| Non-oxide ceramics exhibit a number of important properties that make them ideal for technologically important applications (thermal and chemical stability, high strength and hardness, wear-resistance, light weight, and a range of electronic and optical properties). Unfortunately, traditional methodologies to these types of materials are limited to fairly simple shapes and complex processed forms cannot be attained through these methods. The establishment of the polymeric precursor approach has allowed for the generation of advanced materials, such as refractory non-oxide ceramics, with controlled compositions, under moderate conditions, and in processed forms.; The goal of the work described in this dissertation was both to develop new processible precursors to technologically important ceramics and to achieve the formation of advanced materials in processed forms. One aspect of this research exploited previously developed preceramic precursors to boron carbide, boron nitride and silicon carbide for the generation of a wide variety of advanced materials: (1) ultra-high temperature ceramic (UHTC) structural materials composed of hafnium boride and related composite materials, (2) the quaternary borocarbide superconductors, and (3) on the nanoscale, non-oxide ceramic nanotubules.; The generation of the UHTC and the quaternary borocarbide materials was achieved through a method that employs a processible polymer/metal(s) dispersion followed by subsequent pyrolyses. In the case of the UHTC, hafnium oxide, hafnium, or hafnium boride powders were dispersed in a suitable precursor to afford hafnium borides or related composite materials (HfB2/HfC, HfB2/HfN, HfB2/SiC) in high yields and purities. The quaternary borocarbide superconducting materials were produced from pyrolyses of dispersions containing appropriate stoichiometric amounts of transition metal, lanthanide metal, and the polyhexenyldecaborane polymer.; Both chemical vapor deposition (CVD) based routes employing a molecular precursor and porous alumina templating routes paired with solution-based methodologies are shown to generate non-oxide ceramic nanotubules of boron carbide, boron nitride and silicon carbide compositions.; In the final phase of this work, a new metal-catalyzed route to poly(1-alkenyl- o-carborane) homopolymers and related copolymers was developed. Both homopolymers of 1-alkenyl-o-carboranes (1-vinyl-, 1-butenyl-, 1-hexenyl-) and copolymers of 1-hexenyl-o-carborane and allyltrimethylsilane or 1-hexenyl-o-carborane and 6-hexenyldecaborane were synthesized via the Cp2ZrMe2/B(C6F5) 3 catalyst system. A copolymer containing 1-hexenyl-o-carborane and the cross-linking agent, 6-hexenyldecaborane, was synthetically designed which exhibits initial cross-linking at ∼250°C and then converts in 75% yields to boron carbide at 1250°C. |
