Optically Transparent Polyimide Aerogels

Aerogels are highly porous, low-density solids with extremely small pore sizes, fabricated by forming a gel from a solution in the wet-gel state that is then converted to the dry-solid state without compaction of the porous architecture. Aerogels make excellent electrical, thermal, and acoustic insulators. However, most inorganic silica aerogels are fragile and shed dust. The NASA Glenn team is the first to synthesize three-dimensional polymer aerogel networks of polyimides cross-linked with multifunctional amine monomers. Compared to silica aerogels, these aerogels retain small pore sizes and low thermal conductivities, but are distinguished by their flexibility. Polyimide aerogels are not brittle, fragile, or dusty like silica aerogels. Plus, polyimide aerogels possess the beneficial characteristics and strength of polyimide materials. The results are cross-linked polyimide aerogels with little shrinkage, low densities, high compression and tensile strengths, and good moisture resistance. They can be fabricated or machined into net shape parts, which are strong and stiff, or cast as thin flexible films with good tensile properties. Extremely customizable, polyimide aerogels can be formed into any configuration (e.g., wrapped around a pipe, sewn into protective clothing, or molded into a panel to act as a heat shield in a car). In short, Glenn's innovation improves the performance, adaptability, and affordability of aerogels in a broad number of applications.

Polyamides are polymers that are similar to polyimides (another polymer that has been developed for use in aerogels). However, because the amide link is a single chain while the imide link is a ring structure, polyamide aerogels can be made less stiff than polyimides, even though a similar fabrication process is used. The precursor materials can be made from any combination of diamine and diacid chloride. Furthermore, NASA Glenn researchers have found methods for using combinations of diamines and disecondary amines to produce polyamide aerogels with tunable glass transition temperatures, for greater control of features such as flexibility or water-resistance. In the first step of the fabrication process, an oligomeric solution is produced that is stable and can be prepared and stored indefinitely as stock solutions prior to cross-linking. This unique feature allows for the preparation and transport of tailor-made polyamide solutions, which can later be turned into gels via the addition of a small amount of cross-linker. When the cross-linking agent is added, the solution can be cast in a variety of forms such as thin films and monoliths. To remove the solvent, one or more solvent exchanges can be performed, and then the gel is subjected to supercritical drying to form a polyamide aerogel. NASA Glenn's polyamide aerogels can be fully integrated with the fabrication techniques and products of polyimide aerogel fabrication, so hybrid materials which have the properties of both classes are easily prepared. As the first aerogels to be composed of cross-linked polyamides, these materials combine flexibility and transparency in a way that sets them apart from all other polymeric aerogels.

Researchers at NASA's Glenn Research Center have developed an approach to significantly improve the mechanical properties and durability of aerogels without adversely affecting their desirable properties. This approach involves coating conformally and cross-linking the individual skeletal aerogel nanoparticles with engineering polymers such as isocyanates, epoxies, polyimides, and polystyrene. The mechanism of cross-linking has been carefully investigated and is made possible by two reactions: a reaction between the cross-linker and the surface of the aerogel framework and a reaction propagated by the cross-linker with itself. By tailoring the aerogel surface chemistry, Glenn's approach accommodates a variety of different polymer cross-linkers, including isocyanates, acrylates, epoxies, polyimides, and polystyreneenabling customization for specific mission requirements. For example, polystyrene cross-linked aerogels are extremely hydrophobic, while polyimide versions can be used at higher temperatures. Recent work has led to the development of strong aerogels with better elastic properties, maintaining their shape even after repeated compression cycling. By tailoring the internal structure of the silica gels in combination with a polymer conformal coating, the aerogels may be dried at the ambient condition without supercritical fluid extraction.

Traditional aerogels are produced by sol-gel chemistry where a dilute polymer solution is taken to gelation. Polymer Aerogel 3D printing requires a high viscosity sol for stackable extrusion; however, this limits the time frame to print the materials prior to gelation. In response to this issue, NASA researchers have developed a novel dual solvent process to be used in additive manufacturing (3D printing). A dual-solvent formulation is employed during polymer aerogel precursor preparation to enable 3D printing of self-supporting structures. The system combines a high–boiling point aprotic solvent, which supports polymerization and network formation during aerogel synthesis, with a secondary low–boiling point solvent that partially evaporates during extrusion and printing. Preferential evaporation of the low–boiling component increases the local solids concentration and material viscosity at the nozzle and immediately after deposition, enabling filament stackability and shape retention without premature gelation. This approach decouples printability from bulk gel chemistry, allowing precise control of rheology during printing while preserving the desired aerogel microstructure and porosity after drying. A Two-Pot System: • Pot 1 contains a cross-linked polyamic acid solution and acetic anhydride or water scavenger, dissolved into a mix of high and low boiling point solvents (e.g., Dimethyl Sulfoxide (DMSO), n-methylpyrrolidone (NMP), or Dimethylformadie (DMF), with acetone or tetrahydrofuran (THF), ethanol, or methanol. • Pot 2 contains a base catalyst (e.g., trimethylamine or pyridine) and optionally a thickening agent (e.g., polyvinyl alcohol or polyvinyl acetate) to match viscosities. Dual-Solvent Chemistry: The low boiling point solvent evaporates rapidly upon extrusion, increasing the polymer concentration and viscosity, allowing the aerogel to retain its shape and gel quickly. • Additive Manufacturing Process: The two solutions are mixed at the extrusion tip of a syringe/nozzle-based 3D printer. This enables low-viscosity flow pre-extrusion and rapid solidification post-extrusion—solving a key challenge in 3D printing aerogels.

To overcome the challenges of conventional molding, researchers at NASA Glenn have developed a rapid prototyping approach for three-dimensional printing of polymer aerogels using deposition into a viscous, sacrificial support medium. The sacrificial support stabilizes the aerogel deposition, allowing precise layer-by-layer construction of self-supporting aerogel networks that would otherwise be unprintable in air. Following printing and gelation of the polymer network, the printed structure is gently removed from the sacrificial medium, yielding a freestanding aerogel precursor with high shape fidelity. This method decouples printability from intrinsic material viscosity and enables rapid iteration of aerogel geometries, offering a scalable pathway for additive manufacturing of ultra-lightweight, architected polymer aerogels with tailored geometries, while retaining microstructural, mechanical, and thermal properties. The method involves: 1. Forming a solution comprised of a polymer precursor, cross-linker, solvent, and catalyst to create a dilute polymer solution. 2. 3D printing the polymer precursor directly into the sacrificial support medium. 3. Following printing and network formation, the structure is removed from the sacrificial medium through a low-stress extraction process, yielding a freestanding polymer aerogel precursor that retains the as-printed geometry with high fidelity. The sacrificial medium functions as a temporary, conformal support matrix that stabilizes each deposited droplet or filament in situ, enabling freeform construction of aerogel. This strategy enables the fabrication of highly porous, interconnected networks with controlled feature resolution across multiple length scales, while maintaining the intrinsic low density and high surface area required for aerogel performance.