Free-Form Fabrication Using Electrically Conductive Filaments

Many researchers have attempted to use polymer-ceramic composites to improve the thermal and dielectric performance of polymer insulation for high voltage, high temperature electronics. However, using composite materials has been challenging due to manufacturing issues like incomplete mixing, inhomogeneous properties, and void formation. Here, NASA has developed a method of preparing and extruding polymer-ceramic composites that results in high-quality, flexible composite ribbons. To achieve this, pellets of a thermoplastic (e.g., polyphenylsulfone or PPSU) are coated with an additive then mixed with particles of a ceramic (e.g., boron nitride or BN) as shown in the image below. After mixing the coated polymer with the ceramic particles, the blended material was processed into ribbons or films by twin-screw extrusion. The resulting ribbons are highly flexible, well-mixed, and void free, enabled by the coated additive and by using a particle mixture of micronized BN and nanoparticles of hexagonal BN (hBN). The polymer-ceramic composite showed tunable dielectric and thermal properties depending on the exact processing method and composite makeup. Compared to the base polymer material, the composite ribbons showed comparable or improved dielectric properties and enhanced thermal conductivity, allowing the composite to be used as electrical insulation in high-power, high-temperature conditions. The related patent is now available to license. Please note that NASA does not manufacturer products itself for commercial sale.

There has been much interest in developing polymeric nanocomposites with ultrahigh thermal conductivities, such as with exfoliated graphite or with carbon nanotubes. These materials exhibit thermal conductivity of 3,000 W/mK measured experimentally and up to 6,600 W/mK predicted from theoretical calculations. However, when added to polymers, the expected thermal conductivity enhancement is not realized due to poor interfacial thermal transfer. This technology is a method of forming carbon-based fillers to be incorporated into highly thermal conductive nanocomposite materials. Formation methods include treatment of an expanded graphite with an alcohol/water mixture followed by further exfoliation of the graphite to form extremely thin carbon nanosheets that are on the order of between about 2 and about 10 nanometers in thickness. The carbon nanosheets can be functionalized and incorporated as fillers in polymer nanocomposites with extremely high thermal conductivities.

This NASA invention enables several benefits that mitigate limitations associated with conventional ATP systems, including the following: (1) avoids obtuse head rotation or cross-tool translation when laying adjunct tape plies, (2) simultaneously places tape on both sides of a part via two robots, (3) eliminates external anchoring frame requirements, and (4) translates parts during build while also translating the applicator head. The ability to perform simultaneous layup on opposite sides of the component, as well as reduction of head rotation reversal during bidirectional tape layup, offers increased layup speed. The invention offers increased placement accuracy as a result of reduced movement between tape layup operations and the eliminated need for an anchoring frame (facilitated by simultaneous pressure extrusion of prepreg by the two robots). NASA’s automated tow/tape placement system has two key unique features: the use of two opposed ATP cars to enable a tool-less process, and an on-the-fly reversal tape/tow laydown tooling head. The system uses two opposing (i.e., underside-to-underside) ATP cars, and can build parts vertically, horizontally, or at any other angle, depending on the workspace available. The ATP die wheels can be reversed or turned to draw the composite back and forth at different angles to create a layer-by-layer composite structure. Both cars can dispense TPC tape – thus, either car can function as an opposing tool surface while the other performs prepreg lay-up. For structures that do not vary in thickness, both cars can lay tape at the same time – doubling layup speed. Current ATP robots must rotate the large tooling head, or traverse panels without layering tape to achieve bidirectional layup, where each additional movement introduces alignment error. To increase layup rate while simultaneously minimizing misalignment, NASA’s system incorporates an on-the-fly reversal tape/tow laydown tooling head to enable efficient bidirectional layup.

Carbon nanotubes (CNTs) show promise for multifunctional materials for a range of applications due to their outstanding combination of mechanical, electrical and thermal properties. However, these promising mechanical properties have not translated well to CNT nanocomposites fabricated by conventional methods due to the weak load transfer between tubes or tube bundles. In this invention, the carbon nanotube forms such as sheets and yarns were modified by in-situ polymerization with polyaniline, a -conjugated conductive polymer. The resulting CNT nanocomposites were subsequently post-processed to improve mechanical properties by hot pressing and carbonization. A significant improvement of mechanical properties of the polyaniline/carbon nanotube nanocomposites was achieved through a combination of stretching, polymerization, hot pressing, and carbonization.

The new composite developed by NASA incorporates PGS and CNTs to enhance its thermal conductivity while preserving the mechanical properties of the underlying carbon fiber polymer composite. NASA has also improved the composite manufacturing process to ensure better thermal conductivity not only on the surface, but also through the thickness of the material. This was achieved by adding perforations that enable the additives to spread through the composite. The process for developing this innovative, highly thermally conductive hybrid carbon fiber polymer composite involves several steps. Firstly, a CNT-doped polymer resin is prepared to improve the matrix's thermal conductivity, which is then infused into a carbon fiber fabric. Secondly, PGS is treated to enhance its mechanical interface with the composite. Thirdly, perforation is done on the pyrolytic graphite sheet to improve the thermal conductivity through the thickness of the material by allowing CNT-doped resin to flow and better interlaminar mechanical strength. Finally, the layup of PGS and CNT-CF polymer is optimized. Initial testing of the composite has shown significant increases in thermal conductivity compared to typical carbon fiber composites, with a more than tenfold increase. The composite also has higher thermal conductivity than aluminum alloys, with more than twice the thermal conductivity of the Aluminum 6061 typically used in the aerospace industry. For this new material, NASA has completed a proof-of-concept demonstration and work continues to use the material in a heat exchanger system and further characterize the properties including longevity and radiation impact analysis.