3D Construction of Biologically Derived Materials

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.

Current scaffold designs and materials do not provide all of the appropriate cues necessary to mimic in-vivo conditions for tissue engineering and stem cell engineering applications. It has been hypothesized that many biomaterials, such as bone, muscle, brain and heart tissue exhibit piezoelectric and ferroelectric properties. Typical cell seeding environments incorporate biochemical cues and more recently mechanical stimuli, however, electrical cues have just recently been incorporated in standard in-vitro examinations. In order to develop their potential further, novel scaffolds are required to provide adequate cues in the in-vitro environment to direct stem cells to differentiate down controlled pathways or develop novel tissue constructs. This invention is for a scaffold that provides for such cues by mimicking the native biological environment, including biochemical, topographical, mechanical and electrical cues.

NASA's new technique for generating recyclable feedstocks for on-demand additive manufacturing employs the high-yield reversibility of the Diels-Alder reaction between maleimide and furan functionalities, utilizing the exceedingly favorable interaction between specific chemical functionalities, often termed "click reactions" due to their rapid rate and high efficiency. Integration of these moieties within a polymer coating on epoxy microparticle enables reversible assembly into macroscopic, free-standing articles. This click chemistry can be activated and reversed through the application of heat. Monomer species can be used to incorporate these functionalities into polyimide materials, which provide excellent mechanical, thermal, and electrical properties for space applications. Copoly (carbonate urethane) has been shown to be a viable coating material in the generation of polymer-coated epoxy microparticle systems and is amenable to being processed through a variety of approaches (e.g., filaments and slurries for 3D printing, compression molding, etc.). The polymeric materials are grown from the surfaces of in-house fabricated epoxy microparticles. The thermal and mechanical properties of the microparticles can be readily tuned by changes in composition. There are a number of potential applications for this NASA technology ranging from use of these materials for recyclable/repurpose-able articles (structural, decorative, etc.) to simple children's toys. More demanding uses such as for replacement parts in complex industrial systems are also possible. For long term space missions, it is envisioned that these feedstocks would be integrated into secondary spacecraft structures such that no additional concerns would be introduced due to in-space chemical reactions and no additional mass would be required.

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.

The technology is a method to increase automation of Additive Manufacturing (AM) through augmentation of the Fused Filament Fabrication (FFF) process. It can significantly increase the speed of 3D printing by automating the removal of printed components from the build platform without the need for additional hardware, which increases printing throughput. The method can also be leveraged to perform automated object testing and characterization. The method includes embedding into the manufacturing instructions methods to fabricate directly onto the build platform an actuator tool, such as a linear spring. The deposition head can be leveraged as a robotic manipulator of the actuator tool to bend, cock, and release the linear spring to strike the target manufactured object and move it off the build platform of the machine they were manufactured on. The ability for an object to 'fly off of the machine that made it' essentially enables automated clearing of the processed build volume. The technology can also be used for testing the AM machine or the feedstock material by successively fabricating prototypes of the manufactured object, and taking measurements from sensors as the actuator strikes the prototype. This provides automated testing for quality control, machine calibration, material origins, and counterfeit detection.