Concepts for Smart Protective High-Temperature Coatings

The need for environmental resistance is a critical material barrier to the operation of fossil systems with the improved energy efficiencies and emissions performance described by the goals of the Vision 21 concept of the U.S. Department of Energy’s Office of Fossil Energy. All fossil fuel-derived processes contain reactive species and high-temperature degradation arising from reactions of solids with gases and condensible products often limits performance or materials lifetimes such that efficiency, emission, and/or economic targets or requirements are not realized. Therefore, historically, the development of materials for fossil-fuel combustion and conversion systems has been closely linked to corrosion studies of alloys and ceramics in appropriate environments. This project is somewhat different from such studies in that it focuses on the feasibility of new routes to controlling the critical chemical and mechanical phenomena that collectively form the basis for environmental protection in relevant fossil environments by exploring compositional and microstructural manipulations and cooperative phenomena that have not necessarily been examined in any detail to date. This can hopefully lead to concepts for “smart” coatings or materials that have the ability to sense and respond appropriately to a particular set or series of environmental conditions in order to provide high-temperature corrosion protection. The strategies being explored involve cooperative or in-place oxidation or sulfidation reactions of multiphase alloys.[1,2] The first material systems to be evaluated involve silicides as there is some evidence that such materials have enhanced resistance in oxidizing-sulfidizing and sulfidizing environments and in air/oxygen at very high temperatures.[3] In this regard, molybdenum silicides may prove to be of particular interest. Molybdenum is known to sulfidize fairly slowly[4] and there has been recent progress in developing Mo-Si-B systems with improved oxidation resistance at high and intermediate temperatures.[5-11] Consequently, Mo-Si-B alloys with different compositions and phase morphologies were oxidized in dry air at 1200°C under cyclic oxidation conditions. In addition, elevated-temperature oxidation-sulfidation exposures of Mo-Mo5SiB2-Mo3Si alloys also were conducted. In this way, the specific effects of the multiphase nature (composition, morphology) of the Mo-Si-B system on protective product formation are being evaluated.