Structural Ceramics: Kanthal Super, MoSi2-based materials, Operation > 1575oC Aluminum forms stable oxide [1](Sundberg, Malmqvist

et al. 2004). The oxides providing a good oxidation resistance on electric heating elements of metallic alloys and intermetallics are Al2O3, Cr2O3 and SiO2. Surface layers of chromia protect the NiCr alloys, alumina the FeCrAl alloys and silica the MoSi2-based heating elements. Almost thermodynamically stable of these oxides and provides the best protection in reducing and oxygen decient atmospheres. However, MoSi -based materials, such as KanthalSuper 1800oC, but above 1300oC silica scale develops and deters the performance. But alloying with Aluminum, Mo(Si,Al)2, Al2O3 develops a oxidation protective scale. [1-3] MAX-phases, 312 i.e., Ti3SiC2 is another remarkably studied material, oxidation resistance below 1000oC is acceptable but above this temperature decreases remarkably, forming a mixture of TiO2 and SiO2. [14-8]. In vacuum of H2 atmosphere1800 oC. Max phase (Ti2AlC) is being studied for oxidation resistance and two contradictory observations were recorded, Basoum found unstable oxide.[1] Oxidation Prevention Coatings. High-temperature phase stability and tribological properties of laser clad Mo2Ni3Si/NiSi metal silicide coatings.[2] (Lu and Wang 2004) Serious room-temperature brittleness is the main obstacle preventing the materials from industrial applications [2911]. Whereas while testing and processing TiC-NiAl composites Bewlay et.al mentioned that The potential increased temperature capability is ~200C for both bulk average temperature and maximum surface temperature, as compared to current single crystal superalloys[13](B. P. Bewlay) (time of report is not mentioned). Refractory metal three phase Mo2.7Nb8.9Si7.7B silicide alloy with MA as the crucial processing step. After consolidation by hydrogen sintering and HIP a triplex UFG microstructure with the sizes of all three phases ranging clearly in the sub-micron range was obtained. Tensile tests revealed structural superplasticity with strain to failures as high as 400% at 1400 C.

Improving the creep resistance beyond that of third generation single-crystal Ni-based superalloys may be achieved by a further coarsening of the microstructure through advanced thermo-mechanical processing.[3] (Jhanno, Heilmaier et al. 2007)(tests limited to 1400C) The addition of as little as 1 wt.% (_3 at.%) boron improved the oxidation resistance of Mo5Si3 by as much as five orders of magnitude over a temperature range of 8001500C. Multiphase (in-situ composite) intermetallics based on MoSiB compositions around the T1 phase present some unique solutions to these problems (Pesting, Oxidation and poor low temperature fracture toughness) No dislocation motion was observed in this phase, T1

(Mo5Si3Bx) , but some of the dislocation motion was observed in T2 [4](Akinc, Meyer et al. 1999) SIBOR coated samples showed no evidence of MoO3 sublimation up to 1650 oC for 30 h in synthetic air The approach is exemplified with a refractory metal-based alloy of composition Mo8.9Si7.7B (in at.%) as a potential candidate for ultra-high temperature structural applications in oxidizing environment. The above-mentioned composition corresponds in weight percent to Mo3%Si1%B. [5] (Jhanno, Heilmaier et al. 2004) The oxidation of CVI composite above 1000 was much faster than that of MSI and CVI+MSI composites [6] Many industrial applications require materials with fracture toughness levels in the vicinity of 10 MPa m1/2, while turbine applications require toughness levels of 15 MPa m1/2 or higher Fiber Reinforced Composites; Ceramic matrices reinforced with continuous ceramic fibers have exhibited the highest toughness levels, with values often exceeding 30 MPa m1/2. . SiC /fiber-SiC matrix composites are a good example of such materials. These SiC/SiC composites have a relatively weak fiber matrix interfacial bond, which leads to debonding and energy absorption due to fiber pullout. Such composites fracture by the mechanism of ``graceful failure'', rather than catastrophically. However, such toughening mechanisms can be degraded by environmental attack of the interface at elevated temperatures Ductile metal toughened composites can reach toughness levels as high as 25 MPa m1/2. However, metal-reinforced composite use-temperatures are limited by the oxidation resistance and melting point of the metal phase. Transformation toughening is an important toughening approach associated with zirconia

ceramics. Here, a tetragonal-to-monoclinic phase transformation occurs, which shields the crack tip from theapplied stresses, and effectively toughens the material.Partially stabilized zirconia (PSZ) is the primary example of this type of toughening, where low temperature toughness levels can reach 15 MPa m1/2. However, a drawback of transformation toughening is that toughness decreases with increasing temperature, due to the thermodynamics of the phase transformation thermodynamics of the phase transformation. Discontinuously reinforced ceramic composites have typically employed ceramic whiskers or particles as the reinforcing phases. An example is SiC whisker reinforced Si3N4. Toughening mechanisms here are crack deflection and crack bridging. Discontinuous ceramic composites can reach toughness levels of 10 MPa m1/2. One important variant of this approach is the in-situ toughening of Si3N4 due to presence of elongated grains Si3N4.due to the presence of elongated grains. MoSi2 -Al2O3 composites show graceful failure because thermal matching of coefficients of Alumina and Molybdenum disilicide.[10]( Bartlett AH,
sprayed MoSi2/Al2O3 Industrial Heating, January,1996 .) Castro RG, Butt DP, Kung H, Petrovic JJ, Zurecki Z. Plasma

MoSi2-SiC composites SiC is used in both whiskers[711-15] and particulate[715-18] form, high temperature fracture toughness is improved significantly whereas low temperature toughness remains on the lower side.[715] Si3N4 additions; It has been observed that Si3N4 additions to MoSi2 completely eliminate the MoSi2 oxidation pest behavior,due to basic changes in the oxidation mechanisms [19]( Hebsur MG, Nathal MV. Strong, tough, and pest-resistant MoSi2 -base hybrid composite for structural applications. In: Nathal MV, Darolia R, Liu CT, Martin PL, Miracle DB, Wagner R et al., editors. Structural Intermetallics 1997. Warrendale (USA): TMS, 1997. p. 949) when composites were synthesized with elongated Si3N4 grains fracture toughness upto 15Mpam1/2 was achieved [20]. MoSi2-Si3N4-SiC composites; Such composites with MoSi2-Si3N4 matrix and SiC fiber reinforcements showed graceful failure at RT and excellent impact strength upto 1400oC.[720]. Alloying to MoSi2; It has been shown [721] that some orientations of MoSi2 single crystals exhibit macroscopic compressive ductility at temperatures as low as -100oC. These observations suggest that alloying may be a means to promote dislocation plasticity in MoSi2 at lower

temperatures, thus lowering the brittle-to-ductile transition and increasing room temperature fracture toughness. The theoretical aspects of the atomic bonding in MoSi2 and the potential alloying species that might lower the brittle-to-ductile transition temperature have been recently studied from a first principles approach [726,27] These calculations have suggested that alloying additions of Mg, V, Nb, Tc, and Al to the C11 MoSi2 crystal structure may enhance ductility, while additions of Ge, P, and Re are predicted to have the reverse effect. So far studied alloying elements are niobium,vanadium, tantalum, chromium, zirconium, rhenium, and aluminum. With the exception of aluminum, all of these alloying species are thought to reside on the molybdenum lattice sites. Aluminum is thought to substitute for silicon. Aluminum and Rhenium does not improve the room temperature fracture toughness although high temperature hardening is obtained by Re[732,33]. [7](Petrovic 2000) Probability of SiC reinforced with SiC fiber may be another option, their fracture toughness should remain almost similar, as there is no loss of materials other than Carbon as reported by TGA by Matteo et al [8](Pavese, Fino et al. 2008) One such practical fiber reinforced composite were prepared and tested for mechanical properties by Donghai et al. He has reported multiphase coatings better than single phase coating as tested by other referees[95,11,12,13,14]. PIP-SiC interphase exhibit standard toughened fracture behavior even though after thermal oxidation Can this be tested for 1600 as done by Fino et al? [9](Ding, Zhou et al. 2012) Another Al2O3/TiC/(MoSi2+Mo2B5) Multilayer Composites Prepared by Tape Casting was tested for three point bending at room temperature and elevated temperatutre , 1300~1400 oC and

it was observed that composite showed considerable displacement even for room temperature tests. [10],(Guo-Jun Zhang 1999)] Tested materials C/SiC showed 40~50 percent reduction in residual tensile strength after exposure to high temperature when tested by Nie [11](Nie, Xu et al. 2008) Upon annealing at 1500C, the microstructure coarsened,Fig. 6, which shows the annealed microstructure of the Nb26Ti22Si6Cr3Hf2Al (at%) alloy. X-ray diffraction from before and after annealing shows that there are no phases created or lost during this heating process,[12(Dicks, Wang et al. 2009)].

References:
[1]Sundberg, M., G. Malmqvist, et al. (2004). "Alumina forming high temperature silicides and carbides." Ceramics International 30(7): 1899-1904. [2] Lu, X. D. and H. M. Wang (2004). "High-temperature phase stability and tribological properties of laser clad Mo2Ni3Si/NiSi metal silicide coatings." Acta Materialia 52(18): 5419-5426. [3] Jhanno, P., M. Heilmaier, et al. (2007). "Assessment of the high temperature deformation behavior of molybdenum silicide alloys." Materials Science and Engineering: A 463(12): 216-223. 4] Akinc, M., M. K. Meyer, et al. (1999). "Boron-doped molybdenum silicides for structural applications." Materials Science and Engineering: A 261(12): 16-23. [5]Jhanno, P., M. Heilmaier, et al. (2004). "Characterization of an industrially processed Mo-based silicide alloy." Intermetallics 12(79): 1005-1009. Petrovic, J. J. (2000). "Toughening strategies for MoSi2-based high temperature structural silicides." Intermetallics 8(911): 1175-1182. [7]Petrovic, J. J. (2000). "Toughening strategies for MoSi2-based high temperature structural silicides." Intermetallics 8(911): 1175-1182. [8] Pavese, M., P. Fino, et al. (2008). "Potential of SiC multilayer ceramics for high temperature applications in oxidising environment." Ceramics International 34(1): 197-203. [9] Ding, D., W. Zhou, et al. (2012). "Mechanical properties and oxidation resistance of SiCf/CVI-SiC composites with PIP-SiC interphase." Ceramics International.(In Press)(Guo-Jun Zhang 1999). [10]Guo-Jun Zhang, y. X.-M. Y. a. T. W. (1999). "Al2O3-TiC(MoSi2-Mo2B5), Multilayer Composite prepared by Tape Casting." European Ceramic Society 19: 2111-2116.

[11] Nie, J., Y. Xu, et al. (2008). "Effect of thermal cycling on modulus and tensile strength of 3D needled C/SiC composite in controlled environments." Materials Science and Engineering: A 497(1-2): 235-238. [12] Dicks, R., F. Wang, et al. (2009). "The manufacture of a niobium/niobium-silicide-based alloy using direct laser fabrication." Journal of Materials Processing Technology 209(4): 1752-1757. [13] B. P. Bewlay, M. R. J. a. P. R. S. "Processing High-Temperature Refractory-Metal Silicide In-Situ Composites." JOM 51(4): 32-36.

Sharif AA, Misra A, Petrovic JJ, Mitchell TE. Intermetallics 2001;9:869. [10] Kajuch J, Rigney JD, Lewandowski JJ. Mater Sci Eng A 1991;A155:59. [11] Liu CT, Stringer J, Mundy JN, Horton LL, Angelini P. Intermetallics 1997;5:579. Fig SiC/graphite Composite (2-D lay-up)