3D Printable Polymer Aerogels Using a Two-Pot Dual Solvent Method
Manufacturing
3D Printable Polymer Aerogels Using a Two-Pot Dual Solvent Method (LEW-TOPS-177)
A novel approach for overcoming manufacturing challenges associated with 3D printed aerogels.
Overview
Researchers at NASA’s Glenn Research Center have developed a two-pot, dual-solvent system to overcome long-standing manufacturing challenges associated with 3D printed aerogels. These ultralight, porous materials are known for their exceptional thermal, acoustic, and vibration insulation properties. The new approach enables the creation of complex, finely detailed aerogel structures using additive manufacturing, expanding their potential applications across aerospace, automotive, construction, and electronics industries.
The Technology
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.
Benefits
- Complex Geometries: Enables intricate 3D aerogel structures not possible with traditional molding.
- On-Demand Manufacturing: Supports in-place, point-of-use production using direct ink writing.
- Customizable Formulations: Allows incorporation of functional additives during printing.
- Improved Shelf Life: Dual-solvent system extends the usable life of the polymer solution.
- Versatile Use: Formulations are compatible with both 3D printing and traditional molding processes.
Applications
- Thermal Insulation: Electronics, spacecraft, aircraft, pipelines, and buildings.
- Acoustic Insulation: Aircraft engines (including eVTOLs), automotive, and architectural acoustics.
- Vibration Damping: Aerospace, marine, industrial, and automotive systems.
- Advanced Manufacturing: Coatings, adhesives, and other post-extrusion curing applications.
Technology Details
Manufacturing
LEW-TOPS-177
LEW-20062-1
NASA, TOPS, 3D Printed UV-curable Polymer Aerogels (LEW-TOPS-171), https://technology.nasa.gov/patent/LEW-TOPS-171
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Rapid Aerogel Prototyping Using 3D Printing
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.
Polymer Cross-Linked Aerogels (X-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.
Optically Transparent Polyimide Aerogels
Innovators at NASA Glenn have devised a new method for harnessing the high transmission and clarity associated with optical glasses in a robust polyimide aerogel. This process uses sol-gel synthesis technology with aromatic dianhydrides and diamines as the precursors, and a trifunctional triacid chloride that arranges itself into a three-dimensional (3D) matrix with a low refractive index. The liquid portion of the gel is then removed by supercritical fluid extraction in order to produce the polyimide aerogel and maintain the desired 3D structure without pore collapse. The result is a cross-linked polyimide aerogel that allows for light wave transmittance while retaining low thermal conductivity. This unique material can be made into thin blocks, or highly flexible films as thin as 0.5 mm. While some embodiments have a yellow color, other embodiments may be nearly colorless. When compared to high-opacity polyimide aerogels, they have much greater surface area (up to 880 m2/g) and a very homogenous pore size (10 to 20 nm) with only a minor penalty in density (0.15 g/cc vs 0.10 g/cc). These strong, optically transparent aerogels incorporate a number of unique properties with applicability to a host of potential new applications, making this innovation a game-changer in the global aerogel market. Glenn welcomes co-development opportunities.
Aerogel Reinforced Composites
GRC's aluminosilicate aerogel composites are fabricated using a sol-gel technique. A sol is formed by hydrolyzing an alumina dispersion in acid solution; the alumina may be combined with a silicon precursor to create a sol.
Fabrics, papers, and felts are used as reinforcing fibers to form an aerogel composite. The aerogel adheres to the reinforcement without use of sizing or organic binders. (In the case of sized fabrics, the sizing is first removed by heat cleaning.) Composites can be fabricated in a batch process, impregnating individual layers of paper, felt or fabric with the precursor sol, or in a roll-to-roll process. The sol is allowed to gel, and then aged for several days prior to supercritical drying using liquid CO2. Heat treatment of the super critically dried composites can be used to tailor the alumina or Aluminosilicate crystal structure and pore size.
In contrast to commercially available insulations, GRC's innovation provides extremely low thermal conductivity (60 mW/m-K at 900°C in argon) at high temperatures, thus enabling use at higher temperatures and improving applicability. In addition, GRC's unique process provides very good adhesion of the aerogel to its reinforcing fibers in alumina papers and zirconia felts, eliminating the spalling seen in other aerogel composites. Finally, GRC's innovation demonstrates low density and extreme resilience to high temperatures and harsh conditions. Seven layers of composite material of 1.25 mm/layer produced a temperature drop of 700°C when tested in the 8-foot high-temperature wind tunnel (8 HTT) at NASA's Langley Research Center. The technology also has withstood heat tests of up to 1200°C. In combination with other insulators, it has withstood fluxes of up to 65 W/cm2, producing a temperature drop of 625°C across 8 mm.
Durable 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.
