Thermal properties of polymer derived Si-O-C-N ceramics

The main objective of the thesis is to study the thermal properties of Si-based polymer derived ceramics (PDCs) at elevated temperatures and to classify the main factors affecting the thermal transport through these ceramics. The polymer derived ceramics with the chemistry Si- O-C-N were prepared starting from commercial polycarbosilane, polysiloxane, and polysilazane precursors. These precursors are cross-linked at room temperature to obtain the preceramic, followed by controlled pyrolysis (at different temperatures ranging from 1200 oC to 1800 oC in argon, nitrogen or carbon-di-oxide atmospheres), to get the final ceramic. The first part of the thesis discusses on development and studies of dense polymer derived thin disks having a basic chemistry, Si-C, Si-O- C, and, Si-C-N-O, developed via a casting technique followed by specific pyrolysis cycles. Having a thickness in the range of 100 μm- 300 μm, these ceramic disks were studied to be nanocrystalline/amorphous at least up to a temperature of 1400 oC and were found to have a significant amount of Cfree phase existing in them along with the intended chemistry. The high-temperature thermal properties were primarily investigated on ceramics prepared at a pyrolysis temperature of 1200 oC (ceramic still in nanocrystalline/amorphous glassy phase). The disks were found to have very low expansion coefficients (CTE) measured up to ~900 oC and the thermal diffusivity (k) and thermal conductivity (l) of these disks were also measured. An attempt to understand the influence of the different phases in a SiOC ceramic (mainly the Cfree phase, studied by enriching the carbon percentages using DVB) in determining the final thermal properties was also conducted. The influence of carbon enrichment on the mechanical properties of these disks is also studied as a sub-part of this work. The second part of the work deals with testing the possibility to use these ceramics for high-temperature insulation applications. ‘Reticulated’ ceramic foams of relatively same chemistries as that of the disks were prepared by a template replica approach, using polyurethane (PU) foams (more open-celled to more closed-celled types of PU foams were used in the study) as the template. Porous structures having densities ranging from as low as 0.02 g.cm-3 to 0.56 g.cm-3 and with a porosity ~ 80 % to ~99% were prepared and tested. The developed foams showed excellent thermal stability up to a temperature of 1400 oC and possessed very low thermal expansion. The thermal conductivity measured on them at RT gave values in the range 0.03 W.m-1.K-1- 0.25 W.m-1.K-1. A Gibson-Ashby modeling approach to explain the thermal conductivity of the porous ceramics was also attempted. The developed foams were also found to be mechanically rigid. In a nutshell, the thesis work studies the thermal properties of Si-O-C- N ceramics in detail and probes into the possibility to develop these class of Si-O-C-N ceramics into promising high-temperature insulation material.