Sol-gel precursors to HfB2 and ZrB2 are processed by high-energy ultrasonication of Hf,Zr oxychloride hydrates, triethyl borate, and phenolic resin to form precipitate-free sols that turn into stable gels with no catalyst addition. Both precursor concentration and structure (a sol or a gel) are found to influence the synthesis of the diboride phase at high temperature. Decreasing sol concentration increases powder surface area from 3.6 to 6.8m(2)/g, whereas heat-treating a gel leads to residual oxides and carbides. Particles are either fine spherical particles, unique elongated rods, and/or platelets, indicating particle growth with directional coarsening. Investigation of the conversion process to ZrB2 indicates that a multistep reaction is likely taking place with: (1) ZrC formation, (2) ZrC reacts with B2O3 or ZrC reacts with B2O3 and C to form ZrB2. At low temperatures, ZrC formation is limiting, while at higher temperatures the reaction of ZrC to ZrB2 becomes rate limiting. ZrC is found to be a direct reducing agent for B2O3 at low temperature (similar to 1200 degrees C) to form ZrB2 and ZrO2, whereas at high temperatures (similar to 1500 degrees C) it reacts with B2O3 and C to form pure ZrB2.
Multiwalled carbon nanotubes were dispersed in a silicon carbide matrix to examine nanotube influence on mechanical properties of the resulting composite. The ceramic matrix was generated through high temperature conversion of poly(methylsilyne), a preceramic polymeric precursor. Nanotube alkylation was explored using two functionalization schemes: organic peroxide workup and alkyllithium displacement of fluorinated nanotubes, which promoted extensive mixing within precursor solutions, thereby ensuring nanotube dispersion within the polymer matrix while facilitating interfacial bonding. The former scheme was less effective at displacing inner nanotube shell bound fluorine and resulted in lower alkyl chain grafting density on the outer shell. Polymer nanocomposites were pyrolyzed and consolidated using an optimized spark plasma sintering scheme to generate fully densified ceramics. The pure polymer-derived ceramic displayed exceptional Young's modulus and Vickers microhardness of 126 +/- 12 and 9.6 +/- 0.5 GPa, respectively, while maintaining a fracture toughness of 2.8 +/- 0.3 MPa center dot m1/2. Increased sintering time further augmented the fracture toughness to 3.6 +/- 0.4MPa center dot m1/2, approaching the 4MPa center dot m1/2 that characterizes pure silicon carbide, while maintaining both Young's modulus and microhardness. Nanotube addition resulted in some loss of the intrinsic mechanical properties, but enhanced monolith damage tolerance behavior, raising the Vickers indent force needed to induce cracks to an excess of 98.1N in contrast to the pure polymer-derived sample, which began crack propagation below 49.0 N.
Si3N4 nanocomposites reinforced with 1-, 2-, and 6-vol% single-walled carbon nanotubes (SWNTs) were processed using spark plasma sintering (SPS) in order to control the thermal and electrical properties of the ceramic. Only 2-vol% SWNTs additions were used to decrease the room temperature thermal conductivity by 62% over the monolith and 6-vol% SWNTs was used to transform the insulating ceramic into a metallic electrical conductor (92Sm-1). We found that densification of the nanocomposites was inhibited with increasing SWNT concentration however, the phase transformation from α- to β-Si3N4 was not. After SPS, we found evidence of SWNT survival in addition to sintering induced defects detected by monitoring SWNT peak intensity ratios using Raman spectroscopy. Our results show that SWNTs can be used to effectively increase electrical conductivity and lower thermal conductivity of Si3N4 due to electrical transport enhancement and thermal scattering of phonons by SWNTs using SPS. © 2010 Elsevier Ltd.
Carbon-carbon (C-C) composites are ideal for use as aerospace vehicle structural materials; however, they lack high-temperature oxidation resistance requiring environmental barrier coatings for application. Ultra high-temperature ceramics (UHTCs) form oxides that inhibit oxygen diffusion at high temperature are candidate thermal protection system materials at temperatures >1600 degrees C. Oxidation protection for C-C composites can be achieved by duplicating the self-generating oxide chemistry of bulk UHTCs formed by a composite effect upon oxidation of ZrB2-SiC composite fillers. Dynamic Nonequilibrium Thermogravimetric Analysis (DNE-TGA) is used to evaluate oxidation in situ mass changes, isothermally at 1600 degrees C. Pure SiC-based fillers are ineffective at protecting C-C from oxidation, whereas ZrB2-SiC filled C-C composites retain up to 90% initial mass. B2O3 in SiO2 scale reduces initial viscosity of self-generating coating, allowing oxide layer to spread across C-C surface, forming a protective oxide layer. Formation of a ZrO2-SiO2 glass-ceramic coating on C-C composite is believed to be responsible for enhanced oxidation protection. The glass-ceramic coating compares to bulk monolithic ZrB2-SiC ceramic oxide scale formed during DNE-TGA where a comparable glass-ceramic chemistry and surface layer forms, limiting oxygen diffusion.