Modeling and experimental characterization of Blackglas(TM) polymer pyrolysis to ceramic and thermodynamic characterization of Blackglas(TM) ceramic

The transformation of Blackglas(TM) polymer to ceramic is characterized by TGA-RGA/MS, Si29 and C13 NMR. Si29 NMR reveals a dependence between the postcure temperature and the microstructure of the resin. The postcure temperature that appears to give optimal mechanical and oxidative properties of Blackglas(TM) ceramic is around 150°C.; The pyrolysis processing models, which are the Lumped Parameters Model (LPM), the Mechanistic Kinetic Model (MKM) and the Redistribution Reaction Model (RRM), are developed to provide an effective window of processing parameters rather than a costly, time-consuming trial and error approach. The Lumped Parameters Model (LPM) is developed to study the effects of various parameters such as temperature, curing conditions and heating rates on mass loss during the pyrolysis of resin and green composites. It can be used for the model-predictive control of the pyrolysis process; The Mechanistic Kinetic Model (MKM) is developed on the basis of known chemistry and architecture of the polysiloxane for the transformation of Blackglas(TM) polymer to ceramic and the evolution of gases. The effects of various heating protocols on the outgassing kinetics have been studied to develop an optimum protocol for a rapid pyrolysis process which gives a composite with desirable mechanical properties; The Redistribution Reaction Model (RRM) is proposed to describe how the microcompositions of silicon oxycarbide change with respect to temperature, and to the ratio O/Si in the polymer precursor.; A Thermodynamic Additivity Model (TAM) is developed to estimate the heat capacity, standard heat of formation and entropy of Blackglas(TM) ceramic by means of the Neumann Kopp rule and the available thermodynamic data of the Si-C and Si-O systems. Thermal stability of this ceramic is investigated by constructing predominance diagrams, and it is shown that the internal degradation reactions, which account for a significant loss of strength, will proceed further in the Blackglas(TM) matrix than in the Nicalon fibers. This probably will induce failure in the matrix at lower temperatures than in the fibers. The predominance diagrams also explain the high temperature oxidation, reduction and volatilization experiments on silicon and silicon carbide in high vacuum.