19 Dec 2004. / Published through the Information Bridge: DOE Scientific and Technical Information. "IS-T 2315" Vikas Behrani. 12/19/2004. Report is also available in paper and microfiche from NTIS.

The alloy Mo-3Si-1B (wt%) may have the fracture toughness and oxidation resistance required for use as jet turbine engine blades. Mo-3Si-1B (wt%) forms a three-phase mixture of and #945;-Moss, A15 (Mo3Si) and T2 (Mo5SiB2). It has been observed that at high-temperatures, the A15 and T2 intermetallics form a oxidation resistant borosilicate glass coating. To achieve the proper combination of mechanical and thermal properties, the material must have a molybdenum matrix with a fine dispersion of intermetallics to produce a continuous protective layer. In this project, reactive sintering of molybdenum, Si3N4 and BN powders was used to create a semi-continuous molybdenum matrix with a fine dispersion of the A15 and T2 intermetallics. Sintering of the materials was further enhanced by the use of submicron-sized reactants. X-ray diffraction analysis was used verify the desired phases were formed. It was determined that formation of the A15 intermetallic phases begins as low as 1200?nd formation of T2 begins at 1300? The reactions are complete by 1400? Samples with bulk densities as high as 95% of theoretical were produced. Scanning electron microscopy images reveal a microstructure with dispersed intermetallics in a semi-continuous molybdenum matrix with grain sizes on the order of 1-4 and #956;m. It was found that by varying parameters such as mixing method and heating rates, it is possible to engineer the final microstructure, changing the level of dispersion of the intermetallics and continuity of the matrix.

MoSiB alloys show promise as the next-generation turbine blade material due to their high-temperature strength and oxidation resistance afforded by a protective borosilicate surface layer. Powder processing and reactive synthesis of these alloys has proven to be a viable method and offers several advantages over conventional melt processing routes. Microstructures obtained have well-dispersed intermetallics in a continuous matrix of molybdenum solid-solution (Mo-ss). However, bend testing of pure Mo and Mo-ss samples has shown that, while the powder processing route can produce ductile Mo metal, the hardening effect of Si and B in solid-solution renders the matrix brittle. Testing at elevated temperatures (200°C) was performed in order to determine the ductile-to-brittle transition temperature of the metal as an indication of ductility. Methods of ductilizing the Mo-ss matrix such as annealing and alloying additions have been investigated.

Transition Metal (TM) silicides are potential materials for different high temperature applications due to their high melting points and chemical stability at elevated temperatures. In the present work, the possible use of Gr (VIB) disilicides: MoSi2 and CrSi2 for high temperature structural application and thermopower generation respectively are investigated. Literature reports on MoSi2 indicate this material to have excellent mechanical and thermal behaviors at temperatures greater than 1273 K. The major problems limiting its use are the low temperature brittleness and oxidation at intermediate temperatures and form the scope of this work. Also, CrSi2 is reported to be a narrow band gap semiconductor. Its feasibility as a thermoelectric material for power generation is investigated. The first chapter briefly summarizes the literature on MoSi2 and CrSi2 relevant to structural and thermoelectric applications respectively. Based on the available literature, the scope of further work is discussed. The second chapter describes the methods of synthesis employed for these materials and the characterization techniques adopted. Some experimental setups like thermal conductivity and hot pressing unit that were fabricated as part of the work are described in detail. The thermal conductivity apparatus is based on the principle of parallel heat flow technique. It allows accurate measurement of K and S in the temperature range 300-700 K. The induction based hot-pressing unit allows compaction of polycrystalline powders to near theoretical densities thereby allowing quantitative evaluation of the physical properties. In the third chapter, an understanding of ductility/brittleness based of electron charge density distribution is attempted. The electron charge density in Tin and simple metals (BCC and FCC) is analyzed using Bader’s Atoms in Molecule (AIM) theory. Also the relevant surface and dislocation energies in these materials are calculated according to the Rice Model. It is found that the electron densities at the critical points correlate in a simple way with the relevant stacking fault and surface energetics. Based on these results, a ductility parameter (DM odel) based on electron charge distribution, to predict the effects of chemical substitutions on ductility/brittleness in materials is proposed. In the fourth chapter, possible elements to impart ductility in MoSi2 are identified based on the DM odel values. Calculations indicate, Nb, Ta, Al, Mg and Ga to be suitable candidates for improving ductility in MoSi2. Also oxidation studies based on present experiments and reported literature data reveal, Al to improve the intermediate temperature (773-873 K) oxidation behavior. Thus to simultaneously improve the low temperature ductility and oxidation resistance, Nb and Al were identified as suitable candidates. In the fifth chapter, the experimental data of Nb and Al co-substituted MoSi2 samples are reported. Oxidation studies carried out by thermogravimetry show improved oxidation resistance in Nb and Al co-substituted samples compared to pure MoSi2 in the temperature range of 773-873 K. Mechanical characterization was carried out for (Mo0.99Nb0.01)(Si0.96Al0.04)2 co-substituted composition. Compression testing at room temperature show plastic deformation at low strain rates (10−3 /sec). Indentation experiments show a reduction in the hardness and stiffness compared to pure MoSi2. There is also an increase in the fracture toughness (K1C ) value with the fracture modes being predominantly transgranular. The sixth chapter describes the structural, thermal and transport properties of CrSi2. Structural refinement was carried out by Rietveld method and the positional, thermal parameters and occupancy were fixed. Thermo-gravimetric analysis shows oxidation resistance in powdered samples upto 1000 K. Thermal expansion (α) studies reveal anisotropy in the α values with an unusual decrease in the average αV values between 500 and 600 K. Measurements of electrical resistivity and seebeck coefficient indicate a degenerate semiconducting behavior. Electronic band structure calculations indicate a narrow indirect band gap (EG) material with EG~0.35 eV. Thermal conductivity (K) measurements show a decrease in K value with increasing temperature. Calculation of the thermoelectric figure of merit (ZT) show a maximum value of 0.18 at 800 K for the temperature range studied. Based on an analysis of the experimental and theoretical results, it is identified that further improvements in ZT of CrSi2 may be possible by reducing the lattice thermal conductivity and optimization of the carrier concentration. In chapter seven, the effect of particle size on ZT of CrSi2 is studied. Nano powders of CrSi2 were prepared by mechanical milling. Contamination is found to be a major problem during milling and the different milling parameters (milling speed, atmosphere, dispersant etc) were optimized to minimize contamination. The milled powders were further hot pressed to achieve high densities in a short duration thereby minimizing the grain growth. It is observed that the lattice thermal conductivity is reduced significantly with decreasing grain size. Measurements of ZT show a maximum value of 0.20 in the milled sample compared to 0.14 in arc melted CrSi2 at 600 K. In chapter eight the effect of chemical substitutions on ZT of CrSi2 is studied. Mn substitutions in Cr site were carried out to study the effect of atomic mass on lattice thermal conductivity (KP ). Al substitutions in Si site were carried out to tune the Fermi level. Results of Mn substitution show a large decrease in KP but also a reduction in the thermoelectric power factor (S2σ). The maximum ZT observed in the Mn substituted samples was 0.12 at 600 K. Al substitution results in an increase in the thermoelectric power factor and a subsequent increase in ZT. The maximum ZT observed was 0.27 at 700 K for 10% substitution of Al in Si site. The work reported in the thesis has been carried out by the candidate as a part of the Ph.D. training programme at Materials Research Centre, Indian Institute of Science, Bangalore, India. He hopes that this work would constitute a worthwhile contribution towards (a) basic understanding of ductility/brittleness in materials and understanding the effects of chemical substitutions, (b) Suitability of chemically substituted MoSi2 to overcome the problems of low temperature brittleness and oxidation. (c) Development of CrSi2 as a high temperature thermoelectric material.