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 1800degreesC (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 2000degreesC 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 1600degreesC, 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. (C) 2004 Kluwer Academic Publishers