Design and Evaluation of High Emissivity Coatings for Carbon/Carbon Composites

During atmospheric re-entry, the hypersonic leading edges can experience enormous heat fluxes, with surface temperatures greater than 1600℃ expected. While carbon/carbon (C/C) is a candidate material for leading edge structures, it is prone to oxidation and ablation damage above 500℃. Ablation-resistant coatings can protect the C/C, while emissivity can be engineered to lower the leading-edge surface temperature via radiative cooling. In this dissertation, a novel bilayer coating system and a multilayer coating system based on individual layers consisting of ultra-high temperature ceramics (borides, carbides), refractory oxides (zirconia), and rare-earth oxide as emissivity modifiers were applied to a C/C surface via pack cementation and plasma spray. Ablation tests were performed to evaluate the efficacy of the multilayer coatings in simulated high heat flux environments. The spectral emittance of the rare-earth modified topcoat ZrO₂ was measured at high temperatures up to 1200℃ using a benchtop emissometer. ZrO₂ stabilized with 6 mol% Sm₂O₃ demonstrated a maximum spectral emissivity of 0.99 at λ = 12.5 µm proving its effectiveness in cooling the leading edge surface through enhanced thermal radiation.

The bilayer coating system comprised of Sm₂O₃-stabilized ZrO₂ topcoat layer and SiC intermediate sublayer on C/C. This coating significantly improved the ablation resistance of C/C by reducing the mass ablation rate by ~71%. Despite a significant thermal expansion coefficient mismatch between the substrate and the coating, a well-defined mechanical adhesion characterized by the anchors was observed in pre- and post-ablated coating microstructures, indicating their influence on improving ablation resistance.

The multilayer coating architecture consisted of SiC, ZrB₂-SiC, ZrC-ZrO₂ sublayers and a Sm₂O₃-ZrO₂ topcoat. The as-sprayed coating microstructure demonstrated well-defined adhesion between the layers and the substrate without forming major voids or cracks. The multilayer coating with optimized sublayer thickness demonstrated excellent ablation and mass erosion resistance as they reduced the mass ablation rate of C/C by ~90% after being subjected to an aggressive oxyacetylene torch heating for 60 s. During testing, the Sm₂O₃-stabilized ZrO₂ topcoat acted as oxygen and thermal barrier, protecting the underlying sublayers from oxidation-induced damage while maintaining a constant surface temperature of ~2100 ℃. Additionally, the high spectral emittance of topcoat material contributed to efficient outward heat transfer via thermal radiation from the external surface while maintaining a constant temperature.