A New Class of Strong and Flexible Carbon Fiber Reinforced Phenolic Composites

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.

The invention includes an exposed surface cap with a specially formulated coating, an insulator base adjacent to the cap with another specially formulated coating, and one or more pins that extend from the cap through the insulator base to tie the cap and base together through ceramic bonding and mechanical attachment. The cap and insulator base have corresponding depressions and projections that mate and allow for differences in thermal expansion of the cap and base. The cap includes a high-temperature, low density, carbonaceous, fibrous material whose surface is optionally treated with a High Efficiency Tantalum-based Ceramic Composite (HETC) formulation, the fibrous material being drawn from the group consisting of silicon carbide foam and similar porous, high temperature materials. The insulator base and pin(s) contain similar material. The mechanical design is arranged so that thermal expansion differences in the component materials (e.g., cap and insulator base) are easily tolerated. It is applicable to both sharp and blunt leading edge vehicles. This extends the possible application of fibrous insulation to the wing leading edge and/or nose cap on a hypersonic vehicle. The lightweight system comprises a treated carbonaceous cap composed of Refractory Oxidation-resistant Ceramic Carbon Insulation (ROCCI), which provides dimensional stability to the outer mold line, while the fibrous base material provides maximum thermal insulation for the vehicle structure. The composite has graded surface treatments applied by impregnation to both the cap and base. These treatments enable it to survive in an aero-convectively heated environment of high-speed planetary entry. The exact cap and base materials are chosen in combination with modified surface treatments and a specially formulated surface coating, taking into account the duration of exposure and expected surface temperatures for the particular application.

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.

The invention provides a family of low density, flexible ablators comprising of a flexible fibrous substrate and a polymer resin. The flexible ablators can withstand a wide range of heating rates (40-540 Watts/cm2) with the upper limit of survivable heat flux being comparable to the survivable heat flux for rigid ablators, such as PICA and Avcoat. The amount and composition of polymer resin can be readily tailored to specific mission requirements. The material can be manufactured via a monolithic approach using versatile manufacturing methods to produce large area heat shields, which provides a material with fewer seams or gaps. The goals of the work are primarily twofold: (i) to develop flexible, ablative Thermal Protection System (TPS) material on a large, blunt shape body which provides aerodynamic drag during hypervelocity atmospheric entry or re-entry, without perishing from heating by the bow shock wave that envelopes the body; and (ii) to provide a relatively inexpensive TPS material that can be bonded to a substrate, that is unaffected by deflections, by differences in thermal expansion or by contraction of a TPS shield, and that is suitable for windward and leeward surfaces of conventional robotic and human entry vehicles that would otherwise employ a rigid TPS shield. This technology produces large areas of heat shields that can be relatively easily attached on the exterior of spacecraft.

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.