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A new powder processing approach to produce oxidation resistant molybdenum alloys for high temperature use has been developed. Oxidation protection is provided by fine dispersion of silica glass particles within a molybdenum matrix. As the molybdenum oxidizes, the glass is exposed and melts to form a self-healing protective oxide coating. Additionally, homogeneously dispersed Mo5SiB2 and/or Mo2B provide boria upon oxidation which reduces glass viscosity and allows flowing glass to coat the surface while remaining solid internally. This is similar to the oxidation protection used in Mo-3Si-1B (wt%) systems; however embedding the glass directly into the Mo matrix and eliminating the Mo3Si (A15) phase provides the same volume of glass at lower volume fractions of brittle phases and also without embrittling Si impurities in solution in Mo. Additionally the glass composition can be tailored for different applications and different temperatures beyond that achievable in Mo-Si-B based systems. A variety of microstructures, compositions and additional components for improved oxidation protection are also explored, and mechanisms of the oxidation protection are discussed.

The development of molybdenum - silicon - boron (Mo-Si-B) composites having a combination of high temperature strength, creep, and oxidation residence has the potential to substantially increase the efficiency of gas turbines. The refractory nature of the αMo, Mo3Si (A15), and Mo5SiB2 (T2) phases results in good strength and creep resistance up to 1300°C. At this temperature, the formation of a borosilicate surface scale from the two intermetallic phases is able to provide oxidation resistance. However, realization of these advantages has been prevented by both a high brittle to ductile transition temperature and difficulty in forming the initial surface borosilicate to provide bulk oxidation resistance. This dissertation addresses two factors pertaining to this material system: 1) improvements to powder processing techniques, and 2) development of compositions for oxidation resistance at 1300°C. The processing of Mo-Si-B composites is strongly tied to their mechanical properties by establishing the αMo matrix, limiting impurity content, and reducing silicon supersaturation. These microstructural aspects control the brittle to ductile transition temperature which has traditionally been too high for implementation of Mo-Si-B composites. The processing here built upon the previously developed powder processing with silicon and boron nitrides which allowed for a low oxygen content and sintering of fine starting powders. Adjustments were made to the firing cycle based upon dew point measurements made during the hydrogen de-oxidation stage. Under a relatively high gas flow rate, 90% of the total water generated occurred during a ramp of 2°C /min between 450 and 800°C followed by a hold of 30 minutes. The oxidation resistance of Mo-Si-B composites was studied for a wide range of compositions. Silicon to boron atomic ratios were varied from 1 to 5 and iron, nickel, cobalt, yttria, and manganese were included as minor additions. In all these compositions, the αMo volume fraction was kept over 50% to ensure the potential toughness of the composite. For the oxidized surface glass, a silica fraction of 80 to 85% was found to be necessary for the borosilicate to have a sufficiently high viscosity and low oxygen permeability for oxidation resistance at 1300°C. For the Mo-Si-B bulk composition this corresponds to a Si/B atomic ration of 2 to 2.5. Higher viscosity compositions failed due to spallation of poorly attached, high silica scales. Lower viscosity compositions failed from continuous oxidation, either through open channels or repetitive MoO3 bubble growth and popping. Additionally, around 1% manganese was necessary for initial spreading of the borosilicate at 1300°C. In conjunction with flowing air to prevent MoO3 accumulation, oxidation weight loss rates below 0.05 mg/cm2-hr were measured. Finally, a theory is proposed here to describe the mechanisms responsible for the development of oxidation resistance. This theory involves three stages associated with: 1) generation of an initial surface borosilicate, 2) thickening of the borosilicate layer, and 3) slow parabolic oxidation controlled by the high silica surface scale.

Mo-Si-B alloys are a leading candidate for the next generation of jet turbine engine blades and have the potential to raise operating temperatures by 300-400°C. The alloys of interest are a three-phase mixture of the molybdenum solid solution (Moss) and two intermetallic phases, Mo3Si (A15) and Mo5SiB2 (T2). A novel powder metallurgical method was developed which uses the reaction of molybdenum, silicon nitride (Si3N4) and boron nitride (BN) powders to synthesize a fine dispersion of intermetallics in a Moss matrix. The covalent nitrides are stable in oxidizing environments up to 1000ºC, allowing for fine particle processing. The process developed uses standard powder processing techniques to create Mo-Si-B alloys in a less complex and expensive manner than previously demonstrated. This powder metallurgy approach yields a fine dispersion of intermetallics in the Moss matrix with average grain sizes of 2-4μm. Densities up to 95% of theoretical were attained from pressureless sintering at 1600°C and full theoretical density was achieved by hot-isostatic pressing (HIP). Sintering and HIPing at 1300°C reduced the grain sizes of all three phases by over a factor of two. Microstructure examination by electron back-scatter diffraction imaging was used to precisely define the location of the phases and to measure the volume fractions and grain size distributions. Microstructural quantification techniques including two-point correlation functions were used to quantify microstructural features and correlate the BN reactant powder size and morphology to the distribution of the intermetallic phases. High-temperature tensile tests were conducted and yield strengths of 580MPa at 1100°C and 480MPa at 1200°C were measured for the Mo-2Si-1Bwt.% alloy. The yield strength of the Mo-3Si-1Bwt.% alloy was 680MPa at 1100°C and 420MPa at 1300°C. A review of the pertinent literature reveals that these are among the highest yield strengths measured for these compositions. The oxidation resistance in air at 1000 and 1100°C was examined. The protective borosilicate surface layer formed quickly due to the close spacing of intermetallic particles and pre-oxidation treatment was developed to further limit the transient oxidation behavior. An oxidation model was developed which factors in the different stages of oxidation to predict compositions that minimize oxidation.