Fine-diameter (∼ 10–15 µm), polymer-derived SiC fibers were characterized. The average tensile strength of the fibers was ∼ 2.8 GPa, although some lots had average strengths exceeding 3.5 GPa. Microstructure observations showed that fibers had fine grain sizes (mostly ∼0.05–0.2 µm), high densities (∼3.1–3.2 g'cm3), and small residual pore sizes (≤0.1 µm). Elemental analysis showed that fibers had near-stoichiometric composition. Electron and X-ray diffraction analyses indicated that fibers were primarily beta silicon carbide, with a minor amount of the alpha phase. A small amount of graphitic carbon was detected in some samples using high resolution transmission electron microscopy. The residual oxygen content in the fibers was ≤0.1 wt%. Fibers exhibited good thermomechanical stability, as heat treatment at 1800°C for 4h in argon resulted in only an ∼ 8% decrease in strength.

Directionally solidified fibers with nominal mullite compositions of 3Al2O3·2SiO2 were grown by the laser heated float zone (LHFZ) method at NASA Lewis. High resolution digital images from an optical microscope evidence the formation of a liquid-liquid miscibility gap during crystal growth. Experimental evidence shows that the formation of mullite in aluminosilicate melts is in fact preceded by liquid immiscibility. The average fiber tensile strength is 1.15 GPa at room temperature. The mullite fibers retained 80 % of their room temperature tensile strength at 1450 °C. SEM analysis revealed that the fibers were strongly faceted and that the facets act as critical flaws. Examined in TEM, these mullite single crystals are free of dislocations, low angle boundaries and voids. Single crystal mullite showed a high degree of oxygen vacancy ordering. Regardless of the starting composition, the degree of order observed in polycrystalline fibers was lower than that observed in the mullite single crystals.

In-situ composite fibers produced by directional solidification of two phase oxide eutectics are one means of producing fibers with good strength and higher creep resistance than single crystal fibers. In this work, directionally solidified alumina-yttria stabilized zirconia eutectic fibers have been grown by the laser heated float zone (LHFZ) method at NASA Lewis. The average tensile strength of the alumina-zirconia (60.8 m/o Al2O3; 39.2 m/o ZrO2 (9.5 m/o Y2O3)) eutectic fibers was 1.2 GPa at room temperature. The high temperature tensile strength and creep resistance of the eutectic fiber were determined and compared to single crystal Al2O3.

To improve the dispersion of silicon nitride whiskers in aqueous suspensions, a standard dispersant used in glass fiber industry, 3-aminopropyltriethoxysilane (APS) is added. It was found that the viscosity of the whisker suspensions is lowered and the centrifuged density of the suspensions is increased with the addition of the APS. The pH values of suspensions before and after the addition of APS indicate that APS extracts H+ ions from the solutions and the adsorption of APS on silicon nitride is saturated in our experiment. Our results indicate a colloidal route to the processing of ceramic composites with silicon nitride whiskers as reinforcements.

The three–point bending strength of TiC whiskers was measured in a scanning electron microscope. The whisker samples have ∼ 50µm length and 2∼4µm diameter and are commercially available as reinforcements for composite materials. The distribution of the bending strengths of the whiskers showed a double peak around 5.2GPa and 30.4GPa, respectively. The difference in these values is attributed to differences in the cleavage strength of two crystal planes depending on whisker growth direction.

Polycrystalline zirconia-coated single crystal sapphire fiber displays reconstruction of the sapphire surface in regions of contact with zirconia grains. This is a concern where ZrO2 -coated sapphire fiber is desired for reinforcement of ceramic matrices. Previous work has demonstrated pitting is partially attributed to impurity-induced transient liquid phase formation with local dissolution of alumina; however, the extent of reconstruction witnessed via microscopy suggests that other mechanisms are active. The present study has addressed the issue of solid solubility and interdiffusivity to more thoroughly understand the solid state mechanisms contributing to pitting. Single crystal sapphire and zirconia were ion implanted with zirconium and yttrium, and aluminum, respectively, and then subjected to diffusion anneals at 1200° - 1600°C to study redistribution of implanted cations. Secondary Ion Mass Spectroscopy (SIMS) was used to profile the redistribution of implanted ions for measurement of diffusion coefficients and solubility limits after heat treatments. The results will offer a significant set of data on interface stability in the alumina/zirconia system.

Resistivity control has been conducted by solid–state reaction of two different perovskite–type oxides. One is La0.5Ba0.5CoO3−δ (LBC) which showed metallic conduction, and its resistivity, ρ was 10−3 Ω.cm at 20 °C. The other is Ba0.998Sb0.002TiO3 (BT) which showed positive temperature coefficient of resistivity (PTCR) effect. The sintered body of the mixiure of the two oxides did not show PTCR effect. The logarithm of the resistivity of the sintered body, log ρmix was expressed using the resistivity of LBC, ρLBC, the molar ratio of BT, x, and temperature dependent constant, α(T) as

log ρmix = (l–x) log PLBC + xα(T)

which holds for 0 ≤ x ≤ 0.8 at the temperature ranging from 20 to 240° C ρmix changed by about 8 orders of magnitude at room temperature. X–ray diffraction analysis suggested that metal ions at the A–site move from one perovskite–type oxide to another and that the sintered body consisted of two perovskite–type oxides different from starting ones.

Nickel-alumina composites have the potential to be high performance materials. Alumina, with its excellent oxidation resistance, combined with a ductile phase such as nickel may provide a tough material with a lower density and higher Young's modulus, overall, a higher specific modulus than typical Superalloys. Dense, interpenetrating Ni-Al2O3 composites were synthesized using a displacement reaction between NiO and aluminum. The resulting composites were characterized in terms of their mechanical properties such as hardness, flexure strength, fracture toughness and elastic constants. The synthesis, characterization, and mechanical properties, as well as the effect of the interpenetrating microstructure on the toughening mechanisms and other properties will be discussed.

Displacement reactions may play an important role in in situ processing technologies for the production of metal-ceramic composites. To better understand such reactions displacement reactions between NiO and Al were studied at high temperatures. Different reaction layers with periodic structures were observed involving Al2O3, Al3Ni, Al3Ni2, Ni and Al. The experimental observations are presented and discussed with regard to the reaction mechanism.

Chemically bonded ceramics appear to be a promising alternative route for near-net shape fabrication of multi-phase ceramic matrix composites (CMC's). The hydraulic (and refractory) properties of fine mono-calcium aluminate (CaAl2O4) powders were used as the chemically bonding matrix phase, while calcia stabilized zirconia powders were the second phase material. Samples containing up to 70 wt% (55 vol%) zirconia have been successfully compacted and sintered.

Various processing techniques were evaluated. Processing was optimized based on material properties, dilatometry and simultaneous thermal analysis (DTA'TGA ). The physical characteristics of this novel CMC were characterized by hardness, density, and fracture toughness testing. Microstructures were evaluated by SEM and phase identification was verified using XRD.

In-situ synthesis of a composite of MoSi2-Al2O3 was carried out by reacting a thermite mixture consisting of MoO3, Al, and Si powders. The reaction was found to be extremely fast and violent, and a diluent was required to moderate the reaction. Thermal behavior of the thermite mixture was studied using DTA at different heating rates, and DTA was interrupted at different temperatures to determine the reaction mechanism. X-ray characterization of the products obtained at different temperatures reveals that the mechanism consists of a reduction of MoO3 by Al to MoO2 followed by a simultaneous oxidation of Al to Al2O3 and synthesis reaction between reduced Mo and Si to form MoSi2. The rate determining step is found to be reduction of MoO2 by Al and oxidation of Al to Al2O3. The thermite reaction was moderated by adding Mo and Si to the mixture of MoO3, Al, and Si such that the ratio of MoSi2 to the thermite was in the range of 60:40 to 90:10.

Phase equilibria and properties of ceramics in the NbB2 – CrB2 system were studied. Continuous solid solutions were found showing high activation energy (96 kcal'mol) of formation which is due to large disparity of atomic radii between Cr and Nb. Pure NbB2 and CrB2 ceramics were prepared by hot pressing at 2100 and 1800°C, respectively, at 20 MPa for 0.5 hour. Both materials exhibited closed porosity which was eliminated by the addition of Al2O3 and SiC. Thermogravimetric studies showed different mechanisms of oxidation of the diborides. The presence of Al2O3 and SiC improved the oxidation resistance, hardness, and fracture toughness of CrB2 ceramics. The additives increased the hardness of NbB2 ceramics but did not significantly affect their toughness.

The formation of crystalline α-Si3N4 filaments grown inside the pore channels of HT-carbon fibers from a 2D C/C-SiC composite is investigated by transmission electron microscopy. Precipitation of α-Si3N4 is promoted by a low carbonization heat treatment of the C/C material prior to liquid silicon infiltration and results from the interaction of a highly reactive nitrogen-rich vapor phase released from the fiber and silicon vapor diffusing ahead of the SiC reaction front into the porous microtexture of the fiber.

The influence of the addition of impurities and changes in the oxygen partial pressure on the formation of metal-ceramic microstructures by partial reduction of ternary or higher ceramic oxides was experimentally investigated in the model system Fe-Mn-C at constant temperature and total pressure. Electron microscopy studies were performed for microstructural characterization, phase identification and chemical analysis. It was observed that the addition of dopants such as BaO, CaO, MgO, SrO, Al2O3, Cr2 O3 or ZrO2 to the initial, polycrystalline oxide solid solution (Fel−xMnx)1−ΔO strongly influences the location and rate of metal precipitation during reduction. Experimental observations are discussed based on solubility limits and the segregation of dopants.

Si powders synthesized by the laser pyrolysis of silane can be nitrided at 1200–1250°C, producing an improved reaction bonded silicon nitride. This RBSN is a potential matrix for composites since it can be formed at temperatures which do not degrade the strengths of commercially available amorphous ceramic fibers. However, the density of the RBSN matrix has been limited to about 75% using the silane-derived Si powder. Combining Si powders and preceramic polymers offers an approach for increasing the density and mechanical properties of the reaction-formed Si3N4 matrix. The incorporation of polysilazanes inhibited the nitridation at 1250°C, but samples could be effectively nitrided at 1400°C. These higher nitriding temperatures are compatible with SCS-6 and other lowoxygen, crystalline SiC fibers which can be used as reinforcements for ceramic composites.

Polymer infiltration/pyrolysis (PIP) processing has the potential to become an affordable means of manufacturing continuous fiber-reinforced ceramic-matrix components. The PIP method is very similar to the well-known polymer-matrix and carbon-carbon composite manufacturing techniques, the major difference being the use of a preceramic polymer in place of the organic polymer or carbon precursor. To date, the majority of research in the field of preceramic polymers has centered on precursors to silicon carbide (SiC). The Southwest Research Institute (SwRI) has focused on the development of polymeric precursors to silicon nitride (Si3N4) because its high-temperature strength, resistance to oxidation, and other properties make it an attractive candidate for many advanced high-temperature structural applications. PIP Si3N4 composites with NICALON SiC fiber reinforcement have exhibited good fracture toughness (KIC ∼ 16MPa·m1/ 2). We report here processing, microstructure and preliminary mechanical properties of two new PIP Si3N4 composites. One is reinforced with Tonen Si3N4 fiber (plain weave) while the other is reinforced with ALMAX Al2O3 fiber (8 Harness satin weave).

Dispersion morphology of fine SiC particles in Si3N4/xSiC (x=0, 10, 20, 30wt%, average size: 0.03/µ m) composites was statistically analyzed, and typical properties of the composites such as creep, electric and thermal conductivity were investigated. The dispersion morphology of SiC particles was analyzed by observing the ECR-plasma etched surface of the sintered composites using scanning electron microscopy. SiC particles in Si3N4/SiC composites were distributed both within Si3N4 grains and on Si3N4 grain boundary, but 90% or more of them was located on the grain boundary. For the composites with 20-30wt%SiC, the SiC particles on the grain boundary clearly formed a three-dimensional network structure surrounding a few or more Si3N4 crystalline grains.

A Si3N4/SiC composite with a three-dimensional network structure of SiC particles, named particles cellulation composite (PCC), was artificially made by pressing the granulated Si3N4 powder (less than 500 µ m diameter) discontinuously coated with SiC particles (average size: 0.4 µ m). The creep deformation of PCC was reduced to about 60%.of that of the composites with SiC particles randomly dispersed. Electrical and thermal properties were also improved. These results suggest that the formation of three-dimensional network structure by the second phase particles in a composite would considerably improve its mechanical property as well as electrical and thermal properties.

Alumina (Al2O3) test bars containing a small (5-10%) volume of titanium diboride (TiB2) or zirconium diboride (ZrB2) particles have been pressed and sintered (pressureless) in an argon atmosphere. The microstructure of the sintered bodies was characterized by X-ray diffraction and a range of microscopical techniques and shows that 3ppm (by volume) of oxygen present in the argon caused the boride particles in the surface regions of the test bars to oxidize during sintering, to a greater extent in the Al2O3-TiB2 composites. Mechanisms of oxidation are discussed. The boride particles retarded the densification of the composites, to a greater extent in the Al2O3-ZrB2 bodies. However, densification in the Al2O3-ZrB2 system was enhanced by sintering in an Ar-4% H2 atmosphere. The decrease in flexural strength due to the retardation of sintering has been overcome in both types of composite.

Partial reduction reactions in the Ni-Al-O system, starting with the spinel compound NiAl2O4, are used to form metal-ceramic microstructures in situ. Two different morphologies of nearly pure Ni particles, equiaxed and rod-like, form within a ceramic matrix depending on the choice of processing parameters. Electron microscopy studies were performed for microstructural characterization, phase identification and chemical analysis. The fracture toughness of the Ni-Al2O3 mixture was significantly improved with respect to that of the original spinel phase. It is shown that cracking at the original spinel grain boundaries, likely due to the large volume changes associated with the reduction reaction, can be avoided by the addition of small amounts of ZrO2. It is seen that ZrO2 also acts as a nucleation site for the precipitating metal and hence allows morphology control in microstructures obtained by partial reduction reactions.

Since the Lanxide process was advanced for forming of Al2O3 ceramic composite by directed oxidation of Al alloys, much work has been done with various mechanisms being proposed. The mechanisms have claimed that only certain dopants are essential to the growth process. Nevertheless, no united consensus has yet been reached. In the present work, Al alloy containing 5% Mg was oxidised in air for 12 hours at 1150°C with or without surface dopants of MgO or Pd. The resultant composites showed very different microstructures. Without any surface doping, the alloy did not develop any portion of composite as the initial intimate oxide film stops further oxidation. This intimate oxide film can either be broken off by mechanical means or penetrated by reaction with surface dopants, so that the composite can grow and develop. The results show that the previously reported incubation time is not only related to reaction processes but also to the initial mechanical disturbances. Doping with Pd made the composite darker in colour as the grains of the alumina ceramic matrix and inclusions of Al metal are finer. This shows that Pd may make the top oxide layer less intimate, and more nucleation sites are therefore available for oxidation. A new model is presented for oxide sustained growth based on the existence of oxygen active top surface layer and the capillary flow of molten metal around ceramic phase.