Mark M. Opeka

Oxidation-based materials selection for 2000°C + hypersonic aerosurfaces: Theoretical considerations and historical experience

Hypersonic flight involves extremely high velocities and gas temperatures with the attendant necessity for thermal protection systems (TPS). New high temperature materials are needed for these TPS systems. A systematic investigation of the thermodynamics of potential materials revealed that low oxidation rate materials, which form pure scales of SiO2, Al2O3, Cr2O3, or BeO, cannot be utilized at temperatures of 1800°C (and above) due to disruptively high vapor pressures which arise at the interface of the base material and the scale. Vapor pressure considerations provide significant insight into the relatively good oxidation resistance of ZrB2- and HfB2-based materials at 2000°C and above. These materials form multi-oxide scales composed of a refractory crystalline oxide (skeleton) and a glass component, and this compositional approach is recommended for further development. The oxidation resistance of ZrB2-SiC and other non-oxide materials is improved, to at least 1600°C, by compositional modifications which promote immiscibility in the glass component of the scale. Other candidate materials forming high temperature oxides, such as rare earth compounds, are largely unexplored for high temperature applications and may be attractive candidates for hypersonic TPS materials.

Mechanical, Thermal, and Oxidation Properties of Refractory Hafnium and zirconium Compounds

Abstract The thermal conductivity, thermal expansion, Youngs Modulus, flexural strength, and brittle–plastic deformation transition temperature were determined for HfB2, HfC0·98, HfC0·67, and HfN0·92 ceramics. The oxidation resistance of ceramics in the ZrB2–ZrC–SiC system was characterized as a function of composition and processing technique. The thermal conductivity of HfB2 exceeded that of the other materials by a factor of 5 at room temperature and by a factor of 2·5 at 820°C. The transition temperature of HfC exhibited a strong stoichiometry dependence, decreasing from 2200°C for HfC0·98 to 1100°C for HfC0·67 ceramics. The transition temperature of HfB2 was 1100°C. The ZrB2/ZrC/SiC ceramics were prepared from mixtures of Zr (or ZrC), SiB4, and C using displacement reactions. The ceramics with ZrB2 as a predominant phase had high oxidation resistance up to 1500°C compared to pure ZrB2 and ZrC ceramics. The ceramics with ZrB2/SiC molar ratio of 2 (25 vol% SiC), containing little or no ZrC, were the most oxidation resistant.

Designing for ultrahigh-temperature applications: The mechanical and thermal properties of HfB2, HfCx, HfNx and αHf(N)

The thermal conductivity, thermal expansion, Youngs Modulus, flexural strength, and brittle-plastic deformation transition temperature were determined for HfB2, HfC0.98, HfC0.67, and HfN0.92 ceramics. The mechanical behavior of αHf(N) solid solutions was also studied. The thermal conductivity of modified HfB2 exceeded that of the other materials by a factor of 5 at room temperature and by a factor of 2.5 at 820°C. The transition temperature of HfC exhibited a strong stoichiometry dependence, decreasing from 2200°C for HfC0.98 to 1100°C for HfC0.67 ceramics. The transition temperature of HfB2 was 1100°C. Pure HfB2 was found to have a strength of 340 MPa in 4 point bending, that was constant from room temperature to 1600°C, while a HfB2 + 10% HfCx had a higher room temperature bend strength of 440 MPa, but that dropped to 200 MPa at 1600°C. The data generated by this effort was inputted into finite element models to predict material response in internally heated nozzle tests. The theoretical model required accurate material properties, realistic thermal boundary conditions, transient heat transfer analysis, and a good understanding of the displacement constraints. The results of the modeling suggest that HfB2 should survive the high thermal stresses generated during the nozzle test primarily because of its superior thermal conductivity. The comparison the theoretical failure calculations to the observed response in actual test conditions show quite good agreement implying that the behavior of the design is well understood.

A Model for Transitions in Oxidation Regimes of ZrB2

A mechanistic model that interprets the transition in oxidation behavior of zirconium diboride as the temperature is varied from 600°C to 2500°C is presented. Available thermodynamic data and literature data for vapor pressures, oxygen permeability in boria, and viscosity of boria were used to evaluate the model. Three regimes and the temperatures of transition between them were identified. In the intermediate temperature regime, viz., 1000°C to 1800°C, good correspondence was obtained between theory and experiments for weight gain, recession, and scale thickness as functions of temperature and oxygen partial pressure. In this regime, the rate-limiting step is the diffusion of dissolved oxygen through a film of liquid boria in capillaries at the base of the oxidation product. At lower temperatures, an external boria scale forms, but it was not found to contribute significantly to oxidation resistance. Comparison with literature data on recession is very good, but weight gain is predicted to be higher than experimentally observed unless flow of viscous boria is included. At higher temperatures, the boria is lost by evaporation, and the oxidation rate is limited by diffusion of molecular oxygen through the capillaries between nearly columnar blocks of the oxide MO2.; this regime is soon followed by a rapid acceleration of recession due to vaporization of the oxide MO2 itself.