Evaluation of Rare-Earth Element Dopants (Sm and Er) Effect on the Ablation Resistance and Emittance Tailoring of ZrB2/SiC Sintered Billets

Hypersonic flight causes ultra-high surface temperatures which are most intense on sharp leading edges. One way of reducing the surface temperature is to apply a high emittance ceramic (HEC) on the leading edge, increasing the radiation component of heat transfer. An ideal HEC must have a high emittance, while also possessing a strong ablation resistance. From a scientific standpoint, it would be helpful if emittance could be tailored at different wavelengths. For example, materials with tailorable emittance could be used to improve the efficiency of engines, thermo-photo voltaic cells, and other applications. The approach used to create a ceramic with tailorable emittance was to use two different rare-earth elements, adding them to an ultra-high temperature ceramic (UHTC) in small quantities. The samarium element was added to increase the emittance of the UHTC over a large wavelength range (visible to near infrared wavelengths, consistent with the temperature range expected for hypersonic flight), and the erbium element was added to decrease the emittance at specific wavelength ranges. The goal of this study was to create an UHTC with tailorable emittance while maintaining the required ablation resistance. Therefore, ZBS billets with five different Sm to Er ratios and with a nominal total amount of 3 mol.% dopant incorporated were prepared by sintering in vacuum to 2000 °C. The ablation resistance was evaluated by using an oxyacetylene torch and observing at exposure times of 60 s and 300 s, whereas the emittance was evaluated at the Air Force Research Lab facilities via a laser heating testing. The results for the ablation testing showed that ZrB₂-SiC (ZBS) billets co-doped with Sm and Er formed a beneficial c₁-(Sm/Er)_0.2Zr_0.8O_1.9 oxide scale as the majority phase, which is more thermally stable than the m-ZrO₂ oxide scale typically formed in oxidized ZBS systems, resulting in a more adherent oxide scale to the unreacted material. The crystalline oxide scale and the amorphous phase were formed by a convection cell mechanism where the c₁-(Sm/Er)_0.2Zr_0.8O_1.9 crystalline islands precipitate, grow, and coalesce. Moreover, differences in surface temperatures between ZBS samples with different dopant ratios suggest differences in spectral absorptance/emittance between each of the five compositions evaluated. Despite that the emittance profiles with varying Sm:Er molar ratios were similar because m-ZrO₂ was formed as the major oxide phase, the emittance study showed that the erbium oxide influences the emittance profile, as can be noted by the maximum and minimum emittance peaks. Furthermore, results showed that the emittance varies as a function of dopant(s) molar ratios and temperature at shorter wavelength ranges. These changes in the emittance are caused by the different Sm and Er concentration on the surface. Future work should be focused on producing the beneficial c₁-(Sm/Er)_0.2Zr_0.9O_1.8 phase directly from the manufacturing process, and therefore, maximize the effect of varying the Sm:Er molar ratios to tailor the emittance. Nonetheless, this study represents the first generation and reported emittance data of UHTC doping ZBS systems with both Sm and Er elements.