables for an extended period with higher reliability than commercial devices. The photodiode used a composite light absorber consisting of an organic bulk heterojunction embedded into an elastic polymer matrix. It is discovered that the elastic polymer matrix not only improves the morphology of the bulk heterojunction for obtaining the desired mechanical properties but also alters its electronic band structure and improves the electrical properties that lead to a reduced dark current and enhanced photovoltage in the stretchable photodiode. The work has demonstrated high fidelity measurements and longtime monitoring of heat rate variability and oxygen saturation, potentially enabling next-generation wearable photoplethysmography devices for point-of-care diagnosis of cardiovascular diseases in a more accessible and affordable way.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

High-performance piezoelectric composites via β phase programming

Polymer-ceramic piezoelectric composites, combining high piezoelectricity and mechanical flexibility, have attracted increasing interest in both academia and industry. However, their piezoelectric activity is largely limited by intrinsically low crystallinity and weak spontaneous polarization. Here, we propose a Ti 3 C 2 T x MXene anchoring method to manipulate the intermolecular interactions within the all-trans conformation of a polymer matrix. Employing phase-field simulation and molecular dynamics calculations, we show that OH surface terminations on the Ti 3 C 2 T x nanosheets offer hydrogen bonding with the fluoropolymer matrix, leading to dipole alignment and enhanced net spontaneous polarization of the polymer-ceramic composites. We then translated this interfacial bonding strategy into electrospinning to boost the piezoelectric response of samarium doped Pb (Mg1/3Nb 2/3 )O 3 -PbTiO 3 /polyvinylidene fluoride composite nanofibers by 160% via Ti 3 C 2 T x nanosheets inclusion. With excellent piezoelectric and mechanical attributes, the as-electrospun piezoelectric nanofibers can be easily integrated into the conventional shoe insoles to form a foot sensor network for all-around gait patterns monitoring, walking habits identification and Metatarsalgi prognosis. This work utilizes the interfacial coupling mechanism of intermolecular anchoring as a strategy to develop high-performance piezoelectric composites for wearable electronics.

36 MATERIALS SCIENCE↗

Annual report for DOE VTO

Carbon fiber (CF)/polymer composites are a transformative class of high-performance, lightweight material, where high aspect-ratio CFs reinforce a polymer matrix and exceed the strength of steel alloys at a fraction of the density. Despite the advantages of such a class of material, the broader implementation of CF composites in a range of automotive, aerospace, and energy applications is hindered by limitations of current manufacturing methods. These current techniques (e.g., hand lay-up, wet filament winding) are costly and impose severe limitations on fiber placement, orientation, and angle, and thus a composite’s ultimate properties. Today’s CF composites are expensive to manufacture, limited in form factor, and utilize costly and sub-optimal continuous filament CF. Advanced additive manufacturing (AM) processes, combined with computational design optimization and new approaches to resin development, offer alternative design and manufacturing paradigms that have the realistic potential to lift these constraints. Such integrated AM approaches could thus help to realize the full potential of CF composite materials. One relevant application of CF composite materials where manufacturing constraints limit the cost-benefit ratio is in the manufacture of high-performance composite pressure vessels for onboard compressed natural gas (CNG) storage. Current CNG storage vessels (Types 3–5) are made from load-bearing filament-wound carbon-fiber composite and are ~3.5 times as expensive as an all-metallic Type-1 vessel. This cost is invariably tied to the complex and labor-intensive nature of conventional filament winding processes and the large volumes of expensive high tensile-strength CF tow feedstock required in manufacture. Our proposed approach to CNG storage vessel manufacture is based on a combination of AM technologies for CF composite printing and design optimization tools that were pioneered at Lawrence Livermore National Laboratory (LLNL), with advances in resin/composite formulation enabled by chemical and nano-material modification. Through the successful development of this technology, LLNL seeks to demonstrate the capability for advanced CNG storage vessel manufacture at reduced cost with no reduction in performance versus the most advanced, extant Type-5 designs.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Additive manufacturing of carbon fiber-reinforced thermoset composites via in-situ thermal curing

Fiber-reinforced polymer composites are lightweight structural materials widely used in the transportation and energy industries. Current approaches for the manufacture of composites require expensive tooling and long, energy-intensive processing, resulting in a high cost of manufacturing, limited design complexity, and low fabrication rates. Here, we report rapid, scalable, and energy-efficient additive manufacturing of fiber-reinforced thermoset composites, while eliminating the need for tooling or molds. Use of a thermoresponsive thermoset resin as the matrix of composites and localized, remote heating of carbon fiber reinforcements via photothermal conversion enables rapid, in-situ curing of composites without further post-processing. Rapid curing and phase transformation of the matrix thermoset, from a liquid or viscous resin to a rigid polymer, immediately upon deposition by a robotic platform, allows for the high-fidelity, freeform manufacturing of discontinuous and continuous fiber-reinforced composites without using sacrificial support materials. This method is applicable to a variety of industries and will enable rapid and scalable manufacture of composite parts and tooling as well as on-demand repair of composite structures.

36 MATERIALS SCIENCE↗

Sizing comingled CF/PA 6 fibers with cellulose nanofibrils for enhanced performance properties

Compatibility between the reinforcing phase and the polymer matrix is critical to achieving the desired mechanical and thermal performance of composite materials. Several mechanisms can enhance this interfacial interaction, including surface treatments (e.g., oxidation, plasma, or irradiation), in-situ nanoparticle deposition, and fiber sizing. Here, in this study, cellulose nanofibrils (CNF) were employed as a sustainable sizing agent to modify the interface in commingled carbon fiber (CF)/polyamide 6 (PA 6) yarns, in which CF and PA6 filaments are intimately blended to enable simultaneous consolidation. A 0.25 wt% CNF aqueous suspension was applied under bath sonication to ensure uniform dispersion and minimize agglomeration. CNF-sized and unsized yarns were used to fabricate unidirectional composite plates via filament winding on a flat mandrel, followed by compression molding. Scanning electron microscopy confirmed CNF presence on both CF and PA6 filaments. CNF-sized composites exhibited increments in interlaminar shear strength (ILSS) by 50%, flexural strength by 11%, and tensile strength by 2.5% compared to unsized composites. Thermal analysis showed minimal changes in degradation temperature and crystallinity. These findings demonstrate that CNF sizing enhances interfacial bonding and mechanical performance, offering a scalable and environmentally friendly strategy for thermoplastic composite manufacturing along with yarn/tow handleability.

Cellulose nanofibrils (CNF)↗

Boron‐polymer composites engineered for compression molding, foaming, and additive manufacturing

Abstract Boron (specifically 10 B) is the element of choice to shield thermal neutrons due to its large (n, α) cross‐section; however, very few polymer composites containing high boron concentrations are available. This study aimed to determine the maximum possible amount of boron that could be introduced into a polymer matrix. Diverse manufacturing techniques, ranging from additive manufacturing to compression molding, were employed to fabricate inks and filaments for 3D printing, foams, and flexible pads. Composites using siloxanes, poly(lactic acid), and acrylonitrile butadiene styrene containing up to 80 wt% boron were sucessufully fabricated. The addition of known plasticizers (polyethylene glycol) and reinforcing agents (carbon nanofibers and fumed silica) helped to overcome fabrication problems such as clogging of the printing nozzle or crumbling of compression molded parts. In addition, the thermal‐mechanical properties of these novel boron composites were determined and shown to vary according to boron concentration, presence of additives, and fabrication techniques utilized.

36 MATERIALS SCIENCE↗

Tracking copper nanofiller evolution in polysiloxane during processing into SiOC ceramic

Polymer-derived ceramics (PDCs) remain at the forefront of research for a variety of applications including ultra-high-temperature ceramics, energy storage and functional coatings. Despite their wide use, questions remain about the complex structural transition from polymer to ceramic and how local structure influences the final microstructure and resulting properties. This is further complicated when nanofillers are introduced to tailor structural and functional properties, as nanoparticle surfaces can interact with the matrix and influence the resulting structure. The inclusion of crystalline nanofiller produces a mixed crystalline–amorphous composite, which poses characterization challenges. With this study, we aim to address these challenges with a local-scale structural study that probes changes in a polysiloxane matrix with incorporated copper nanofiller. Composites were processed at three unique temperatures to capture mixing, pyrolysis and initial crystallization stages for the pre-ceramic polymer. We observed the evolution of the nanofiller with electron microscopy and applied synchrotron X-ray diffraction with differential pair distribution function (d-PDF) analysis to monitor changes in the matrix's local structure and interactions with the nanofiller. The application of the d-PDF to PDC materials is novel and informs future studies to understand interfacial interactions between nanofiller and matrix throughout PDC processing.

Chemistry↗

In-Silico Design of Next Generation Cellulose-Derived Packaging Materials (CRADA Final Report)

Developing sustainable solutions for single-use packaging is an important objective to combat the environmental crisis of plastics pollution. Most embodiments of cellulose-based packaging materials, including CellophaneTM, are completely biodegradable in both terrestrial and marine environments. However, petroleum-derived alternatives offer some performance advantages for metrics such as moisture barriers and mechanical properties. This project leverages molecular dynamics simulation to investigate how molecular modifications to cellulose-based polymer assemblies impact their material properties. An important performance criterion for the modified materials was to retain biodegradability; thus, modifications by naturally occurring, biodegradable additives were the focus of this study. Specifically, we developed models with xylan and lignin of varying monomeric compositions into the cellulose matrix. The mechanical properties were investigated by performing stress-strain simulations, and the water barrier and hydrophobicity were investigated by simulating the water contact angle. Our findings indicate that the incorporation of xylan into the cellulose matrix tends to increase the mechanical properties with an optimal loading of ~27 wt%. We also predict that orienting the nanoscale directionality of the xylan chains such that they are perpendicular to the cellulose fibrils will dramatically increase mechanical strength. In contrast, the incorporation of lignin tends to weaken the composite at all loadings investigated. Simulations of water contact angle predicted that coating polymers on the surface of the cellulose assembly creates a more hydrophobic surface than incorporating them throughout the matrix. Of the coatings investigated, lignin resulted in the most hydrophobic surface, followed by pectin and keratin, which both imparted modest increases in hydrophobicity. Future experimental work done by Futamura will focus on designing material prototypes to capitalize on the predictions of performance enhancement obtained from molecular modeling. While substantial progress was made by the simulations performed in this project, there still exists a vast parameter space that we were unable to investigate, including branching, functional group decoration, and degree of polymerization of polymer additives. However, the methods developed in this initial investigation will facilitate more rapid evaluation of the impact of molecular characteristics on the performance of biopolymer composite materials and thereby accelerate future materials discovery efforts in this area.

36 MATERIALS SCIENCE↗

Chemical recycling of polymer composites induced by selective variable frequency microwave heating

Abstract The application of variable frequency microwave (VFM) heating to achieve rapid thermal depolymerization of polymer composites is reported for the first time. The thermal and chemical influence of composite additives on polymer decomposition has been studied for a set of chemically recyclable polymers, including polyphthalaldehyde, polypropylene carbonate, two polyhydroxyalkanoates, and nylon 6. Carbon‐based additives, specifically nanocarbon particles, were used as effective microwave absorbers to controllably degrade the surrounding polymer matrix into valuable, monomeric compounds. Depolymerization and byproduct confirmation were quantified by gel permeation chromatography and nuclear magnetic resonance spectroscopy. Synergistic effects can be leveraged from pre‐treating composite samples to further reduce the total microwave energy required to depolymerize composite samples. This study establishes the use of VFM heating for chemical recycling of polymer composites that can be leveraged toward a plastic circular economy.

Polymer Science↗

Effect of Remnant Carbon and Etching of Particles on Pyrolysis Bonded Silicon Carbide (PBSC)

Silicon carbide (SiC) formed through pyrolysis of preceramic polymers loaded with SiC particles has gained significant attention for applications such as coatings, composite matrix modifications, and most importantly additive manufacturing. This work presents combined synchrotron XRD, Raman spectroscopy, scanning electron microscopy, nano-indentation, and Vickers indentation of pyrolysis bonded SiC to shed light on the changes of composition and mechanical properties of these materials. Characterization was performed on samples that were heat treated ranging from the synthesis 850 °C up to 1500 °C. Pre-treatments of the powders prior to pellet synthesis, such as heat treatment and etching using a hydrofluoric acid (HF), were investigated. It is shown that the degradation of mechanical properties when exposed to higher temperatures is due to the burnout of amorphous carbon clusters remnant of the pyrolysis process of the preceramic polymer. Furthermore, prior HF etching and removal of the native oxide layer of the powders showed improved density and hardness values in the final pellets. The average Vickers hardness of the control samples were 4.59 GPa and later 3.74 GPa when exposed to 1500 °C, while the samples synthesized using powders that were etched with HF had an average hardness value of 9.37 GPa and later 6.86 GPa when exposed to 1500 °C.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Joining Light Metals with Polymer Composites Through Metal Overcasting

This work investigates a unique technique to join aluminum (Al) and magnesium (Mg) alloys to carbon fiber reinforced polymer (CFRP) composites without the use of adhesives or mechanical fasteners. The joints were made using an overcasting technique where the molten alloys were cast around the polymer composites using high pressure die casting method. Rapid cooling during casting allowed the composite to be embedded inside the cast metal without causing any gross damage to the former even though the molten metal temperature exceeded the melting point of the composite matrix by several 100’s of deg. C. The metal/composite interface was examined using optical microscopy and x-ray imaging and the joint strength was examined through tensile testing. Although evidence of polymer melting was evident in the x-ray images, the embedded section of the composite coupons retained their overall shape and integrity. Preliminary tension tests on Al/CFRP composites showed strength degradation of the CFRP and it failed near the metal/CFRP interface (outside the joint). Strength degradation in the CFRP suggests that the overcasting process needs further optimization to minimize thermal excursion in the CFRP. Nevertheless, the overcasting process shows great promise as a unique joining technique with application in fabricating light-weight structures for automotive and transportation industries.

overcasting, Casting, Mg Castings, Al Casting, Joi↗

Defects vibrations engineering for enhancing interfacial thermal transport in polymer composites

To push upper boundaries of thermal conductivity in polymer composites, understanding of thermal transport mechanisms is crucial. Despite extensive simulations, systematic experimental investigation on thermal transport in polymer composites is limited. To better understand thermal transport processes, we design polymer composites with perfect fillers (graphite) and defective fillers (graphite oxide), using polyvinyl alcohol (PVA) as a matrix model. Measured thermal conductivities of ~1.38 ± 0.22 W m -1 K -1 in PVA/defective filler composites is higher than those of ~0.86 ± 0.21 W m -1 K -1 in PVA/perfect filler composites, while measured thermal conductivities in defective fillers are lower than those of perfect fillers. We identify how thermal transport occurs across heterogeneous interfaces. Thermal transport measurements, neutron scattering, quantum mechanical modeling, and molecular dynamics simulations reveal that vibrational coupling between PVA and defective fillers at PVA/filler interfaces enhances thermal conductivity, suggesting that defects in polymer composites improve thermal transport by promoting this vibrational coupling.

42 ENGINEERING↗

Aqueous-Based Polyimine Functionalization of Cellulose Nanofibrils for Effective Drying and Polymer Composite Reinforcement

Here a simple strategy was developed to synthesize polyimine-coated cellulose nanofibrils (CNF) for effective CNF drying and composite reinforcement. The polyimine was synthesized in an aqueous medium using a selective hydrophilic and hydrophobic component that forces the polyimine to precipitate, which prevents the reverse imine reaction. The polyimine coating allowed the CNF to be easily oven-dried while maintaining a fibrillar morphology to provide mechanical reinforcement in poly(ethylene terephthalate glycol) (PETG) composites. In comparison, poor mechanical performance and a heterogeneous fracture surface were observed when the coated CNF were incorporated into poly(l-lactide) (PLA) composites. It is hypothesized that intermolecular aromatic–aromatic interactions are formed at the interface between fibers and the polymer matrix in the PETG system, while no such phenomena occur in the PLA system. Overall, this facile strategy to produce modified, easily dried CNF can be adapted to produce polyimine-coated CNF with unique functionalities that are useful in a range of applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

3D printed lignin/polymer composite with enhanced mechanical and anti-thermal-aging performance

Lignin is the most abundant natural aromatic polymer globally but is still underutilized as a renewable material, even with its versatile properties. One approach to using lignin is to incorporate it in polymer composites, but this application is often limited by the poor mechanical performance of the resultant composite due to the poor interfacial adhesion. Following the structure–property relationship, stronger interactions were designed to be enhanced by alternating the functional groups of lignin. Here, this study applied a demethylation method to hardwood lignin (Ori-Lig) to introduce more phenolic hydroxyl groups. Research studies with rheology behavior and molecular simulations demonstrated that an increased phenolic hydroxyl content could improve the adhesion between the modified lignin (OH-Lig) and the polymer matrix at the interface. The tensile performance of the samples from the fused depositional modeling (FDM) 3D printing technique was also improved due to the improved interfacial adhesion. Specifically, by adding 10 wt% of the modified lignin, the tensile strength of the 3D printed samples could reach 46.1 MPa (40.2 MPa of Polyamide 12, PA12), and Young’s Modulus could be improved to 1.73 GPa (1.48 GPa of PA12). OH-Lig also improved anti-aging performance so that the tensile strength of the OH-Lig composite after thermo-aging (100 h at 140 °C) remained ~48MPa. The enhanced mechanical performance with anti-aging properties indicated that the OH-Lig composite may replace PA12 to reduce the use of petrol-based materials. This work showed the method of purposefully designing and modifying lignin structures to fulfill the interaction requirements between lignin and polymer matrix. The as-prepared lignin could be used to prepare functional composites to achieve improved mechanical performance and targeted functions at the same time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Subsurface spectroscopy of heterogeneous materials using optical wavefront shaping

Plastic-bonded explosives and propellants consist of energetic molecular crystals embedded in a polymer matrix that also includes additives, such as taggants, plasticizers, grit, antioxidants, etc. Furthermore, this heterogeneous composition renders these materials optically opaque, limiting optical characterization techniques (e.g., Raman spectroscopy) to probing chemical reactions at the sur-face. However, many reactions of interest are believed to occur inside the material where current optical techniques can not probe. To address this challenge, we have developed a new optical technique that utilizes feedback assisted wavefront shaping (using spatial light modulators) to focus probe light inside a heterogeneous material, such that we can perform subsurface spectroscopy. Recently, we demonstrated this technique by monitoring subsurface photodegradation and thermal degradation of Eu-doped molecular crystals using both fluorescence and Raman spectroscopy. Based off these successes we are now looking into improvements to this technique to allow for greater time resolution, including replacing our spatial light modulators with fast digital mirror devices, using ns optical phase conjugation, and self-healing optical beams.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Particle‐Size‐Dependent Lithium‐Ion Transport in PEO/LLZO Composite Electrolytes

Lithium-metal batteries with solid electrolytes can deliver higher energy density and improved safety than conventional Li-ion batteries. Among solid electrolyte candidates, polymer/ceramic composite electrolytes are attractive because they combine polymer flexibility with the high ionic conductivity of ceramics. However, whether ceramic fillers synergistically reduce polarization losses in the polymer matrix remains unclear. A central unknown is the critical polymer/ceramic interfacial resistance (Rint,crit), below which adding ceramics lowers electrolyte overpotential. Here, we present the first macroscale model framework to quantify R int,crit for composite electrolytes based on polyethylene oxide (PEO) and Ta-doped Li 7 La 3 Zr 2 O 12 (LLZO). A 1D model for DC-polarization of tri-layer cells (PEO-LiTFSI/LLZO/PEO-LiTFSI) shows that LLZO surface functionalization reduces the PEO/LLZO interfacial resistance, consistent with electrochemical impedance measurements. Extending to a 2D composite model, we show notably that Rint,crit scales linearly with LLZO particle diameter and shifts toward experimentally accessible values (e.g., 28.8 Ωcm 2 ) as particle size increases. At fixed ceramic volume fraction, larger LLZO particles reduce the number of interfacial crossings, driving more current through the ceramic phase and lowering concentration polarization. In contrast, R int,crit is largely independent of ceramic volume fraction. These results demonstrate that ceramic filler-size engineering can enable synergistic, energy-efficient transport in polymer/ceramic composite electrolytes.

25 ENERGY STORAGE↗