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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

Organometallic Polymeric Conductors

For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for over 150 days in air at ambient temperature. The conductivity of the films dropped only half an order of magnitude in that time. Films aged under vacuum at ambient temperature diminished slightly in conductivity in the first day, but did not change thereafter. An experimental design approach will be applied to maximize the efficiency of the laboratory effort. The material properties (initial and long term) will also be monitored and assessed. The experimental results will add to the existing database for electrically conductive polymer materials. Attachments: 1) Synthesis Crystal Structure, and Polymerization of 1,2:5,6:9,10-Tribenzo-3,7,11,13-tetradehydro(14) annulene. 2) Reinvestigation of the Photocyclization of 1,4-Phenylene Bis(phenylmaleic anhydride): Preparation and Structure of (5)Helicene 5,6:9,10-Dianhydride. 3) Preparation and Structure Charecterization of a Platinum Catecholate Complex Containing Two 3-Ethynyltheophone Groups. and 4) Rigid-Rod Polymers Based on Noncoplanar 4,4'-Biphenyldiamines: A Review of Polymer Properties vs Configuration of Diamines.

Youngs, Wiley J.↗

Ceramic matrix and resin matrix composites: A comparison

The underlying theory of continuous fiber reinforcement of ceramic matrix and resin matrix composites, their fabrication, microstructure, physical and mechanical properties are contrasted. The growing use of organometallic polymers as precursors to ceramic matrices is discussed as a means of providing low temperature processing capability without the fiber degradation encountered with more conventional ceramic processing techniques. Examples of ceramic matrix composites derived from particulate-filled, high char yield polymers and silsesquioxane precursors are provided.

Hurwitz, Frances I.↗

Ceramic matrix and resin matrix composites - A comparison

The underlying theory of continuous fiber reinforcement of ceramic matrix and resin matrix composites, their fabrication, microstructure, physical and mechanical properties are contrasted. The growing use of organometallic polymers as precursors to ceramic matrices is discussed as a means of providing low temperature processing capability without the fiber degradation encountered with more conventional ceramic processing techniques. Examples of ceramic matrix composites derived from particulate-filled, high char yield polymers and silsesquioxane precursors are provided.

Hurwitz, Frances I.↗

Robust, High-Performing Maize–Perovskite-Based Solar Cells with Improved Stability

Herein, we focus on improving the long-term chemical and thermomechan-ical stability of perovskite solar cells (PSCs), two major challenges currently limiting their commercial deployment. Our strategy incorporates a long-chain starch polymer into the perovskite precursor. The starch polymer confers multiple beneficial effects by forming hydrogen bonds with the methylammonium iodide precursor, templating perovskite growth that results in a compact and homogeneous film deposited in a simple one-step coating (antisolvent-free). The inclusion of starch in the methylammonium lead iodide films strongly improves their thermomechanical and environmental stability while maintaining a high photovoltaic performance. The fracture energy (G c ) of the film is increased to above 5 J/m 2 by creating a nanocomposite that provides intrinsic reinforcement at grain boundaries. Additionally, improved optoelectronic properties achieved with the starch polymer enable good photostability of the active layer and enhanced resistance to thermal cycling.

14 SOLAR ENERGY↗

3D-printed electrode, gas diffusion electrode (GDE) and gas diffusion layer (GDL) for fuel cell applications

An electrocatalytically active ink composition is used with an additive manufacturing process, such as 3D printing, to produce electrodes having consistent, adaptable, and high surface area structures. The electrocatalytically active ink composition includes a mixed powdered precursor and a polymer matrix. The mixed powdered precursor includes a carbon source, a dopant source, and/or a metal-containing catalyst. The material and electrochemical properties of the ink composition may facilitate 3D printing of electrochemically active electrodes for energy conversion and storage devices, and may allow fine-tuning of macro- and microstructures to develop electrodes having improved activity and efficiency.

Lee, Kwan-Soo↗

High optical transparency polymer aerogels using low refractive index monomers

A method of producing a polymer aerogel includes dissolving precursors into a solvent, wherein the precursors include monomers, crosslinkers, a controlling agent and an initiator to form a precursor solution, wherein at least one of the monomers or at least one of the crosslinkers has a refractive index of 1.5 or lower, polymerizing the precursor solution to form a gel polymer, and removing the solvent from the gel polymer to produce the polymer aerogel. A method of producing a polymer aerogel include dissolving precursors into a solvent, wherein the precursors include monomers, crosslinkers, a controlling agent and an initiator to form a precursor solution, polymerizing the precursor solution to form a gel polymer, removing the solvent from the gel polymer to produce the polymer aerogel, and reducing a refractive index of one of either the gel polymer or the polymer aerogel.

Bulger, Eli↗

Materials for the biorefinery: high bio-content, shape memory Kraft lignin-derived non-isocyanate polyurethane foams using a non-toxic protocol

Polyurethanes are among the top six polymers produced in the world and are widely used in the automotive, furniture, construction and appliance industry for their light weight, impact resistance, and insulating properties. However, the use of hazardous diisocyanates used in polyurethane formulations has led many to search for more sustainable alternatives. The lignin component of biomass has been targeted to replace the often toxic and petroleum-derived precursors to polymer synthesis in support of the biorefinery concept where natural materials are used as the feedstock for commodity plastics. The use of lignin is often hampered due to its low reactivity, heterogeneity and the necessity of employing extensive purification and/or functionalization measures to ensure materials are of comparable quality. In this report, a unique method is presented for the synthesis and processing of a non-toxic, non-isocyanate polyurethane foam utilizing unmodified Kraft lignin and a biobased curing agent. Here, raw Kraft lignin is functionalized with green organic carbonates and a non-toxic approach is taken to solubilize the precursors with a curing agent from renewable fatty acids enabling rapid gel-times. For the first time, a NIPU foam from lignin is synthesized while the structure–property relationship of different reaction mixtures is studied demonstrating shape memory capacity and 100% biobased carbon content.

36 MATERIALS SCIENCE↗

A molecular design approach towards elastic and multifunctional polymer electronics

Next-generation wearable electronics require enhanced mechanical robustness and device complexity. Besides previously reported softness and stretchability, desired merits for practical use include elasticity, solvent resistance, facile patternability and high charge carrier mobility. Here, we show a molecular design concept that simultaneously achieves all these targeted properties in both polymeric semiconductors and dielectrics, without compromising electrical performance. This is enabled by covalently-embedded in-situ rubber matrix (iRUM) formation through good mixing of iRUM precursors with polymer electronic materials, and finely-controlled composite film morphology built on azide crosslinking chemistry which leverages different reactivities with C–H and C=C bonds. The high covalent crosslinking density results in both superior elasticity and solvent resistance. When applied in stretchable transistors, the iRUM-semiconductor film retained its mobility after stretching to 100% strain, and exhibited record-high mobility retention of 1 cm 2 V -1 s -1 after 1000 stretching-releasing cycles at 50% strain. The cycling life was stably extended to 5000 cycles, five times longer than all reported semiconductors. Furthermore, we fabricated elastic transistors via consecutively photo-patterning of the dielectric and semiconducting layers, demonstrating the potential of solution-processed multilayer device manufacturing. The iRUM represents a molecule-level design approach towards robust skin-inspired electronics.

42 ENGINEERING↗

Hydrogels for isotopic neutron emitters and antineutrino detection and related detection systems and methods

Scintillation compositions comprising a gadolinium compound and a scintillation compound in a polymer matrix precursor. The scintillation compound comprises strontium diiodide, fac-tris(2-phenylpyridine)iridium (Ir(ppy)3), a quinine compound, or combinations thereof, or 2-(4-biphenylyl)-5 phenyl-1,3,4-oxadiazole (PBD), 2-(4-tert-butylphenyl)-5-(4-phenylphenyl)-1,3,4-oxadiazole (b-PBD), 2,5-diphenyl oxazole (PPO), 1,4-bis(5-phenyloxazol-2-yl) benzene (POPOP), or combinations thereof. Hydrogels comprising the gadolinium compound and scintillation compound in a polymer matrix are also disclosed, as are related systems and methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

AOI [1]: Passive Wireless Sensor Systems Fabricated by Direct-Writing for Temperature and Health Monitoring of Energy Systems in Harsh-Environments (Final Report)

Researchers at West Virginia University (WVU) propose to demonstrate a wireless, high-temperature sensor system for monitoring the temperature and health of energy-system components. The active sensor and electronics for wireless communication will be composed entirely of an electroceramic materials (conductive ceramics) which are capable of withstanding the harsh-environments required for fossil energy-based technologies. This work will focus primarily on the fabrication and testing of temperature (thermocouples and thermistors) and health (strain/stress and crack propagation sensors) that function at extreme temperatures (up to 700-1700ºC). The electronics will accompany the high-temperature sensor, which will include a passive wireless communication circuit that allows the transmission of the data based on the LCR resonance principle to a near-by reader antenna. This passive transmission of data will reduce the need for interconnect wires near the active, and possibly rotating, energy-system component. The research will include process development to permit the 2D/3D direct-writing of the entire sensor and communication circuit onto the energy-system component. The direct-writing will be facilitated by using silicon-based polymer-derived precursors to form the high-temperature, stable electroceramic compositions. In addition, methods for direct-writing the circuit onto a fugitive carrier substrate will be completed, which will permit a “peel-and-stick”-like transfer of the sensor circuit to the energy-system component. This feature will allow the economical and precise placement of the sensor circuit onto components of various shapes and locations, without altering the geometry and active features of the manufactured component, or the removal (or decommissioning) of the component for installation. The proposed work will be directed at the following areas: 1) Investigation of phase formation, sintering/grain growth, and electrical properties of polymer-derived electroceramic composites; 2) Definition of processes to direct-write through ink-jet and robo-casting the polymer-derived electroceramic composites onto oxide and polymer surfaces; 3) Development of methods to form monolithic "peel-and-stick" preforms that will efficiently transfer the sensor circuit to ceramic surfaces after thermal treatment; 4) Design of passive wireless LCR circuits and receiver (reader) antennas for communication and testing at high temperatures; 5) Investigation of the passive wireless sensor system developed (and method of transferring sensor system) for temperature and stress/strain measurements on a SOFC repeat unit and a singular gas turbine blade prototype as example applications.

01 COAL, LIGNITE, AND PEAT↗

Accessibility and Mechanical Stability of Nanoporous Zinc Oxide and Aluminum Oxide Coatings Synthesized via Infiltration of Polymer Templates

The conformal nanoporous inorganic coatings with accessible pores that are stable under applied thermal and mechanical stresses represent an important class of materials used in the design of sensors, optical coatings, and biomedical systems. Here, we synthesize porous AlO x and ZnO coatings by the sequential infiltration synthesis (SIS) of two types of polymers that enable the design of porous conformal coatings—polymers of intrinsic microporosity (PIM) and block co-polymer (BCP) templates. Using quartz crystal microbalance (QCM), we show that alumina precursors infiltrate both polymer templates four times more efficiently than zinc oxide precursors. Using the quartz crystal microbalance (QCM) technique, we provide a comprehensive study on the room temperature accessibility to water and ethanol of pores in block copolymers (BCPs) and porous polymer templates using polystyrene-block-poly-4-vinyl pyridine (PS75-b-P4VP25) and polymers of intrinsic microporosity (PIM-1), polymer templates modified by swelling, and porous inorganic coatings such as AlO x and ZnO synthesized by SIS using such templates. Importantly, we demonstrate that no structural damage occurs in inorganic nanoporous AlO x and ZnO coatings synthesized via infiltration of the polymer templates during the water freezing/melting cycling tests, suggesting excellent mechanical stability of the coatings, even though the hardness of the inorganic nanoporous coating is affected by the polymer and precursor selections. We show that the hardness of the coatings is further improved by their annealing at 900 °C for 1 h, though for all the cases except ZnO obtained using the BCP template, this annealing has a negligible effect on the porosity of the material, as is confirmed by the consistency in the optical characteristics. These findings unravel new potential for the materials being used across various environment and temperature conditions.

36 MATERIALS SCIENCE↗

Phenolic Resin Derived Hard Carbon Anode for Sodium-Ion Batteries: A Review

Sodium-ion batteries are complementary to lithium-ion batteries for grid-scale energy storage applications due to lower cost, safety, and potential for sustainable supply chains. The past decade has witnessed enormous research efforts in developing hard carbon anode materials for sodium-ion batteries. Phenolic resins have received significant attention as hard carbon precursors due to their high carbon yield, highly cross-linked structure, low cost, mature technology, and excellent electrochemical performance of corresponding hard carbon anode. This Review exclusively highlights the state-of-the-art preparation of hard carbon from phenolic resins, and the electrochemical performance in sodium-ion batteries. Cross-linked resins are prepared from three phenolic monomers (phenol, resorcinol, and phloroglucinol) to produce hard carbon. The effects of carbonization temperature on the microstructure, and electrochemical properties of hard carbon have been summarized here. Hard carbon formation, and sodium storage mechanisms have been briefly outlined. Finally, this Review provides an industrial perspective on hard carbon production at scale.

aromatic compounds↗

Photocatalytic Hydrogen Evolution Using Mesoporous Honeycomb Iron Titanate

Mesoporous honeycomb iron titanate using a sol-gel, evaporation-induced self-assembly method is synthesized. A triblock copolymer, F127, serves as a structure-directing agents, with iron chloride and titanium (IV) isopropoxide as inorganic precursors. The strong intermolecular force of attraction among urea, metal precursors, and polymer led to the formation of the mesoporous honeycomb structure. The study of physicochemical properties using different techniques reveals the formation of microstructures with a remarkable degree of porosity. The amorphous iron titanate outperforms the photochemical generation of H 2 due to its disorderly structural arrangement and incomplete crystal formation. The randomness on the structure provides more area for catalytic reaction by providing more contact with the reactant and superior light absorption capability. The high amount of hydrogen gas, 40.66 mmolg -1 h -1 , is observed in the investigation over 3 h of activity for the iron titanate honeycomb sample. This yield is a more significant amount compared to the obtained for the commercially available TiO 2 (23.78 mmolg -1 h -1 ). The iron titanate materials synthesized with low-cost materials and methods are very effective and have the potential for hydrogen generation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Probing the Mechanism of Cadmium Sulfide Cluster Nucleation and Growth via Sequential Infiltration Synthesis

Few-atom metal chalcogenide clusters may be realized through the sequential infiltration of metal–organic precursors in polymer films. However, the underlying nucleation and growth mechanisms that allow for cluster synthesis with near atomic-scale precision are not fully resolved. The kinetics of the sequential infiltration synthesis (SIS) method that control the nucleation and growth mechanisms of primarily Cd 4 S 4 -core clusters within a poly­(4-vinylpyridine) (P4VP) matrix are probed with in situ UV–visible absorbance spectroscopy. Density functional theory (DFT) calculations that allow simulation of the optical properties of cluster fragments further reveal the thermodynamics that guide cluster growth within the P4VP matrix. Here, we conclude that a reactive capture mechanism for cluster nucleation and growth is dominant, although transient dimethyl cadmium adduction to the polymer backbone may contribute to cluster nucleation under shorter metal–organic purge process conditions. Grazing incidence X-ray diffraction (GI-XRD) and X-ray absorption spectroscopy (XAS) analyses further corroborate the cluster size and atom connectivity throughout the stepwise synthesis.

Jayaweera, Nuwanthaka P. [Argonne National Laborat↗