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<p dir="ltr">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. <a href="" target="_blank">The spectral emittance of the rare-earth modified topcoat ZrO₂ was measured at high temperatures up to 1200</a>℃ 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.</p><p dir="ltr"><a href="" target="_blank">The bilayer coating system comprised of Sm₂O₃-stabilized ZrO₂ topcoat layer and SiC intermediate sublayer on C/C. </a><a href="" target="_blank">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.</a></p><p dir="ltr"><a href="" target="_blank">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</a> 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.</p>

The development of thermal barrier coatings (TBCs) has been undoubtedly the most critical advancement in materials technology for modern gas turbine engines. TBCs are widely used in gas turbine engines for both power-generation and propulsion applications. Metallic oxidation-resistant coatings (ORCs) are also widely employed as a stand-alone protective coating or bond coat for TBCs in many high-temperature applications. Among the widely studied durability issues in these high-temperature protective coatings, one critical challenge that received greater attention in recent years is their resistance to high-temperature degradation due to corrosive deposits arising from fuel impurities and CMAS (calcium-magnesium-alumino-silicate) sand deposits from air ingestion. The presence of vanadium, sulfur, phosphorus, sodium and calcium impurities in alternative fuels warrants a clear understanding of high-temperature materials degradation for the development of fuel-flexible gas turbine engines. Degradation due to CMAS is a critical problem for gas turbine components operating in a dust-laden environment. In this study, high-temperature degradation due to aggressive deposits such as V2O5, P2O5, Na2SO4, NaVO3, CaSO4 and a laboratory-synthesized CMAS sand for free-standing air plasma sprayed (APS) yttria stabilized zirconia (YSZ), the topcoat of the TBC system, and APS CoNiCrAlY, the bond coat of the TBC system or a stand-alone ORC, is examined. Phase transformations and microstructural development were examined by using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. This study demonstrated that the V2O5 melt degrades the APS YSZ through the formation of ZrV2O7 and YVO4 at temperatures below 747°C and above 747°C, respectively. Formation of YVO4 leads to the depletion of the Y2O3 stabilizer and the deleterious transformation of the YSZ to the monoclinic ZrO2 phase. The investigation on the YSZ degradation by Na2SO4 and a Na2SO4 + V2O5 mixture (50-50 mol. %) demonstrated that Na2SO4 itself did not degrade the YSZ, however, in the presence of V2O5, Na2SO4 formed vanadates such as NaVO3 that degraded the YSZ through YVO4 formation at temperature as low as 700°C. The APS YSZ was found to react with the P2O5 melt by forming ZrP2O7 at all temperatures. This interaction led to the depletion of ZrO2 in the YSZ (i.e., enrichment of Y2O3 in t' -YSZ) and promoted the formation of the fluorite-cubic ZrO2 phase. Above 1250°C, CMAS deposits were observed to readily infiltrate and significantly dissolve the YSZ coating via thermochemical interactions. Upon cooling, zirconia reprecipitated with a spherical morphology and a composition that depended on the local melt chemistry. The molten CMAS attack destabilized the YSZ through the detrimental phase transformation (t - > t - > f + m). Free standing APS CoNiCrAlY was also prone to degradation by corrosive molten deposits. The V2O5 melt degraded the APS CoNiCrAlY through various reactions involving acidic dissolution of the protective oxide scale, which yielded substitutional-solid solution vanadates such as (Co,Ni)3(VO4)2 and (Cr,Al)VO4. The molten P2O5, on the other hand, was found to consume the bond coat constituents significantly via reactions that formed both Ni/Co rich phosphates and Cr/Al rich phosphates. Sulfate deposits such as Na2SO4, when tested in encapsulation, damaged the CoNiCrAlY by Type I acidic fluxing hot corrosion mechanisms at 1000°C that resulted in accelerated oxidation and sulfidation. The formation of a protective continuous Al2O3 oxide scale by preoxidation treatment significantly delayed the hot corrosion of CoNiCrAlY by sulfates. However, CoNiCrAlY in both as-sprayed and preoxidized condition suffered a significant damage by CaSO4 deposits via a basic fluxing mechanism that yielded CaCrO4 and CaAl2O4. The CMAS melt also dissolved the protective Al2O3 oxide scale developed on CoNiCrAlY by forming anorthite platelets and spinel oxides. Based on the detailed investigation on degradation of the APS YSZ and CoNiCrAlY by various corrosive deposits, an experimental attempt was carried out to mitigate the melt-induced deposit attack. Experimental results from this study demonstrate, for the first time, that an oxide overlay produced by electrophoretic deposition (EPD) can effectively perform as an environmental barrier overlay for APS TBCs. The EPD protective overlay has a uniform and easily-controllable thickness, uniformly distributed closed pores and tailored chemistry. The EPD Al2O3 and MgO overlays were successful in protecting the APS YSZ TBCs against CMAS attack and hot corrosion attack (e.g., sulfate and vanadate), respectively. Furnace thermal cyclic oxidation testing of overlay-modified TBCs on bond-coated superalloy also demonstrated the good adhesive durability of the EPD Al2O3 overlay.