ULTRA-HIGH TEMPERATURE

CERAMIC COATINGS
Multilayer ceramic coatings appear to offer the best oxidation protection for carbon-carbon composites that make up the structure of future hypersonic space vehicles. Erica L. Corral*
University of Arizona Tucson, Arizona
Fig. 1 Illustrations of re-entry and hypersonic test vehicles researched at NASA and USAF. Images are from NASA Dryden Flight Research Center and Air Force Office of Scientific Research.

ltra high temperature ceramics (UHTCs) have been identified as a class of materials with the potential to withstand extreme aerothermal heating environments. For example, diboride and carbide-based ceramics possess melting temperatures in excess of 3000C. Table 1 lists a range of candidate high-temperature ceramics that have decomposition or melting temperatures above 1600C. Current work at the University of Arizona in collaboration with Sandia National Laboratories focuses on adherent, continuous coatings of SiC and ZrB2 for enhanced oxidation protection of carboncarbon composites. ZrB2 was chosen based on its high melting point, and SiC can provide oxidation protection at lower temperatures. The combination of both materials would synergistically provide oxidation protection over a wide range of temperatures. Based on previous research, no single coating material appears to be sufficiently protective. Therefore, multilayer ceramic coatings engineered to provide necessary oxidation resistance for C-C composites and high temperature oxidation testing will be the focus of this article.

Hypersonic flight vehicles Advanced thermal protection systems are needed to mitigate effects of aerothermal heating that otherwise limit the performance of hypersonic flight vehicles. A variety of mission profiles are being proposed with different thermal loads and temperatures. For example, a single use, unmanned vehicle that has a flight profile lasting only minutes can reach a maximum temperature of ~ 2800C. Figure 1 shows hypersonic vehicle designs that are being researched for NASA and the United States Air Force. However, hypersonic vehicles require coatings that will protect structures against temperatures in excess of 2800C, enabling them to maintain tensile strength and oxidation resistance. Carbon-carbon composites provide high strength and low density, but they oxidize in air at temperatures >500C, and need thermal protection systems (TPS) to survive aerothermal heating. Oxidation protection Applying UHTC coatings to carbon-carbon composites for oxidation protection is a viable approach to TPS design if the coating can be engineered to have the following qualities:

*Member of ASM International

Table 1 Thermal and physical properties of UHTCs and refractory ceramics

Ceramic material SiC ZrB2 HfB2 HfC ZrC Decomposition and melting temperature Td and Tm, C (F) Td=1600 (2910) Tm=2730 (4950) Tm=3200 (5790) Tm=3250 (5880) Tm=3890 (7030) Tm=3530 (6390) Density, g/cm3 3.22 6.08 10.50 12.22 6.73 Oxidation products in air SiO2 + CO2 ZrO2 + B2O3 HfO + B2O3 HfO + CO2 ZrO2 + CO2

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 Adherent and continuous to provide erosion resistance and limit the mechanisms of evaporation. Prevent oxygen permeation through the coating and reduce the diffusion of oxygen to the substrate. Mechanically compatible to resist coating spallation due to thermal expansion mismatch during extreme thermal heating. Easily processed so that they can be made reproducibly and reliably. An adherent and continuous coating should also provide erosion resistance and stay intact. The outer coating should be a material that does not oxidize readily, allowing it to function at high service temperatures. However, if a readily-oxidized material is the only choice because of some other design constraints, then an additional mechanism should be introduced that limits oxidation and provides integrity to the porous external oxide coating. For example, a multilayer coating configuration that has a boron-rich bottom layer and a silicon carbide outside layer will be protective if the boron rich layer oxidizes to form a sealing glass when heated. However, this works only if the sealing glass penetrates through the cracks of the SiC layer and limits oxidation of the coating. A coating that prevents oxygen permeation should be free of defects, continuous, and have a low rate of oxygen diffusion. This suggests that the outer coating material should have a low rate of oxygen diffusion through it and through any subsequent oxidation product. Acoating that is mechanically compatible with the substrate during extreme thermal heating should serve as the inner layer, and it should be interlocked within the substrate to increase adherence. On the other hand, if the coating material is not mechanically compatible with the C-C composites, then coating spallation and stress-induced cracking will result. To promote adhesion of dense coatings and prevent delamination, materials that have favorable wetting properties on the C-C composite should be considered. Some materials that are candidates for inner layers include converted carbides, and borate and silicate glasses. The glasses combine thermal stability with appropriate viscosity and wetting to provide protection over a wide range of temperatures, both as coatings and as constituents of the carbon body. To limit cracking and the quantity of oxidation products, special attention should be given to the thickness of the coating layers. To promote better adhesion during processing, pre-treatments to the C-C composite should be considered. Many methods are available to develop coatings with fine-scale microstructures. Technologies include single or multiple methods such as sputter deposition, electroplating, electron beam irradiation, liquid precursor methods, slurry coating, pack cementation, and chemical vapor deposition. Each method has specific advantages for control of coating thickness and material composition that should enable a wide range of microstructures and configurations. Processing approach Multilayer coatings of ZrB2 and SiC on carbon-

carbon composites have been developed in which preceramic polymer/ceramic slurry mixtures coat and infiltrate the composites. In this technology, a process in which preceramic polymers are filled with crystalline ceramic particles has been optimized for composition and pyrolysis heat treatment after each infiltration/coating cycle. Figure 2 shows a cross-section of an infiltrated CC composite coated with SiC. The coating thickness is between 20 and 35 microns. Figure 3 shows the surface of a C-C composite coated with SiC/ZrB2. The segregation of the two materials on the surface can be seen via elemental mapping of silicon (in red) and zirconium (in green). This illustrates the complexity of working with ceOuter layer Substrate material Infiltrated layer 1000 Pm

Fig. 2 SEM cross-section of a carbon-carbon composite infiltrated and coated with multilayers of SiC.
a b

Fig. 3 SEM image showing the surface of a carbon-carbon composite coated with (a) SiC/ZrB2 multilayers and (b) corresponding elemental maps for silicon (red), zirconium (green), and carbon (blue).

ramic precursors to uniformly coat a surface. To make reliable UHTC coatings and to optimize infiltration and adhesion on C-C composites, it is necessary to thoroughly understand the physical and chemical properties of the material to be coated. For this reason, we tried a variety of processing methods and pre-treatments. By controlling the composite pore structure, surface chemistry, and bulk crystallinity, coatings can be applied reproducibly. Both the processing routes and the fiber preforms strongly influence the microstructure of the C-C composites. Variations in the type of fibrous preform, the liquid infiltration, and the final heat treatment allow dramatic enhancement of the graphitization of the carbon matrix and the fibers, as well as the size of graphite crystallites. Specifically, high-temperature heat treatment reduces the amount of open porosity by removing amorphous carbon deposited at the internal surfaces of the material. It also creates microstructures that are more crystalline, and increases the size and orientation of the fiber and matrix crystallites. The pre-treatment is designed to enhance the absorp-

This article included 24 references, which could not be included here. Please contact the author for a complete list. Acknowledgments The author thanks team members from the thermal protection system research team at Sandia National Laboratories for their contributions to this work.

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Fig. 4 SEM micrographs of solar tested SiC/ZrB2 coated specimens show (a) protective and (c) non-protective coating on the surface. In cross-section (b), the protective coating retains the initial shape of the carbon-carbon composite. Part (d) shows that when it is not oxidative-protective and it fails, a large section of the composite near the surface is oxidized.

For more information: Erica L. Corral, University of Arizona, Department of Materials Science & Engineering, 1235 James E. Rogers Way, Tucson, AZ 85721; elcorral@email. arizona.edu; www.arizona. edu.

tion of ceramic coatings by controlling the physical and chemical properties that affect coating infiltration and adhesion. Heat treatments up to 1600C for four hours under vacuum are usually required to affect fiber size and crystallinity, and to influence adhesion properties. Evaluating oxidation Low cost, reliable testing methods for evaluating oxidation-protection materials are needed to advance TPS materials development and the understanding of coating materials. The multilayer coatings of ZrB2 and SiCr were tested at the National Solar Thermal Testing Facility at Sandia National Laboratories, Albuquerque, N.M. Coatings were tested for thermal shock resistance at high temperatures and severe heat-flux conditions in Sandias Solar Furnace. The furnace can accurately control a variable heat-flux up to 800 W/cm2 while continuously monitoring the specimen surface temperature up to 2600C. This test does not include all the hypersonic environmental conditions, which can be achieved only in an actual test flight. However, these test conditions are suitable for studying oxidation resistance at extreme temperature and heat-flux conditions, and are meant to serve as a screening test prior to evaluation at more complex and expensive facilities. A list of ground-based testing methods is shown in Table 2 for comparison. Analysis of multilayer coatings Solar Furnace testing directly duplicates the severe high heat-flux (680 W/cm2) and high-temperature (>2600C) conditions for short periods of time (15 seconds), similar to a hypersonic flight profile. Figures 4 (a) and (b) show SEM micrographs representative of solar-tested surfaces of C-C composites coated with SiC/ZrB2 that provided oxidation protection and those that did not, respectively. Figure 4 (a) shows a C-C composite surface that is coated with SiC and decorated with islands that contain boron and are presumed to be B2O3 parti-

cles. Spot elemental analysis of these small particles showed they contain boron, and that the surrounding area is covered with silicon. X-ray diffraction analysis on the tested surface of the specimen also revealed intense graphite reflections, as well as peaks for SiC, B2O3, and SiO2, indicating that the multilayer coating protected the CC composite from oxidation. Figure 2 (b) shows the cross-section of the tested specimen that survived solar testing, and shows a significant amount of SiC within the C-C composite. It also shows a SiC-rich band of material that formed after high-temperature testing just one mm below the surface. No boron or zirconium-rich particles were detected in the cross-section. It is most likely that the ZrB2 material decomposed to B2O3 and ZrO2 at the surface, where the ZrB2 was exposed to the highest temperature. Figure 4 (c) shows a C-C composite surface that did not provide oxidation protection. It shows exposed weaves of oxidized C-C fibers with agglomerated SiC particles embedded between the layers. The coating composition was most likely not optimized in the specimen. The failed coating resulted from processing variations that did not produce a continuous and protective coating. Spot elemental analysis of the particles confirmed that they contain silicon. X-ray diffraction analysis also showed very low intensity peaks for graphite due to the oxidation of the C-C, and low intensities for the SiC peaks due to the failure and depletion of the coating during solar testing. Figure 4 (d) shows the cross-section of the same specimen that did not provide oxidation protection. The top region shows a thick layer of oxidized C-C material and residual SiC further from the surface of the C-C composite. These results clearly show that multilayer coatings with SiC and ZrB2 provide oxidation protection for C-C composites under severe heat-flux and high-temperature conditions.

Table 2 Ground based testing facilities comparison

Testing method High-temp furnace Oxyacetylene torch Solar Arcjet Heating mode Radiative & convective Convective Radiative Convective w/ some radiative Maximum temperature, C (F) 2000 (3630) >2000 (3630) >2600 (4710) 2000 (3630) >2200 (3990) Maximum heat flux n/a >150 W cm-2 250-800 W cm-2 >250 W cm-2 >250 W cm-2 Oxygen mass flux Poor Poor Fair Good Excellent Atomic oxygen Shear flow Poor Poor Poor Poor Excellent n/a n/a n/a Fair Excellent

Laser subsonic tunnel Radiative w/convective cooling

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