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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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78 records · Page 5

Enhanced Electrocatalytic and Cathode‐Electrolyte Interfacial Properties With a Pr‐Based Simple Perovskite/Ruddlesden‐Popper Nanocomposite Cathode in Protonic Ceramic Fuel Cells

The sluggish kinetics and poor stability of the oxygen reduction reaction (ORR) remain the primary bottleneck for achieving high performance in protonic ceramic fuel cells (PCFCs) at intermediate temperatures (400–650°C). In this work, a Pr-based nanocomposite cathode comprised of simple perovskite phase (PrNi 0.7 Co 0.3 O 3-δ ) and Ruddlesden-Popper phase (Co-doped Pr 4 Ni 3 O 10+δ ) is developed. Although PrNi 0.7 Co 0.3 O 3-δ solely stands as a good cathode with facile proton transfer, combining the superior catalytic activity against oxygen on the Ruddlesden-Popper phase boosts the ORR performance further. The designed nanocomposite cathode outperforms the simple perovskite cathode, attributed to enhanced oxygen absorption and surface diffusion with the Ruddlesden-Popper phase. A precursor-based cathode deposition technique is also developed to achieve cathode grain sizes of ∼100 nm. A single cell with the nanocomposite cathode delivers a peak power density of 1.38 W cm −2 at 650°C, among the highest in reported PCFCs with Pr-based cathodes, with a small degradation rate of 0.145 mV h −1 during 250 h stability test. Further investigation of cathode-electrolyte interface revealed interfacial PrO 2 phase formation, promoted by abundant Pr 6 O 11 in the nanocomposite precursor powder, thereby improving both ohmic resistance and stability. These findings highlight the effectiveness of the nanocomposite cathode and underscore its advantages on interfacial properties.

08 - HYDROGEN↗

Transparent silica aerogel slabs synthesized from nanoparticle colloidal suspensions at near ambient conditions on omniphobic liquid substrates

This paper presents a novel sol-gel method to synthesize large and thick silica aerogel monoliths at near ambient conditions using a commercial aqueous solution of colloidal silica nanoparticles as building blocks. To achieve slabs with high visible transmittance and low thermal conductivity, the method combines the strategies of (i) synthesizing gels on an omniphobic perfluorocarbon liquid substrate, (ii) aging at temperatures above room temperature, and (iii) performing solvent exchange with a low-surface-tension organic solvent prior to ambient drying. The omniphobic liquid substrates were used to prevent cracking and ensure an optically-smooth surface, while nanoparticle building blocks were small (<10 nm) to limit volumetric light scattering. Gels were aged at temperatures between 25 and 80 °C for up to 21 days to make them stronger and stiffer and to reduce shrinkage and cracking during ambient drying. Ambient drying was achieved by first exchanging water in the gel pores for octane, followed by drying in an octane-rich atmosphere to decrease capillary forces. The synthesized nanoparticle-based silica aerogel monoliths had thicknesses up to 5 mm, diameters up to 10 cm, porosities exceeding 80%, and thermal conductivities as low as 0.08 W m –1 K –1 . Notably, the slabs featured visible transmittance exceeding 75% even for slabs as thick as 5 mm. The as-synthesized aerogel monoliths were exposed to TMCS vapor to induce hydrophobic properties resulting in a water contact angle of 140° that prevented water infiltration into the pores and protected the aerogels from water damage. This simple synthesis route conducted at near ambient conditions produces hydrophobic aerogel monoliths with promising optically transparent and thermally insulating properties that can be adhered to glass panes for window insulation and solar-thermal energy conversion applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anomalous Anisotropic Nanoparticle Aggregation in Cu 2 (OH) 3 Br Gels

Aerogels are of interest for their ability to uniformly incorporate nanoscale features into macroscopic assemblies, which enabled applications that require low density, high surface area, and/or bicontinuous networks. The structure of the nanoporous network is intrinsically linked to the macroscopic properties of aerogels. Hence, control of this structure is of paramount importance. Small-angle X-ray scattering (SAXS) is used here to monitor nanoparticle aggregation in situ in Cu 2 (OH) 3 Br aerogels formed via epoxide-assisted gelation. Anomalous anisotropic aggregation is observed in the absence of templating agents and is attributed to the molecular structure of the inorganic nanoparticles themselves. This is a fundamental departure from the models currently used to describe traditional inorganic sol–gel chemistry where nanoparticles are believed to undergo isotropic diffusion- and/or kinetically limited aggregation. Time-resolved SAXS indicates that Cu 2 (OH) 3 Br nanoparticles nucleate rapidly from solution to form unbranched chain-like aggregates rather than branched mass-fractal aggregates. Sizes of primary particles (~1.5 nm) and the chain-like structure of their aggregates are independent of particle concentration (gel density), while rates of particle aggregation, gelation time, and aggregate size are strongly dependent upon particle concentration, which implies that the chemistry of particle formation and the physics of particle aggregation are independent processes. Because the conditions necessary for creating anisotropic structures are not unique to Cu 2 (OH) 3 Br, these results could provide insight into the structure and gelation mechanisms of other inorganic aerogels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low temperature synthesis of CaO-SiO2 glasses having stable liquid-liquid immiscibility by sol-gel process

Calcium silicate glass compositions lying within the liquid-liquid immiscibility dome of the phase diagram, which could not have been prepared by the conventional melting method, were synthesized by the sol-gel process. Hydrolysis and polycondensation of tetraethyl orthosilicate (TEOS) solutions containing up to 20 mol percent calcium nitrate resulted in the formation of clear and transparent gels. The gel formation time decreased with increase in water:TEOS mole ratio, calcium content, and the reaction temperature. Smaller values of gel times in the presence of calcium nitrate are probably caused by lowering of the ionic charge on the sol particles by the salt present. The gelation activation energy, E(sub gel), was evaluated from temperature dependence of the gel time. Presence of Ca(2+) ions or the water:TEOS mole ratio did not have an appreciable effect on the value of E(sub gel). Presence of glycerol in the solution helped in the formation of crack-free monolithic gel specimens. Chemical and structural changes occurring in the gels, as a function of the heat treatments, have been monitored using DTA, TGA, IR-spectroscopy, x ray diffraction, surface area and pore size distribution measurements.

Bansal, Narottam P.↗

Low temperature synthesis of CaO-SiO2 glasses having stable liquid-liquid immiscibility by the sol-gel process

Calcium silicate glass compositions lying within the liquid-liquid immiscibility dome of the phase diagram, which could not have been prepared by the conventional melting method, were synthesized by the sol-gel process. Hydrolysis and polycondensation of tetraethyl orthosilicate (TEOS) solutions containing up to 20 mol percent calcium nitrate resulted in the formation of clear and transparent gels. The gel formation time decreased with increase in water: TEOS mole ratio, calcium content, and the reaction temperature. Smaller values of gel times in the presence of calcium nitrate are probably caused by lowering of the ionic charge on the sol particles by the salt present. The gelation activation energy, E(sub gel), was evaluated from temperature dependence of the gel time. Presence of Ca(2+) ions or the water:TEOS mole ratio did not have an appreciable effect on the value of E(sub gel). Presence of glycerol in the solution helped in the formation of crack-free monolithic gel specimens. Chemical and structural changes occurring in the gels, as a function of the heat treatments, have been monitored using DTA, TGA, IR-spectroscopy, X-ray diffraction, surface area and pore size distribution measurements.

Bansal, N. P.↗

Aerogel Projects Ongoing in MSFC's Engineering Directorate

When we speak of an aerogel material, we are referring more to process and structure am to a specific substance. Aerogel, considered the lightest solid material, has been made from silica for seventy years. Resorcinol-formaldehyde, organic aerogels have been developed more recently. However, aerogel can be made from almost any type of substance, even lead. Because an aerogel is mostly air (about 99 %), the solid substance used will affect the weight very little. The term "aerogel" connotes the sol-gel process used to manufacture the material. The aerogel begins as a liquid "sol," becomes a solid "alcogel," and is then dried to become an "aerogel." The final product has a unique structure, useful for exploitation. It is an "open pore" system with nano-sized particles and pores, has very high surface area, and is highly interconnected. Besides low weight, aerogels have ultimate (lowest) values in other properties: thermal conductivity, refractive index, sound speed, and dielectric constant. Aerogels were first prepared in 1931 by Steven Kistler, who used a supercritical drying step to replace the liquid in a gel with air, preserving the structure (1). Kistler's procedure involved a water-to-alcohol exchange step; in the 1970's, this step was eliminated when a French investigator introduced the use of tetramethylorthosilicate. Still, alcohol drying involved dangerously high temperatures and pressures. In the 1980's, the Microstructured Materials Group at Berkeley Laboratory found that the alcohol in the gel could be replaced with liquid carbon dioxide before supercritical drying, which greatly improved safety (2). 'Me most recent major contribution has been that of Deshpande, Smith and Brinker in New Mexico, who are working to eliminate the supercritical drying step (3). When aerogels were first being developed, they were evaporatively dried. However, the wet gel, when dried, underwent severe shrinkage and cracking; this product was termed "xerogel." When the autoclave drying step was introduced, the final product was without cracks and showed only minimal shrinkage; this product was termed "aerogel." In the 1990's, Deshpande, Smith and Brinker developed an evaporative drying procedure in which the wet gel is chemically "capped" so that the material, which undergoes shrinkage, springs back to its original size when evaporatively dried. This new type of xerogel, while uncracked and almost the same size as the wet gel, differs from the autoclave-dried product in that it is less porous (approximately 70%, as compared to 99% for aerogels).

Shular, David A.↗