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NASA NTRS2024

Post-Synthetic Modification of Yttria-Stabilized Zirconia Aerogels with Silica Coatings for Enhanced Thermal Stability

Maintaining high surface area and porosity at high temperatures is important when considering aerogels for use in thermal management systems. The mesoporous structure of aerogels results in extremely low thermal conductivity, making them lightweight, high performance insulating materials. Maintaining these properties requires innovative routes to suppress sintering and pore collapse as use temperatures rise. The current work aims to improve the pore structure stability of yttria-stabilized zirconia aerogels by the addition of a SiO 2 coating. The functionalization of surface hydroxyl groups by the addition of SiO 2 is hypothesized to mitigate condensation reactions, which are a driving force for shrinkage and pore structure collapse. Zirconia aerogels with 0, 10 and 30 mol% yttria (YO 1.5 ) additions were coated in a tetraethyl orthosilicate (TEOS) solution and exposed to temperatures up to 1200°C. Crystal structure, pore structure, and aerogel morphology were investigated to understand changes in aerogel thermal stability. The SiO 2 coating exhibited a greater influence on pore stability over yttria concentration, with specific surface area of the coated aerogels being twice that of the uncoated aerogels up to 1000°C. However, the presence of the SiO 2 coating promoted rapid sintering and densification at 1200°C, establishing an upper use temperature for SiO 2 and a need to develop other coating chemistries.

aerogel↗

NASA NTRS2023

Optimizing Surfactant Templating of Yttria-Stabilized Zirconia Aerogels for High-Temperature Applications: Effect of Anionic and Nonionic Surfactant

Aerogels, mesoporous materials with extreme material properties including high specific surface area, low density, and low thermal conductivity, can be useful for applications including catalysis, sorption media, and drug delivery. The low thermal conductivity and high surface area of aerogels makes them advantageous as thermal management systems, specifically for aerospace or aeronautics applications. However, the pore collapse and subsequent surface area decrease of aerogels following exposure to high temperatures must be mitigated to allow aerogels to be effectively used in thermal management applications. This work investigates the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic surfactant Pluronic® P-123 as surfactant templates in yttria-stabilized zirconia (YSZ) aerogels. By utilizing surfactant templates, known to influence pore structure, it is anticipated that sintering and densification of the aerogels following high-temperature exposure will be mitigated. It was determined that the addition of SDS and P-123 increased the surface area and pore volume of as-dried aerogels and suppressed crystallite growth at high temperatures. However, the impact of surfactant templates on the surface area and pore volume of heat-treated aerogels was negligible, potentially due to low concentrations of surfactant and the removal of the surfactant following high-temperature exposure.

Yttria-stabilized zirconia aerogels↗

NASA NTRS2005

Numerical Modelling of the Deep Impact Mission Experiment

NASA s Deep Impact Mission (launched January 2005) will provide, for the first time ever, insights into the interior of a comet (Tempel 1) by shooting a approx.370 kg projectile onto the surface of a comets nucleus. Although it is usually assumed that comets consist of a very porous mixture of water ice and rock, little is known about the internal structure and in particular the constitutive material properties of a comet. It is therefore difficult to predict the dimensions of the excavated crater. Estimates of the crater size are based on laboratory experiments of impacts into various target compositions of different densities and porosities using appropriate scaling laws; they range between 10 s of meters up to ~250 m in diameter [1]. The size of the crater depends mainly on the physical process(es) that govern formation: Smaller sizes are expected if (1) strength, rather than gravity, limits crater growth; and, perhaps even more crucially, if (2) internal energy losses by pore-space collapse reduce the coupling efficiency (compaction craters). To investigate the effect of pore space collapse and strength of the target we conducted a suite of numerical experiments and implemented a novel approach for modeling porosity and the compaction of pores in hydrocode calculations.

Wuennemann, K.↗

NASA NTRS1980

Experimental shock metamorphism of lunar soil

Shock experiments in the pressure range 15-73 GPa were performed on lunar soil 15101 in order to investigate the effect of a single impact event on the formation of soil breccias and agglutinates. The study has demonstrated that the propagation of a shock wave emanating from a single impact in porous particulate samples causes collision and shear of grains, collapse of pore spaces, and compaction which is sufficient to indurate soil at low pressures (15-18 GPa) without significant melting (less than 5%). These low pressures create soil breccias or weakly shocked soil fragments from loose regolith. At pressures above 65 GPa, shock melting produces a pumiceous whole-soil glass which is equivalent to agglutinate glass, glass fragments, or ropy glasses depending on the abundance of lithic fragments and relict grains.

Schaal, R. B.↗

NASA NTRSDate not supplied

The Influence of Yttria Content on the Thermal Stability of Yttria-Stabilized Zirconia Aerogels

Aerogels demonstrate extraordinarily low thermal conductivity and low density, presenting a promising form of lightweight insulation for aerospace applications. The primary challenge is stabilization of the highly porous structure at temperatures to 1200 °C. Upon collapse of the pore structure, the favorable thermal properties and low density are diminished. Yttria-stabilized zirconia (YSZ) aerogels are synthesized to investigate the effect of composition on morphology, phase behavior, and thermal stability (specific surface area, pore size distribution). This work demonstrates the improvement in thermal stability of zirconia aerogels with increased yttria content. To develop insight on the influence of structure on thermal stability, the effects of water content and solids loading are studied and in elucidation of the mechanism by which yttria stabilizes the pore structure. With an improved understanding of aerogel structure and performance, metal oxide aerogels can be developed to withstand the extreme environments of space exploration.

Nathaniel Olson↗

NASA NTRSDate not supplied

Enhanced Thermal Stability of High Yttria Concentration YSZ Aerogels

Aerogels demonstrate extraordinarily low thermal conductivity and low density, presenting a promising form of lightweight insulation for aerospace applications. The primary challenge is stabilization of the highly porous structure at temperatures to 1200 °C. Upon collapse of the pore structure, the favorable thermal properties and low density are diminished. Yttria-stabilized zirconia (YSZ) aerogels are synthesized to investigate the effect of composition on morphology, phase behavior, and thermal stability (specific surface area, pore size distribution). This work demonstrates the improvement in thermal stability of zirconia aerogels with increased yttria content. Furthermore, changes in structure and surface chemistry of YSZ aerogels are studied in both oxidizing and inert atmospheres. With an improved understanding of aerogel structure and performance, metal oxide aerogels can be developed to withstand the extreme environments of space exploration.

Nathaniel Olson↗

NASA NTRSDate not supplied

Optimization of Aerogels for High Temperature Applications

Aerogels can be used in spaceflight applications as thermal insulators due to their low density, low thermal conductivity, and tortuous path for solid conduction. However, the aerogel formulation must be optimized to increase the thermal stability of the aerogels as drastic densification and decrease in surface area is often exhibited after high-temperature exposure. Current research investigates yttria-stabilized zirconia (YSZ) aerogels, which have low thermal conductivity and are expected to be used between 600°C and 1000°C. We anticipate that new sol-gel chemistries and processing will yield YSZ aerogels that display retained mesoporous structure, increased surface area, and minimized shrinkage upon exposure to higher temperatures in the projected use range. This work investigates the cationic surfactant, cetrimonium bromide (CTAB), as a templating agent to prevent the collapse of the aerogel pore structure upon gelation and drying. It was determined that adding one-half times the critical micelle concentration (CMC) of CTAB increased the surface area and pore volume of the aerogels, as compared to aerogels without CTAB or with twice the CMC of CTAB, following high-temperature exposure. By optimizing CTAB, the thermal stability of YSZ aerogels can be enhanced to make these materials more efficient when used as thermal management systems.

Rebecca C Walker↗

NASA NTRSDate not supplied

Optimizing Surfactant Templating of Yttria-stabilized Zirconia Aerogels for High-temperature Applications: Effect of Anionic & Nonionic Surfactant

Aerogels are useful thermal insulators due to low density, low thermal conductivity, and a tortuous path for solid conduction. However, the formulation must be optimized to increase thermal stability as drastic densification and surface area decrease is often exhibited after high-temperature exposure. Current research investigates yttria-stabilized zirconia (YSZ) aerogels for expected use between 600°C and 1000°C. We anticipate that new sol-gel chemistries will yield YSZ aerogels with retained mesoporous structure, increased surface area, and minimized shrinkage upon high-temperature exposure. This work investigates the anionic surfactant, sodium dodecyl sulfate (SDS), and the nonionic surfactant, Pluronic® P-123, as templating agents to prevent the collapse of the aerogel pore structure upon gelation and drying. To determine the effect of surfactant, characterization techniques such as nitrogen physisorption, x-ray diffraction, and scanning electron microscopy are used. By optimizing surfactant concentration, the thermal stability of YSZ aerogels can be enhanced, producing more efficient thermal insulators.

Rebecca C. Walker↗

NASA NTRS1992

Deformational mass transport and invasive processes in soil evolution

Channels left in soil by decayed roots and burrowing animals allow organic and inorganic precipitates and detritus to move through soil from above, to depths at which the minuteness of pores restricts further passage. Consecutive translocation-and-root-growth phases stir the soil, constituting an invasive, dilatational process which generates cumulative strains. Below the depths thus affected, mineral dissolution by descending organic acids leads to internal collapse; this softened/condensed precursor horizon is then transformed into soil via biological activity that mixes and expands the evolving residuum through root and micropore-network invasion.

Brimhall, George H.↗

NASA NTRS2021

Optimizing Surfactant Templating of Yttria-Stabilized Zirconia Aerogels for High-Temperature Applications: Effect of Cationic Surfactant

Aerogels can be used in spaceflight applications as thermal insulators due to their low density, low thermal conductivity, and tortuous path for solid conduction. However, the aerogel formulation must be optimized to increase the thermal stability of the aerogels, as a drastic densification and decrease in surface area often is exhibited after high-temperature exposure. This work considers yttria-stabilized zirconia (YSZ) aerogels, whichhave low thermal conductivity and are expected to be used for temperatures between 600°C and 1000°C. It is anticipated that new sol-gel chemistries will yield YSZ aerogels that exhibit retained mesoporous structure, increased surface area, and minimized shrinkage upon exposure to higher temperatures in the expected use range. This work investigates the addition of surfactant to 20 mol% YSZ aerogels. The cationic surfactant, cetrimonium bromide (CTAB), was used as the templating agent, preventing the collapse of the mesoporous structure upon gelation and drying. It was determined that adding one-half times the critical micelle concentration of CTAB increased the surface area of the aerogels by 72% and 41% and increased the pore volume following exposure to 600°C and1000°C, respectively. This level of CTAB had the greatest increase in surface area and pore volume as compared to aerogels without CTAB or with twice the critical micelle concentration of CTAB. By optimizing the concentration of CTAB, the thermal stability ofYSZ aerogels can be enhanced to make these materials more efficient when used as thermal management systems.

Yttria-stabilized zirconia aerogel↗

NASA NTRS1989

Evidence for the abundance of water on Mars now and in the past

This paper discusses evidence for the abundance of water on Mars early in its history, based on the analysis of the Viking 1 and 2 images and the Martian-atmosphere water measurements. It is argued that integrated networks of small valleys in the ancient cratered terrain of Mars may indicate that the planet once possessed a warmer climate. It is pointed out that most Martian outflow channels originate from the regions of collapsed and disrupted terrain, suggesting that they were formed by a catastrophic release of groundwater. The question of the fate of Martian water is discussed, and arguments are presented suggesting that the Martian crust may retain significant porosity to a depth of 10 km and may possess a total pore volume sufficient to store a global layer of water 0.5-1.5 km deep.

Clifford, Stephen M.↗

NASA NTRS1979

Formation of Martian flood features by release of water from confined aquifers

It is proposed that the rapid release of water under great pressure from deeply buried aquifers is responsible for the formation of the Martian channels suggestive of catastrophic flooding (outflow channels). Fine channels in the Martian surface suggest the presence of surface water early in the history of the planet, which would have entered the ground water system through the porous near-surface rocks. Subsequent global cooling would have trapped the ground water under a thick permafrost layer and formed a system of confined aquifers. High pore pressures within the aquifers are considered to have triggered the breakout of water from the aquifers at rates of from 10 to the 5th to 10 to the 7th cu m/sec, which would be prevented from reentering the ground water system by the layer of permafrost. Outflow from the aquifer is also considered to have caused the undermining of adjacent areas and the collapse of the surface to form areas of chaos, often associated with channels.

Carr, M. H.↗

NASA NTRS1999

Effect of osteoblastic culture conditions on the structure of poly(DL-lactic-co-glycolic acid) foam scaffolds

Poly(DL-lactic-co-glycolic acid) (PLGA) foams are an osteoconductive support that holds promise for the development of bone tissue in vitro and implantation into orthopedic defects. Because it is desirable that foams maintain their shape and size, we examined a variety of foams cultured in vitro with osteoblastic cells. Foams were prepared with different porosities and pore sizes by the method of solvent casting/porogen leaching using 80, 85, and 90 wt% NaCl sieved with particle sizes of 150-300 and 300-500 microm and characterized by mercury intrusion porosimetry. Foams seeded with cells were found to have volumes after 7 days in static culture that decreased with increasing porosity: the least porous exhibited no change in volume while the most porous foams decreased by 39 +/- 10%. In addition, a correlation was observed between decreasing foam volume after 7 days in culture and decreasing internal surface area of the foams prior to seeding. Furthermore, foams prepared with the 300-500 microm porogen had lower porosities, greater mean wall thicknesses between adjacent pores, and larger volumes after 7 days in culture than those prepared with the smaller porogen. Two culture conditions for maintaining cells, static and agitated (in a rotary vessel), were found to have similar influences on foam size, cell density, and osteoblastic function for 7 and 14 days in culture. Finally, we examined unseeded foams in aqueous solutions of pH 3.0, 5.0, and 7.4 and found no significant decrease in foam size with degradation. This study demonstrates that adherent osteoblastic cells may collapse very porous PLGA foams prepared by solvent casting/particulate leaching: a potentially undesirable property for repair of orthopedic defects.

NASA Program Fundamental Space Biology↗

NASA NTRS1998

Manufacture of porous biodegradable polymer conduits by an extrusion process for guided tissue regeneration

We have fabricated porous, biodegradable tubular conduits for guided tissue regeneration using a combined solvent casting and extrusion technique. The biodegradable polymers used in this study were poly(DL-lactic-co-glycolic acid) (PLGA) and poly(L-lactic acid) (PLLA). A polymer/salt composite was first prepared by a solvent casting process. After drying, the composite was extruded to form a tubular construct. The salt particles in the construct were then leached out leaving a conduit with an open-pore structure. PLGA was studied as a model polymer to analyze the effects of salt weight fraction, salt particle size, and processing temperature on porosity and pore size of the extruded conduits. The porosity and pore size were found to increase with increasing salt weight fraction. Increasing the salt particle size increased the pore diameter but did not affect the porosity. High extrusion temperatures decreased the pore diameter without altering the porosity. Greater decrease in molecular weight was observed for conduits manufactured at higher temperatures. The mechanical properties of both PLGA and PLLA conduits were tested after degradation in vitro for up to 8 weeks. The modulus and failure strength of PLLA conduits were approximately 10 times higher than those of PLGA conduits. Failure strain was similar for both conduits. After degradation for 8 weeks, the molecular weights of the PLGA and PLLA conduits decreased to 38% and 43% of the initial values, respectively. However, both conduits maintained their shape and did not collapse. The PLGA also remained amorphous throughout the time course, while the crystallinity of PLLA increased from 5.2% to 11.5%. The potential of seeding the conduits with cells for transplantation or with biodegradable polymer microparticles for drug delivery was also tested with dyed microspheres. These porous tubular structures hold great promise for the regeneration of tissues which require tubular scaffolds such as peripheral nerve, long bone, intestine, or blood vessel.

NASA Discipline Cell Biology↗